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188.Журнал Сибирского федерального университета. Сер. Химия №1 2014

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Журнал Сибирского федерального университета
2014
Journal of Siberian Federal University
7 (1)
Химия
Chemistry
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Editorial Advisory Board
Chairman:
Eugene A. Vaganov
Members:
Josef J. Gitelzon
Vasily F. Shabanov
Andrey G. Degermendzhy
Valery L. Mironov
Gennady L. Pashkov
Vladimir V. Shaidurov
Vladimir V. Zuev
Editorial Board:
Editor-in-Chief
Mikhail I. Gladyshev
Founding Editor
Vladimir I. Kolmakov
Managing Editor
Olga F. Alexandrova
Executive Editor for Chemistry
Boris N. Kuznetsov
CONTENTS / СОДЕРЖАНИЕ
Marina A. Smirnova,
Valery E. Tarabanko and Michael Yu. Chernyak
Regeneration of Hydrochloric Acid in the Catalytic Fructose
Conversion to Levulinic Acid
?4?
Leonid N. Alexeiko, Irina G. Maslennikova,
Alexei Yu. Mamaev, Valeriy I. Kharchenko,
Vladimir K. Goncharuk and Valeriy Ya. Kavun
Luminescence and Light Scattering in the Doped ZBLAN and
Tellurite Glasses
? 10 ?
Evgeniya A. Demakova,
Nadezhda A. Egorova and Tatiyana N. Yamskikh
Safety of Goods from Polymer Composites: Organizational and
Methodological Aspects
? 17 ?
П.О. Краснов
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? 23 ?
В.Е. Тарабанько, М.Ю. Черняк,
А.А. Морозов, К.Л. Кайгородов,
Ю.Н. Безбородов, Н.Ф. Орловская, И.В. Надейкин
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Editorial board for Chemistry:
Boris Kuznetsov ? Series Editor,
Professor, Siberian Federal University
Nicolai Chesnokov ? Associate Editor,
Professor, Siberian Federal University
Vladimir Agabekov ? Professor, Institute
of Chemistry of New Materials NAS,
Belarus
Lyubov Altunina ? Professor, Institute
of Petroleum Chemistry, Russian
Academy of Sciences, Siberian Branch
Natalia Bazarnova ? Professor, Altai State
University
Vasili Babkin ? Professor, AE Favorsky
Irkutsk Institute of Chemistry, Russian
Academy of Sciences, Siberian Branch
Vicente Cebolla ? Dr, Instituto de
Carboquimica, CSIC, Spain
Alain Celzard ? Professor, Universite de
Lorreine Institut Universitaire de Frans
Viktor Denisov ? Professor, Siberian
Federal University
Zinfer Ismagilov ? Professor, Boreskov
Institute of Catalysis, Russian Academy
of Sciences, Siberian Branch
Sergey Kachin ? Professor, Siberian
Federal University
Sergey Kirik ? Professor, Siberian Federal
University
Vladimir Likholobov ? Corresponding
Member, RAS, Institute of
Hydrocarbons Processing, Russian
Academy of Sciences, Siberian Branch
Yury Mikhlin ? Professor, Siberian
Federal University
Konstantin Neyman ? ICREA Professor,
Departament de Quimica Fisica
Universitat de Barcelona, Spain
Gennady Pashkov ? Corresponding
Member, RAS, Professor, Siberian
Federal University
Anatoly Rubailo ? Professor, Siberian
Federal University
Tatyana Ryazanova ? Professor, Siberian
State Technological University
Vladimir Sobyanin ? Professor,
Novosibirsk State University
Valery Tarabanko ? Professor, Institute of
Chemistry and Chemical Technology,
Russian Academy of Sciences, Siberian
Branch
Tatiana Shendrik ? Professor, Litvinenko
Institute of Physical Organic Chemistry
and Coal Chemistry, Ukraine
Н.А. Комар, Д.Г. Слащинин,
И.В. Петерсон, М.С. Товбис
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? 36 ?
Н.В. Чесноков, Н.М. Микова,
И.П. Иванов, Б.Н. Кузнецов
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? 42 ?
В.А. Соколенко,
Н.М. Свирская, И.В. Петерсон,
А.А. Кондрасенко, А.И. Рубайло
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А.В. Левданский, Б.Н. Кузнецов
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В.А. Шелехова,
Е.А. Краснов, Э.Ф. Степанова
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Н.М. Иванченко, Б.Н. Кузнецов
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Н.В. Громов, О.П. Таран,
Д.А. Яценко, А.Б. Аюпов,
А. Лоппине-Серани, С. Амони, В.Е. Агабеков
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Б.Н. Кузнецов,
О.В. Яценкова, А.И. Чудина,
А.М. Скрипников, С.А. Козлова,
Н.В. Гарынцева, Н.В. Чесноков
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*=2=?,?=2%!%? SBA-5
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А.А. Червов, П.В. Фабинский,
Н.В. Гавголенко, В.А. Федоров
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Т.А. Корельская, Т.И. Румянцева
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Journal of Siberian Federal University. Chemistry 1 (2014 7) 4-9
~~~
??? 544.478
Regeneration of Hydrochloric Acid
in the Catalytic Fructose Conversion
to Levulinic Acid
Marina A. Smirnovaa,
Valery E. Tarabankoa,b* and Michael Yu. Chernyaka
a
Institute of Chemistry and Chemical Technology SB RAS
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 21.11.2013, received in revised form 14.12.2013, accepted 15.01.2014
The extraction method to regenerate hydrochloric acid as the catalyst of the fructose conversion to
levulinic acid (LA) is developed. The influence of potassium chloride additions on the conversion
and extraction processes is studied. Using HCl and KCl solution as a catalyst and butanol as an
extractant permits to regenerate the catalyst, to decrease catalyst and exractant consumptions in
comparison with usual LA extraction from neutralized water solutions. The extraction degree of
94 % for obtained butyl levulinate is attained by using 2:1 volume ratio of water and butanol phases
in one stage.
Keywords: levulinic acid, butyl levulinate, fructose, acid-catalyzed conversion, hydrochloric acid,
catalyst regeneration.
Introduction
In resent years biomass is known to gain high potential as renewable feedstock for chemical
production. The major components of biomass are hexose carbohydrates, and their transformation
into chemicals is the main direction of sustainable development and ?Green Chemistry?. The main
product of the acid-catalyzed hexose transformation is levulinic acid (4-oxopentanoic acid, LA) [14]. This versatile chemical is applied to produce polymer materials [5-6], pharmaceuticals [7], and
biofuels [8]. In industrial scales wood, agricultural wastes, and hexoses are the raw materials for LA
production [7, 8-12]. Their acid-catalyzed conversion to 5-hydroxymethylfurfural (5-HMF) with its
consequent rehydration produces LA (Fig. 1). The humic substances are formed as a by-product in the
conversion.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: veta@icct.ru
#4#
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Marina A. Smirnova, Valery E. Tarabanko? Regeneration of Hydrochloric Acid in the Catalytic Fructose Conversion?
+
+H
C6H12O6
+2H2O
CH
-3H2O
HOH2C
COOH + HCOOH
3
CHO
O
5-HMF
O LA
Fig. 1
There are many kinds of catalysts for the processes: mineral acids [7, 11], ion-exchange resins [13],
zeolites [14]. The main disadvantages of solid catalysts are their deactivation by tar and low catalytic
activity in water media. Using these catalysts, the high LA yields are attained at low carbohydrate
concentration (0.2 ? 0.3 M). In opposite to solid catalysts, mineral acids have great activity and high
acidity in water media [15-16]. On these reasons the regeneration of gomogeneous and heterogeneous
catalysts becomes the main problem in the conversion processes.
Usually mineral acids are neutralized before extracting the goal product from reaction medium.
To prevent neutralization and lost the catalyst one must extract LA from acid solution and separate
the catalyst and the product in this step. Hence, the effective homogeneous catalytic conversion
has to combine the highest possible LA distribution ratio and minimum HCl distribution ratio for
exractant. A lot of exractants of levuliunic acid are reviewed: ketones [17], ethers [18], alcohols
[19]. Nevertheless, the possibilities of catalyst regeneration when using these exractants are not
studied.
We have recently demonstrated the possibility of catalyst regeneration in hexose conversion in
water-butanol system [19]. Butanol forms the stable two-phase system with water, but concentrated
(5 M) sulphuric and hydrochloric acids are known to give homogeneous solutions with the alcohol.
To prevent homogenization the mixture of sodium sulphate and sulphuric acid as the catalyst (sodium
hydrosulphate with or without addition of sulphuric acid) can be applied. This approach permits to
create stable two-phase system water-butanol with good catalytic activity. Hydrochloric acid is more
active than sulphuric acid and sodium hydrosulphate [20]. Its distribution ratio in the system waterisopentanol is 5 ? 10 times greater than that of sulfuric acid, and HCl is distributed into organic phase
when adding calcium chloride in the water phase [21]. But this catalyst is usually neutralized before
the LA extraction after carbohydrate conversion [22], and the literature data on the hydrochloric acid
regeneration in the process lack.
In this paper the HCl regeneration in the fructose acid-catalyzed conversion to LA and its
derivatives is studied.
Experimental
Fructose of food quality was used in the experiments. Carbohydrate (1 M) conversion in water
solution was carried out in a 250 ml thermostated magnetically stirred glass flask with water condenser
at 95 °C. Hydrochloric acid of 1 M concentration was used as catalyst and 200 g/l potassium chloride
was added into the reaction mass (Fig. 2) [23].
Then the salt concentration was increased to 450 g/l and butanol extraction of LA as butyl
levulinate was carried out at 50 °C. Water and butanol phase aliquots (1 ml) was sampled and analyzed
#5#
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
HCl+KCl (450?/?)
950?
+BuOH+LA
500?
regenereted catalyst,
HCl+KCl
water
phase
HCl+KCl (200?/?)
KCl
crystalline
fructose
organic phase
Marina A. Smirnova, Valery E. Tarabanko? Regeneration of Hydrochloric Acid in the Catalytic Fructose Conversion?
cooling
100?
ButO
O
O
CH3
Fig. 2
by G.L.C. Then the water phase of reaction mixture was cooled to 10 °C and crystalline potassium
chloride was separated. The water solution containing HCl and KCl was used in a new cycle of the
carbohydrate conversion. The catalyst wastes were estimated by the potentiometric titration of butanol
and water phases.
Results and discussion
The potassium chloride addition into the system consisted of HCl, fructose, water, and butanol
lead to the phase separation, but salt additives decreases yield of levulinic acid in the process. To
overcome this contradiction we carried out the catalytic conversion in the solution with low salt
concentration, and then the extraction of LA in a form of butyl ester was carried out at high KCl
content.
LA is completely alkylated in the process, and butyl levulinate is extracted into the butanol phase,
whereas 93-95 % of hydrochloric acid remains in water phase. To convert butyl levulinate into levulinic
acid the acid or alkaline hydrolysis may be applied. Adding KCl slightly decreases the conversion
selectivity (27 mol. %) in comparison with HCl-catalyzed process without salt additions (30 mol. %)
[11]. The experimental results are shown in Table 1.
Extraction with a little volume of butanol (1 : 10 butanol to water ratio) is insufficient, and even
repeated extraction permits to removed only a half of the product. The extraction is more efficient at
higher butanol to water ratio 1 : 2. Under these conditions butyl levulinate is formed in the extraction
system and removed efficiently from water to the organic phase. HCl wastes (a part extracted into
organic phase) in all experiments are of 5 ? 7 %.
Cooling the water phase after extraction precipitates potassium chloride and recycles the
catalyst water solution. This approach allows reducing catalyst consumption by a factor of 10 ? 20 in
comparison with the usual LA extraction after the acid neutralization [24]. Moreover, in this case the
butyl levulinate distribution ratio (k = 34) is almost 10 times greater than for the LA extraction from
neutral water solutions (k = 4) [24-25]. In these conditions the extraction degree of 94 % is attained
by using 1 : 2 volume ratio of butanol and water phases in one stage. To attain such extraction degree
from neutralized solution one should apply six times greater volume ratio of butanol and water phases
of 3 : 1.
#6#
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Marina A. Smirnova, Valery E. Tarabanko? Regeneration of Hydrochloric Acid in the Catalytic Fructose Conversion?
-
-
-
28
4.36
32
5.1
450 in a second extraction
1 : 10
31
105
34
2.54
20
4.5
200 / 450
1:2
35
60
86
34.00
94
7.5
200 recycled conversion, 450
extraction
1:2
34
50
89
20.25
89
5.3
HCl waste, %
-
100
?, %
-
36
D
40
1 : 10
0
But-LA yield,
mol. %
LA concentration
before extraction,
g/l in water phase
-
200 / 450
KCl concentration,
g/l in the steps
of conversion/ext-raction
But-LA
concentration, g/l
in butanol phase
Vorg.Vaq.
Table 1. Influence of KCl additives and butanol volume to the butyl levulinate (But-LA) distribution ratio (D) and
extraction degree (?) in fructose conversion and extraction
Conclusion
The obtained results demonstrate the efficiency of new method to produce levulinic acid and to
separate it from the solution of HCl catalyst. Butanol as extractant and a water solution of hydrochloric
acid and potassium chloride as the catalyst are used in this method. Levulinic acid is recovered from
the catalyst solution in the form of butyl levulinate. This approach allows increasing the extraction efficiency, decreasing the catalyst and extractant consumption in comparison with traditional LA extraction from the neutralized product solution.
Acknowledgements
Financial support from Russian Foundation for Basic Research (Grant No. 13-03-00754) is
gratefully appreciated.
References
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#7#
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335 p.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Marina A. Smirnova, Valery E. Tarabanko? Regeneration of Hydrochloric Acid in the Catalytic Fructose Conversion?
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Journal of Siberian Federal University. Chemistry 1 (2014 7) 10-16
~~~
??? 541.14:54-161.6:535
Luminescence and Light Scattering
in the Doped ZBLAN and Tellurite Glasses
Leonid N. Alexeikoa, Irina G. Maslennikovaa,b,
Alexei Yu. Mamaevb, Valeriy I. Kharchenkoa,b*,
Vladimir K. Goncharuka,b and Valeriy Ya. Kavuna,b
a
Far-Eastern Federal University,
8 Sukhanova Str.,Vladivostok, 690091, Russia
b
Institute of Chemistry FEB RAS,
159 Pr. Stoletiya Vladivostoku, Vladivostok, 690022, Russia
Received 13.11.2013, received in revised form 20.11.2013, accepted 26.12.2013
Some ZBLAN glasses doped with NdF3 and the tellurium-containing glass 90TeO2?10PbO·P2O5 were
studied by physical chemical methods. The temperature dependence of luminescence intensity was
obtained for the ZBLAN glasses. Light scattering of ZBLAN glasses and the tellurium-containing
glass was studied. The luminescence maximum (1054 nm, Nd) and the scattered light maximum (1100
nm) were recorded in the temperature range 25?440°C for the ZBLAN glasses and 25?530°C for the
tellurium-containing glass. The correlation was found between temperature changes in the optical
characteristics and data of differential thermal analysis of the glasses. It was shown that in the optical
temperature dependences there were observed changes in the area of glass transition temperature
Tg, the onset of crystallization Tx and maximum crystallization Tc. It is possible to use the temperature
dependences of optical curves as a control for heat treatment of vitreous samples at glass ceramics
production.
Keywords: ZBLAN glasses, tellurium-containing glasses, luminescence, light scattering, DTA, glass
ceramics.
Introduction
Glassy materials activated by the rare earth elements (RE) are used as an active medium to
create lasers, fiber amplifiers, luminescent sensors. The most promising materials are activated glassceramics [1-3]. Typically, glass-ceramics is obtained by spontaneous crystallization, i.e. the crystal
nanosize phase in the bulk glass is produced under exposition at temperatures slightly above the
glass transition temperature Tg [4-6]. The REs in the crystal composition are as nucleation sites [7, 8].
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: vikharchenko@gmail.com
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Leonid N. Alexeiko, Irina G. Maslennikova? Luminescence and Light Scattering in the Doped ZBLAN and Tellurite?
Glass ceramics refers to the intermediate position between crystals and glasses. It combines the best
properties of crystals ? high mechanical and thermal strength ? and the best characteristics of glasses ?
the possibility of pressing and forming, the ability of extending of optical fiber and carrying out the ion
exchange to create waveguide structures [4].
To produce glass ceramics it is necessary to control the crystallization process directly during
the heat treatment to be able to stop heating at the desired step. Therefore, the purpose of this work
is to study the temperature dependence of spectra of luminescence and scattered light versus thermal
properties of the glasses.
Materials and methods
For synthesis of glass samples there were used tellurium oxide TeO2, fluorides of zirconium ZrF4,
barium BaF2, aluminium AlF3, lanthanum LaF3,ytterbium ErF3, and neodymium NdF3 of the ?pure?
grade, lead metaphosphate Pb(PO3)2 of the ?pure for analysis? grade. The dried initial reagents were
milled by a Retsch vibration mill MM 301 for 30 minutes with frequency of 20 beats per minute.
The ZBLAN glass synthesis was done in the covered platinum crucible by the technique ?a
crucible in a crucible? in the electric furnace of adjustable heating at temperature of 900-950oC for
25?30 minutes. The technique of tellurium glass synthesis was described in [9]. The melt was poured
into the steel rings placed on the nickel mold preheated to 220-300oC. Then the surface was quickly
evened by the hot press, removing the excess vitreous mass. And finally the melt was cooled to the
room temperature.
For research there were used glass powders, pressed into tablets of 2 mm thickness, and transparent
glass samples, poured into steel rings with the outer diameter dout = 1.2 cm and thickness of 1-3 mm.
The glass surface was smooth enough, so they were not polished additionally.
Differential Thermal Analysis (DTA) spectra of the glass powders were recorded in air on a
modernized derivatograph Q?1500 (MOM company) using the covered platinum crucibles at the
heating rate of 5oC per minute.
The temperature dependences of luminescence were obtained for the samples, placed in the thermal
cell, by irradiating of a xenon lamp DKsSH?150 in the range of 340?700 nm selected by a combination
filter SZS23+SZS25. The heating effect on light scattering by the samples was studied at irradiating
with light from 800 nm, selected by the filter IKS1. The angle of the excitation light flux on the sample
surface was 45?, the angle of the recorded flux ? 25?. Intensity measuring of luminescence and scattered
light was carried out with continuous registration on a spectrometer SDL?1 at wavelengths 1054 and
1110 nm, respectively. The sample temperature was varied from 25 to 440°C for the ZBLAN glasses
and from 25 to 530 °C for the tellurium-containing glasses. The heating rate of samples was similar
to the heating rate in DTA and was equal to 5±1 °C/min. The luminescence spectra were recorded
directly during the sample heating.
Results and discussion
Compositions of the studied ZBLAN and tellurium-containing glasses are presented in the Table.
Temperature dependences of the luminescence intensity (? = 1054 nm) of the ZBLAN glasses doped
with NdF3 at various thickness of samples are shown in Fig. 1. The curve shapes are somewhat similar
to the DTA curves of the glasses at heating. In the range of 261?272 °C, there are observed small
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Leonid N. Alexeiko, Irina G. Maslennikova? Luminescence and Light Scattering in the Doped ZBLAN and Tellurite?
Table. Composition of the studied glass samples
Sample
Glass composition, mol%
ZrF4
BaF2
LaF3
AlF3
NaF
NdF3
ZBLAN?1NdF3
53
20
3
3
20
1
-
-
-
ZBLAN?1YbF3
53
20
3
3
20
-
1
-
-
ZBLAN
53
20
4
3
20
-
-
-
-
-
-
-
-
-
-
-
90
10
TeO2?Pb(PO3)2
YbF3
TeO2
Pb(PO3)2
Fig. 1. Temperature dependences of intensity of the neodymium luminescence band (1054 nm) in the ZBLAN?
1NdF3 glass samples of thickness: 1 ? 3 mm; 2 ? 2 mm; 3 ? repeated heating of the sample 2
inflections in the curves. At these temperatures in the ZBLAN glasses, the softening begins, which
is characterized by appearing of a little mobility of structural layers and corresponds to the glass
transition temperature Tg.
At 354 °C the curves pass through a minimum and go to a maximum at 407 °C. On the DTA
curve of the ZBLAN-1NdF3 glass, these values are close to the temperatures of the first crystallization
onset T?1 = 348 °C and the second crystallization onset T?2 = 403 °C (Fig. 2). It should be noted that at
reheating of the cooled crystallized glass sample ZBLAN-1NdF3 the luminescence intensity decreases
monotonously and does not match the parabolic nature (Fig. 1, curve 3). Consequently, the complex
shape of luminescence curves of the original glasses is associated with structural changes at heating
process, as the irreversible crystallization is typical for the ZBLAN glasses.
The sample heating was finished at 440 °C to avoid the beginning of melting and flowing of the
softened glass mass from the ring-shaped molds. Upon cooling, the luminescence intensity increased
monotonously, while there was a slight inflection at 360°C, which corresponds to the crystallization
process (the exothermic effect at 360 °C) in the DTA cooling curve. The Nd 3+ luminescence spectrum
shape varies slightly during the sample heating, while the intensity increases about twice in the cooled
(crystallized) sample (Fig. 3).
The temperature curves of light scattering by the samples of ZBLAN and TeO2?Pb(PO3)2 glasses
are shown in Fig. 4. The curve shapes of the ZBLAN glasses (Fig. 4, curves 1?3) are similar in nature,
which is explained by the same structure of the ZBLAN glass. In the range of 265?268 °C as well
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Fig. 2. DTA curve of the glass powder ZBLAN?1NdF3 recorded at the rate of 5°C/min. in air
Fig. 3. Evolution of the Nd3+ luminescence spectrum shape versus temperature: 1 ? after heating to 440 °C and
cooling to 23 °C; 2 ? before heating, the original sample; 3 ? at 440 °C
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Leonid N. Alexeiko, Irina G. Maslennikova? Luminescence and Light Scattering in the Doped ZBLAN and Tellurite?
Fig. 4. Temperature dependences of light scattering (? = 1100 nm) by the samples of thickness: 1 ? 2.5 mm,
ZBLAN glass; 2 ? 2.5 mm, ZBLAN?1YbF3 glass; 3 ? 2.0 mm, ZBLAN?1NdF3 glass; 4 ? 2.0 mm, tablet of the
ZBLAN?1NdF3 glass powder; 5 ? 2.0 mm, 90TeO2?10Pb(PO3)2 glass; 6 ? 2.0 mm, tablet of the 90TeO2?10Pb(PO3)2
glass powder; 7 ? 2.0 mm, tablet of Al2O3
Fig. 5. DTA curves of the ZBLAN glass for the powder (1) and bulk glass poured into the ring with thickness of
2 mm (2), recorded at the rate of 5°C/min. in air
as for the luminescence curves, there are observed slight inflections, that in the differential curve
corresponds to the glass softening temperature Tg (Fig. 5).
The curves of light scattering have several minima and maxima, and are more complicated in
nature as compared with the luminescence curves. However, one can identify some patterns. Near the
temperature range corresponding to the glass transition temperature Tg, there is observed a decrease
in the scattering intensity, whereas at temperatures at which crystallization begins, the light scattering
intensity increases (Fig. 4). This is well illustrated by the sample ZBLAN?1NdF3 pressed into a tablet
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Leonid N. Alexeiko, Irina G. Maslennikova? Luminescence and Light Scattering in the Doped ZBLAN and Tellurite?
(Fig. 4, curve 4). An influence of temperature characteristics of the sample on the shape of the scattering
and luminescence temperature curves is obvious. This is confirmed by nature of scattering curves of
tellurium-containing samples and aluminum oxide.
Thus, for the 90TeO2?10Pb(PO3)2 samples, contrary to the ZBLAN samples, the changes appear
much later ? in the range of 315?335 °C (Tg ? the beginning 324 °C, the end ? 347 °C), and up to 400°C
for the glass sample (Fig. 4, curve 5) no changes were observed. For the pressed Al2O3 sample in the
whole heating range from 25 to 530 °C no changes were observed, which is rather understandable.
This is a fairly stable compound, Tmelt.(Al2O3) = 2010?2050 °C.
Conclusions
The temperature dependences were studied of luminescence intensity and light scattering for the
samples of ZBLAN and tellurium-containing glasses in the temperature ranges of 25?440 °C and 25?
530 °C, respectively. The correlation was revealed between temperature changes of intensity maxima
of the optical spectra and DTA data of the samples. It was shown that in the optical temperature
dependences, there are observed changes in the glass transition temperature Tg, onset of crystallization
Tx and the crystallization peak Tc of the glasses. The obtained relations between the sample optical
spectra and thermal properties can be used for controlled heat treatment to produce glass ceramics.
Acknowledgements
The work was financially supported by the Ministry of Education and Science of the Russian
Federation within the state contract of the Far Eastern Federal University No. 3.8646.2013.
References
1. Ahrens B., Lцper P., Goldschmidt J.C., Glunz S., Henke B., Miclea P-T., Schweizer S.
Neodymium-doped fluorochlorozirconate glasses as an upconversion model system for high efficiency
solar cell // Phys. Status Solidi A. 2008. V. 205, No. 12. P. 2822-2830.
2. Chaliha R.S., Annapurma K., Tarafder A., Tiwari V.S., Gupta P.K., Karmakar B. Structure,
dielectric and optical properties of transparent Nd3+:KNbO3 nanocrystalline glass-ceramics // Optic.
Mater. 2010. V. 32. P. 1202-1209.
3. Mortier M., Patriarche G. Structural characterization of transparent oxyfluoride glass-ceramics
// J. Mater. Sci. 2000. V. 35. P. 4849-4856.
4. Dantella G., Mortier M., Patriarche G., Vivien D. Er3+ -doped PbF2: Comparison between
nanocrystals in glass-ceramics and bulk single crystals // J. Solid State Chem. 2006. V. 179. P. 19952003.
5. Fedorov V.D., Sakharov V.V., Provorova A.M., Baskov P.V., Churbanov M.F., Shiryaev V.S.,
Poulain M., Poulain Mi., Boutarfaia A. Kinetics of isothermal crystallization of fluoride glasses //
J. Non-Cryst. Solids. 2001. V. 284. P. 79-84.
6. Reben M., Waclawska I., Paluszkiewicz C., ?roda M. Thermal and structural studies of
nanocrystallization of oxyfluoride glasses // J. Thermal Anal. Calorimetry. 2007. V. 88, No. 1. P. 285-289.
7. Kukkonen L.L., Reaney I.M., Furniss D., Seddon A.B. Nucleation and crystallisation behaviour
of transparent, erbium III doped, oxyfluoride glass ceramics for active photonic devices // Phys. Chem.
Glasses. 2001. V. 42, No. 3. P. 265-273.
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Leonid N. Alexeiko, Irina G. Maslennikova? Luminescence and Light Scattering in the Doped ZBLAN and Tellurite?
8. Yu H., Zhou K., Chen R., Song J., Hou Ch., Zhao L. Investigation of the crystallization process
in oxyfluoride glass ceramics codoped with Er3+/Yb3+ // J. Non-Cryst. Solids. 2008. V. 354. P. 36493652.
9. Apakova I.E., Markova T.S., Yanush O.V., Goncharuk V.K., Maslennikova I.G., Polyakova
I.G., Anan?ev A.V., Maximov L.V., Medium-range order and physicochemical properties of (100-?)
(0.5PbO·0.5P2O5)?xTeO2 glasses in terms of the constant stoichiometry grouping concept // Glass
Phys. Chem. 2010. V. 36, No. 6. P. 637-651.
????????????? ? ????????? ?????
? ???????????? ??????? ZBLAN
? ??????????? ???????
?.?. ?????????a, ?.?. ????????????a,?,
?.?. ???????, ?.?. ????????a,?,
?.?. ????????a,?, ?.?. ?????a,?
a
??????????????? ??????????? ???????????,
??????, 690091, ???????????, ??. ????????, 8
?
???????? ????? ??? ???,
??????, 690022, ???????????,
??. ???????? ????????????, 159
??????-??????????? ???????? ??????? ????????? ?????? ZBLAN, ???????????? NdF3, ?
???????????????? ?????? 90TeO2?10PbO·P2O5. ??? ?????? ZBLAN ???????? ?????????????
??????????? ????????????? ?????????????. ??????????? ????????? ????? ? ???????
ZBLAN ? ? ???????????????? ??????. ????????? ????????????? (1054 ??, Nd) ? ?????????
????? (1100 nm) ?????????? ? ?????????? ?????????? 25?440 °C ??? ?????? ZBLAN ?
25?530°C ??? ????????????????? ??????. ?????????? ?????????? ????? ??????????????
??????????? ?????????? ????????????? ? ??????? ????????????????? ????????????
??????? ????????????? ??????. ????????, ??? ? ????????????? ???????????? ??????????
????????????? ??????????? ????????? ? ??????? ?????????? ??????????? Tg, ??????
?????????????? Tx ? ????????? ?????????????? Tc. ???????? ????????????? ?????????????
???????????? ?????????? ?????? ??? ???????? ?????????????? ?????????? ???????? ???
????????? ??????????????.
???????? ?????: ?????? ZBLAN, ???????????????? ??????, ?????????????, ????????? ?????,
???, ??????????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 17-22
~~~
??? 658.62 : 62 ? 02
Safety of Goods from Polymer Composites:
Organizational and Methodological Aspects
Evgeniya A. Demakova,
Nadezhda A. Egorova* and Tatiyana N. Yamskikh
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 13.06.2012, received in revised form 14.08.2012, accepted 05.07.2013
The factors affecting the increase in the chemical danger of goods from polymer composites on the
example of furniture made of laminated chipboards and medium density fiberboards are considered
in the article. The limits of formaldehyde concentration growth due to the deviation of operating
conditions from the standard parameters modeled in order to verify the product safety requirements
are shown.
Keywords: chemical safety, furniture made of laminated chipboards and medium density fiberboards,
information for consumers.
The basic mission of technical regulation ? to ensure safety of Russian citizens from threats
to life and health ? is carried out by the adoption of safety requirements at different stages of the
product life cycle in technical regulations (TR) and declaring obligatory following these requirements
for manufacturers and others who place the products on the market. To ensure consumer safety during
the products operation it is not only necessary for the product to meet TR requirements, but also to
provide all information about the rules and conditions of its safe use.
The magnitude of risk to life and health of the consumer is determined by the degree of conformity
of the requirements related to technical regulations standards to hygienic standards, as well as the actual
conditions of the goods usage. The urgency of the problem and some practical aspects of ensuring
consumers safety will be considered on the example of furniture.
The technical regulations of the Customs Union (CU) ?Furniture Safety? declares that full
compliance of the rules of normal use provide mechanical, chemical, fire and electrical safety of
furniture products. The TR specifies two conditions obligatory for the furniture chemical safety:
1. Mandatory sanitary-epidemiological and hygienic evaluation of polymer composites used in
the manufacture of furniture, as well as finished products for compliance with ?General sanitary-
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: evdemakova@ya.ru
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Evgeniya A. Demakova, Nadezhda A. Egorova? Safety of Goods from Polymer Composites: Organizational?
epidemiological and hygienic requirements for products subject to sanitary-epidemiological supervision
(control).
2. The presence of protective and decorative coatings on the surfaces of furniture parts made of
derived timber products.
The specific requirements for product safety and testing methods are established in international
and national CU member countries` standards, inter-related with the developed TR.
However, in our opinion, neither in the document nor in the relevant standards due attention is
given to the rules of furniture normal usage which ensures its chemical safety.
The discussion of the TR by the experts in the field of word-processing industry in professional
literature has also shown that with the TR entry into force the main problem for the industry will be to
ensure chemical safety of furniture, primarily by the level of formaldehyde emission [1].
It is known that formaldehyde has toxic effects. It irritates the eyes, mucous membranes and
respiratory tracts. It causes headaches and nausea, occurrence of immunopathologic reactions.
International Agency for Research on Cancer (IARC) has classified formaldehyde in Group 2A. The
agent (mixture) may be classified in this category when it is potentially carcinogenic to humans on the
basis of strong evidence [2].
In our opinion the problem of furniture chemical safety, taking into account the level of
formaldehyde emission, has the following organizational and methodological aspects:
1. The possibility of deviation of operating conditions from the modeled parameters of testing
chemical safety of furniture and wood-based panels.
The levels of chemicals released into the air from furniture and wood products, are defined
according to the GOST 30255-95 ?Furniture, wood and polymeric materials. The method to determine
formaldehyde emission and other harmful volatile substances in climate chambers?, which assumes
providing three main parameters during the test:
air temperature ? (23 ± 2) є? ;
relative humidity ? (45 ± 5) %;
air change ? 1 ± 0.1 volume per hour.
To test modular furniture (wardrobes, tables, etc.) as well as wood materials, the saturation of the
camera makes 1 ?2 of the surface area of a product or a sample plate for 1 ?3 of volume.
Primary formaldehyde ? found in laminated chipboards (LCB) during their manufacture, fills the
air spaces between the wood particles. It diffuses to the surface of the plate through the complex system
of internal pores, and then comes into the air. For formaldehyde this process is stretched out over time
because of the low permeability of protective and decorative coatings (laminations). Gradually its
content in the plates reduces, but the destruction of carbamide-formaldehyde resin with formaldehyde
emission extends over the entire life cycle of products, especially at elevated temperature and humidity
of the environment.
The research of chipboard samples by chamber method has shown [3] that at +23 є? increase in
relative humidity from 45 to 70, and 90% causes an increase in formaldehyde emissions, respectively,
1.4 and 1.6 times. A similar increase in relative humidity, while the temperature rises to +30 є? entails
1,9 and 2.4 times increase of formaldehyde content in the air.
It is shown that with the multiplicity of air changes less than 0.5 volume per hour the equilibrium
concentration of formaldehyde in the room comes in 14-16 hours, the approximation of the multiplicity
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Evgeniya A. Demakova, Nadezhda A. Egorova? Safety of Goods from Polymer Composites: Organizational?
of air changes to 1 volume per hour is accompanied by a 3 times decrease in the equilibrium
concentration of formaldehyde.
Consequently, furniture and laminated chipboard panels, which confirmed the chemical safety
in the tests under standard conditions, may release more formaldehyde than Maximum Permissible
Concentration (MPC) in a real-life operation, if the temperature and humidity conditions, air or space
saturation with surfaces of wood materials are different from the simulated values for the relevant
parameters.
2. The difference of formaldehyde emission standards:
? in Hygienic Standards 2.1.6.1338-03 ?Maximum Permissible Concentration of pollutants in the
air of populated areas,? the daily average Maximum Permissible Concentration of formaldehyde
for atmospheric air of populated areas should make 0.003 mg/mі;
? for the purposes of the sanitary-chemical evaluation of furniture according to the GOST 1637193 ?Furniture. General technical conditions?, as well as in accordance with the General sanitaryepidemiological and hygienic requirements for goods subject to sanitary-epidemiological
supervision (control) Maximum Permissible Concentration of formaldehyde released into the
indoor air during furniture usage should make 0.01 mg/mі;
? for the sanitary-chemical evaluation of laminated chipboards (LCB) ? the basic material in a
modern furniture production ? in the GOST R 52078-2003 ?Chipboard plates coated with films
based on thermo reactive polymers? the rate of formaldehyde emission for the E1 grade plates
should make not more than 0.124 mg/mі.
Taking into account the identity of the standard conditions used to test furniture products and
LCB samples in climatic chambers, it is not clear how it is possible to manufacture furniture which
release not more than 0.01 mg/mі formaldehyde into the indoor air with E1 grade panels (with the norm
of formaldehyde emissions to 0.124 mg/mі).
The existence of the considered factors necessitates monitoring of indoor air in order to assess
chemical risks to the furniture consumer in real conditions of its operation.
24 school class rooms in different districts of Krasnoyarsk where the life of the furniture made
from 2 to 18 months at the beginning of the experiment were selected as the object of the study.
The class rooms were equipped with desks and bookshelves made of LCB, student chairs with seats
and backs bent from solid Medium Density Fiberboards manufactured by dry felting (MDF), foiled
with synthetic veneer. All series of measurements were carried out in the heating season ? under
comparable conditions of temperature (22 ± 3 єC) and humidity (45 ± 5%) in all the class rooms
surveyed.
Given the relatively low level of saturation of the rooms with furniture (0.41-0.55 mІ/mі) and
compliance with the parameters of temperature and humidity to the standard values, the insufficient
ventilation has the greatest negative impact on the composition of air in the class rooms. To
assess this effect the most typical adverse operating conditions of two types were simulated in the
experiments.
In the conditions of the first type the concentration of formaldehyde in the classrooms after 12-15
hours without ventilation was measured. Such situation is typical to the beginning of morning classes
and may be regarded as critical, i.e. the most dangerous because of the accumulated concentration of
formaldehyde for the night period without ventilation.
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Evgeniya A. Demakova, Nadezhda A. Egorova? Safety of Goods from Polymer Composites: Organizational?
Fig. 1. Dynamics of the concentration of formaldehyde in the air of classrooms in different experimental
conditions, mg/mі
The second type of operating conditions simulates the danger of formaldehyde accumulation in
the classrooms that are not ventilated for 3-5 hours, when they are not ventilated during the breaks
between classes.
In the models of both types after the first air sampling there was 10-minute intensive ventilation
and the concentration of formaldehyde was measured again using the method of photometric analysis
according to the GOST 30255-95.
The results of air samples tests for formaldehyde content (Fig. 1) clearly demonstrate the influence
of the prolonged absence of ventilation in the rooms and the life of the furniture on this indicator. In the
first half of the year in conditions when there is no ventilation for 12-15 hours the maximum value of
formaldehyde content in the air makes 0.106 mg/mі, the minimum value ? 0.052 mg/mі, and an average
value ? 0.078 mg/mі which reaches 26 times excess of MPC (beam A in Fig. 1) for the atmospheric
air of populated areas ? 0.003 mg/mі. After 10 minutes ventilation the concentration of formaldehyde
decreases and makes from 0.039 to 0.086 mg/mі (beam B in Fig. 1) ? an average to 22 MPC (0.065 mg/mі).
Such multiple excess of hygienic standards constitute a serious threat to the normal state of health for
people staying in the rooms with new furniture made of wood for a long time.
The survey of teachers showed that with the detected concentrations of formaldehyde they do
not feel unpleasant smell and have no concerns about the chemical composition of air. Accordingly,
the motivation for airing is not actual pollution, but the temperature rise over its comfort level +23 ...
+25 є?.
Even in the case of less prolonged absence of air change ? 3 to 5 hours ? in a series of experiments,
the formaldehyde content in the classrooms ranged from 0.028 to 0.071 mg/mі (beam C in Fig. 1) the
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Evgeniya A. Demakova, Nadezhda A. Egorova? Safety of Goods from Polymer Composites: Organizational?
average value of formaldehyde 17 times exceeded MPC (0.050 mg/mі). After 10 minutes through
ventilation the concentration of formaldehyde in the classrooms tested decreased and reached 0.0170.061 mg/mі (beam D in Fig. 1), reduced it an average to 13 MPC (0.040 mg/mі).
In the first part of the second year of furniture usage the situation with formaldehyde pollution
is markedly improved, but it is still far from hygienic norms. So the maximum 12-15 hours lack of
ventilation showed 9-19 times excess of MPC (0.030-0.058 mg/mі), concentration of the toxicant
makes an average 13 MPC (beam E in Fig. 1). After 10 minutes through ventilation the concentration
of formaldehyde in the classrooms tested decreased and reached 0.019-0.053 mg/mі (3-18 ???) (beam
F in Fig. 1).
With 3-5 hours absence of forced air change concentration of formaldehyde in the classrooms
tested ranged from 0.016 to 0.031 mg/mі (5-10 ???), and the average content of formaldehyde in
the air reached 8 ??? (beam G in Fig. 1). After 10 minutes through ventilation concentration of
formaldehyde in the classrooms tested decreased and reached 0.009-0.024 mg/mі (3-8 ???) (beam
H in Fig. 1).
According to TR ?Furniture Safety? rules and conditions for safe product operation should
be specified in the instruction manual. They should focus on the use of a product for its intended
purpose taking into account the allowable loads and protection of the furniture surfaces from water
and temperatures above +40 є?.
In our opinion, it is necessary to specify the microclimate parameters (temperature, relative
humidity and air change), as well as the saturation of the room with furniture, ensuring its chemical
safety. The absence of the requirement to provide such information in TR, in essence, leads to violation
of consumers' rights. They are deprived of the opportunity to obtain all necessary information about
the conditions of the product safe operation, and as a consequence can systematically take risks for
their health and wellness.
References
1. Technical Regulations of the Customs Union 025/2012 ?Safety of furniture products?
[Electronic resource]: the decision of the Eurasian Economic Commission Council of. 15.06.2012 ? 32.
Mode of access: ConsultantPlus.
2. Pylev L.N. Monographs of International Agency for Research on Cancer (IARC) to evaluate
the carcinogenic risk of chemicals to humans // Toxicology Gazette. 1997. ? 1. P. 32-33.
3. GOST R ISO 16000-2-2007. Air in closed space. Part 2. The sampling for formaldehyde content.
Basic principles. ? Entry into force. 01.10.2007. M.: Standartinform, 2008. 19 p.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Evgeniya A. Demakova, Nadezhda A. Egorova? Safety of Goods from Polymer Composites: Organizational?
??????????????-???????????? ???????
??????????? ???????????? ????????????
????????????????? ??????????????? ???????
?.?. ????????,
?.?. ???????, ?.?. ??????
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
??????????? ???????, ???????? ?? ????????? ?????????? ????????? ???????????? ???????
?? ????????????????? ??????????, ?? ??????? ?????? ?? ????????? ????. ???????? ???????
????? ???????????? ????????????? ?????????? ?????????? ??????? ??????? ????????????
??????? ?? ??????????? ???????? ??????????, ???????????? ??? ?????????????
???????????? ????????? ??????????? ????????????.
???????? ?????: ?????????? ????????????, ?????? ?? ????????? ?????????????? ??????????,
?????????? ??? ????????????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 23-30
~~~
??? 544.18, 547.022
???????????? ? ??????????? ?????????
????????????????? ?????? (II)
? ???????? ???????? ?????????
?.?. ???????*
????????? ???????????????
??????????????? ???????????,
??????, 660049, ??????????, ??. ????, 82
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
Received 25.06.2012, received in revised form 14.11.2013, accepted 21.12.2013
????????-?????????? ??????? ?????? ??????????? ????????? B3LYP/6-31G(p,d) ??????????
???????????? ? ??????????? ???????? ????-, ??-, ???- ? ?????????????????????? ??????
(II). ????????, ??? ???????? ??? ??? ???????? ?????????? ??????????? ???????? ?????????.
??? ???? ??????? ??? ?????????? ?????? ???? ??????????, ?? ??????????? ???-?????
????????????????? ?????? (II), ?????????? ??? ????????? ??????????? ?????????. ??????????
???????? ????? ????? ? ??????? ?????????? ????????????? ???????? ????????? ? ?????????
446-550 ??. ?????? ????? ???????????? ??? ????????????? ????????????? ???????????
????????????????? ?????? (II) ??? ???????????????? ??????? ??????? ???????????.
???????? ?????: ???????????????? ???????, ???????????????????, ?????????, ?????????????????? ???????.
????????
???????????????? ?????????? ? ?? ??????????? ???????? ???????? ??????? ? ????????? ???????? ??????????? ?????, ??????? ????????? ? ?????????? ?????. ?????? ???????
???????????? ?????????? ?????? ??????? ? ????????. ???????????? ???????? ???????????? ? ??????? ?????????????? ??????????? ? ???????? ???????????????????? (??) ??? ???????????????? ??????? (???) [1-5].
???? ?? ?????????????? ?????????? ???????? ?? ??????? ?? ????????? ????????
????? ????????? ? ?????????? ???????? ????????? [6-10]. ?? ????????? ???????????
???????? ?? ?????????? ??????, ?? ??????? ????????? ???????? ??????. ??????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: kpo1980@gmail.com
# 23 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????. ???????????? ? ??????????? ????????? ????????????????? ?????? (II) ? ???????? ?????????
???????? ?????????? ?? ??????????? ? ?????????? ????????? ????????? ????????? ?????????????????? ? ??? ????????????? ????????? ??? ???????????? ????????? ?????????.
????????????? ????????, ??????????????? ??????????? ??????? ??? ???????? ????????? ???????????, ??????? ????????????, ??? ?????? ??????????? ?????????? ?? ????????????? ?????????? ?????? ?????????????. ??? ???? ??????????? ???? ?? ???????????????? ??????? ??????????????? ??????????????? ????????? ?????????????? ??? ??????????
? ?????????? ???????????????. ? ?? ????? ????????? ?????????: ? ??????? ??????????? ??
?????? ????? ??????????? ???????? (??? ?????????) ? ??????? 700-900 ??; ??????? ???????? ?? ?? ?????? ????????? ????????? ? ?????? ?????? ???? ?????? ??????? ??????????
?????? ??????????? ????????? (94 ???/????) [11].
??????????? ???????????? ?????????? ? ?? ??????????? ????????? ???? ? ??????????????? ????? ???????? ?????????, ??????? ????? ????????? ????? ???? ? ????? [12]. ??????
???? ????????? ? ???????????? ???????? ????? ?????????? ????????? ? ??????? ? ??????? ???????????? ??????? ??????? ??? ?????? ???????? ???????????? ? ??????? ???????????? ?????????. ??? ???????? ??????? ????? ??????????? ? ????? ???????? ???????????
????????????????????, ??????? ????? ?????????? ??????????? ? ????????. ??? ???? ??????? ????????????, ??? ?????????? ??????????? ?-??????? ????????? ?? ???? ??????????????
?????????? ????? ?????? ?????????????? ??????????? ??????? ??????? ??????????? ???????????? ????????? ?, ??? ?????????, ??????????? ???? ???? ? ??????? ?????????? ???????
??????????. ??????? ????? ?????????????? ????? ?????? ??????? ????????????? ???????????? ???????????? ? ??????????? ????????? ????-, ??-, ???- ? ?????????????????????? ??????
(II) ??? ????????????? ??????? ??? ???.
??????? ? ?????? ????????????
?????????????? ? ??? ??????????? ???????, ? ??????? ????? ???????? ? ?????
?-?????????? (?? ??????) ????????????? ??????????? ?????? ???????? ????????-1,3??????-1,4. ????????? ? ??????? ?????? ?????????? ??????, ??, ??????????????, ???????? ????-, ??-, ???- ? ??????????????. ? ?????? ???????????????? ????????? ?????
?????????????? ??? ? ???????? ?????????? ??????? (???-?????????), ??? ? ?????????????? (?????-?????????). ???????? [12], ??? ?????? ????????? ?????? ?????? ????????
???????????? ?????????????????. ??? ?????????? ? ?????????? ??????????? ?????????
????????????? ??????? ?????? ? ??? ?????????????? ?? ???? ?????????? ???????????
?-???????.
?? ???. 1 ????????? ???????????? ????????? ??????????? ?????????????????????
(??). ????????-?????????? ?????? ?? ??????????????? ? ???????????? ???????? ????????????? ? ??????????? ?????? NWChem [13] ??????? ?????? ??????????? ????????? (DFT) ?
?????????????? ?????????? ???????-??????????????? ?????????? B3LYP [14] ? ??????? ?????? 6-31G(p,d) [15]. ??????????? ????????? ???? ???????? ??????????? ? ?????? ????????
?????? ????????? C2v. ???????? ????????????? ? ???? ???????? ??????????: M=1, 3, 5. ?????
M ? ???????? ??????????????? ???????, ??????? ???????????? ??? M=2S+1, ??? S ? ?????????
???? ???????.
# 24 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????. ???????????? ? ??????????? ????????? ????????????????? ?????? (II) ? ???????? ?????????
???. 1. ???????????? ?????????: ? ? ???????????????????? (1??); ? ? ???-?????????????????? (?-2??);
? ? ?????-?????????????????? (?-2??); ? ? ??????????????????? (3??) ? ? ? ?????????????????????
(4??) ?????? (II)
?????????? ? ??????????
????????? ????????? ???????? ????????????? ??????????? ???????? ?? ?????? ???????.
?? ????. 1 ?????, ??? ??? ????????? ???????? ??????? ??????? ? ??????, ????? ?? ??????????????? ????? ????, ?????????????, ?????? ???????? ????????? ???????? ????????. ???????
????? ???????????? ?????????? ???????????? ???????????? ? ??????????? ???????? ????????? ???????? ? ?????????? ??????????? ???????? ?????????.
?????? ?????????????? ?????????? ??????? (????. 2) ???????, ??? ??? ???????? ?? 1??
? 4?? ? ????? ?????? ?????????? ????????? ????????? ?????? Fe-N. ????????? ??????????
???????? 0,02-0,04 Е. ?????????????, ?????? ??????????????? ??????? ?????????
?????????????, ??? ?????? ????????? ? ?????????? ????????? ?????????? ?? ????? ??????
? ? ??????? ??????????? ?????????? ??? ????????????? ?????????? ???????? ? ?????????
5-? ? 6-? ??????????????? ?????????.
????????? ???????? ????????? ????? N1-Fe-N2 ? N2-Fe-N3 ? 3?? ? N1-Fe-N4 ? ?-2?? ??????
90°, ?? ????? ??????? ????? ? ????????????? ???????? ?????? ????? ? ?????????? ??????????
?? ??? ??????????? ????????? ?????????? ??????????? ???????????? ??????? ?????????? ?????. ? ?-2?? ? 4?? ????? ?? ???????????, ??? ??? ??? ?????????? ?????? ????????????? ??????? ? ?????-??????????, ??? ???????????? ????????????? ? ???-??????????. ???????????? ???????? ?? ??????????????? ????????? ????? ????????????? ???? N1-Fe-N4 ? ?-2??. ???
?????????, ? ?????? ???????? ??????????? ??? ????????????? ???????????? ? ? ???????????
?????????.
?? ???. 2 ????????? ??????????? ????????? ????????? ???????? ??????????? ????????????????????? ? ???????? ???????? ?????????. ????? ???? ? ??????? ??????????? ???????????? ???????? (??), ???? ? ?????? ????????? ??, ?- ? ?-???????? ? ?? ? ?????????????? ????????????? ???????. ??????? ??????? ???????? ?????? ??????? ??????? ??,
# 25 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????. ???????????? ? ??????????? ????????? ????????????????? ?????? (II) ? ???????? ?????????
??????? 1. ?????? ??????? ?????????? ? ????????? ???????? ????????????????, ??
????????
???????? ???????????????
5
1
3
1??
-65461,87
-65463,27
-65461,53
?-2??
-69642,94
-69644,70
-69642,63
?-2??
-69642,95
-69643,81
-69638,04
3??
-73823,95
-73825,44
-73819,33
4??
-78005,04
-78006,45
-78005,22
??????? 2. ?????????????? ????????? ???????
?????????
????? ????? Fe-N1, ?
????????
1??
?-2??
?-2??
3??
4??
2,02
2,01
1,99
2,01
2,01
????? ????? Fe-N2, ?
1,99
1,99
1,98
2,02
2,02
????? ????? Fe-N3, ?
1,99
1,99
1,99
2,01
2,01
????? ????? Fe-N4, ?
1,99
2,01
1,98
1,99
2,02
????????? ???? N1-Fe-N2, ????.
90,12
89,99
90,00
90,09
90,00
????????? ???? N2-Fe-N3, ????.
89,88
89,76
90,00
90,09
90,00
????????? ???? N3-Fe-N4, ????.
89,88
89,99
90,00
89,91
90,00
????????? ???? N1-Fe-N4, ????.
90,12
90,25
90,00
89,91
90,00
??????? ? ?????? ????????? ??. ? ????????? ? ?????? ??????? ????? ??????? ???????????
????????? ??, ? ??????? ? ?? ??????? (????????, ?-por ? ?-benz ? ?-???????? ????????? ?
???????? ??????????????).
????????, ??? ??????????? ????????? ????????? ??????? ??????????? ?????????? ??????????? ????????? ???????????? ??????????? ?-???????? ??????? ? d-?????????? ????? ??????.
???????? ?????? ????? [16] ?????????? ???????? ??????? ???????????? ???????? ?
???????? ????????? ?????????, ?.?. ???? ? ????. ??? ????? ?? ???. 2, ??????? ?-???? ??
???? ?????????? ?????????, ??? ?-???????? ????????????? ?????? ? ?????????? a1. ???????
?????? ???????? (????. 3) ??? ???????? ?? ?-2?? ? 4?? ???????????. ??? ???????? ???????????
????????? ????????????? ??????? ?? ???? ?????????? ??????????? ?-???????, ??? ???????? ? ?? ??????? ????????????. ??? ???????? ?? 1?? ? ?-2?? ??????? ?-???? ???????????
?????????????, ??? ????? ???? ??????????? ????????????? ???????? ?????????????? ????????? ????????? ????????????? ?????? ?? ????????? ? ???????????? ???????????, ?.?. ???
????????? ????????? ???????????? ????????? 1?? ??? ?????????? ??? ?????? ????????-1,3?????-1,4, ?????????? ? ????????? ?????????????. ? ?????? ???????, ?????????? ????????,
??? ??????? ???? ????????? ????????? ? ?????????? 1?? ? 4?? ?????????. ?????????????,
?????????? ?????????? ????? ?????????? ????? ? ???? ?? ??????? ???????? ?????????????
???????????? ???????.
# 26 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???. 2. ?????????????? ????? ???????????? ????????? ????????? ???????: ? ? 1??; ? ? ?-2??; ? ? ?-2??;
? ? 3?? ? ? ? 4??
??????? 3. ??????????? ? ???????????????? ????????? ???????
?????????
??????????? ????? ????? Fe
????????
1??
?-2??
?-2??
3??
4??
1,04
0,90
1,06
1,05
1,06
????????? ???? ????? Fe
1,08
1,01
1,12
1,08
1,08
??????? ?-????, ??
-4,61
-4,95
-4,88
-4,75
-4,61
??????? ?-????, ??
-2,04
-2,08
-2,19
-2,12
-2,04
??????? ?-????, ??
-4,60
-4,89
-4,82
-4,74
-4,60
??????? ?-????, ??
-2,35
-2,29
-2,09
-2,24
-2,35
?r, ???/????
135,01
169,14
82,69
143,48
135,51
550
467
446
495
550
??-??????-????, ??
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????. ???????????? ? ??????????? ????????? ????????????????? ?????? (II) ? ???????? ?????????
? ?????? ??????????? ?-???? ?????????? ?? ?????? ????????, ?? ? ????????. ? 1?? ?
?-2?? ??? ???????????? d-2-????????? ??????, ? ????????? ?????????? ??? ?-???????? ????????????? ??????. ?????? ???? ????????? ?? ??????? ??????????? ????? ?????? ? 1?? ?
?-2?? ????????????? ?????????????? ?????????? ???????, ????????? ?-???? ?? ???????????? ??????????? ?-????????. ???????? ????????? ??????? ?-???? (????. 3) ??? ???????? ??
1?? ? 4?? ?????????? ???????? ??? ?-????.
?? ???? ??????????? ?????????? ?-????, ??? ? ?-????, ???????????? ?-???????? ????????????? ??????. ??? ????? ?????? ???????????? ????? ? ??????????? ?-???? ?????? ?
d-2-????????? ??????. ?????????? ?????????? ?-2??, ??? ?-???????? ????????????? ??????
????????? ????????? ?-????, ??? ????????? ?? ????? ?????? ??????????? ???????? ???????
?????????? ?? ????????? ? ???????.
??? ?????????? ????, ??????????? ??????????? ????????? ?-2?? ??????????? ????????????? ??? ????????????? ????????, ? ????????? ?????????? ????????? ?????????? ????
N1-Fe-N4. ??? ????? ????????? ? ? ????????? ???????????? ?????? ? ?????????? ????? ????? ??????, ???????????? ?? ?????????. ??? ? ?????? ????, ??? ? ????????? ??????????
(????. 3).
? ????? ?????????? ????????, ??? ???????? ???????????? ?????? ? ?????????? ?????
????? ?????? ?? ???? ??????????? ?????? ? ???????. ????????? ????????? ?? ??, ??? ????????
????????? ????????? ???????????? ?? ???????, ? ?????????????, ?????? ?? ???????????????? ??????????? ?????.
???????? ?????????? ??????????? ???????????????? ?????? ? ???????? ?????????
????? ????????? ????, ?????? 1. ?????????????, ????????? ? ??????? ????????? ??????
???????? ????????????. ????? ???????, ??? ????????? ????????????? ????????? ?? ?????
???????-?????????? ???????. ????? ??????? ????????? ??????????? ????????? ? ????? ??????
?? ????? ??????????? ???:
3
1
h?
1
?? o
??,
?? 3 O 2 o 3 ?? 1 O 2 .
??????? ??????? (?r) ?????????? ?????? ????? ??????? ?? ??????? ?????? ??????? ??????????? ? ??????????? ????????? (????. 3) ??????????????? ??.
? ?????????? ????? ??????? ?????, ??? ??? ??, ?? ??????????? ?-2??, ??? ???????? ??
????????????? ??????????? ? ???????? ?????????? ????????? ???????? ??????????? ?????????? ???????, ??????????? ??? ????????? ??????????? ?????????.
??????????? ????????????? ????????? ???????????? ???????? ??????????. ??? ????
?????????? ??????? ????????? ??????? ???????????? ?-???????? ?? ????????? ???????????? ?-????????. ????????-?????????? ?????? ??????????-????????????? ????????? ???????
?? ????? ?????????? ??????? DFT. ???????? ?????? ??????????? ?????? ??? ?????????????
??????? ????????????????? ??????????????. ??????? ? ?????? ?????? ???????????? ?????????? (????. 3) ??????? ????? ????? ?????????? ? ?????? ???????????? ???????? ? ?-???? ??
?-????. ????????? ?????? ?? ?????????, ?? ? ??????? ?????????? ?? ????? ????? ? ?????
??????????????? ???????. ???????????????? ????????????? ? ????????? ????????? ????? ?
# 28 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????. ???????????? ? ??????????? ????????? ????????????????? ?????? (II) ? ???????? ?????????
?????? ?????, ??????????? ? ????????? 446-550 ??, ?????????? 1-5 %, ??? ????????? ??? ???,
???????? ?????????????, ??? ??? ?????????? ????? ????? ? ????????????? ??????? ??.
??????????
? ?????????? ??????????? ?????? ???? ???????????, ??? ?????????? ????? ??????????
????? ??? ???????? ?? ????- ? ????????????????????? ?????? (II) ?????????????? ??????????? ??????? ??????????????? ??????? ?????????, ??? ?????? ????????? ? ?????????? ????????? ?????????? ?? ????? ?????? ? ? ??????? ??????????? ?????????? ??? ?????????????
?????????? ???????? ? ????????? 5-? ? 6-? ??????????????? ?????????. ??? ???? ?? ?????????? ????????????? ???????? ???????? ????????? ?? ????? ?????? ?? ???????????? ??????.
??????????? ????????? ????????? ??????? ????????????????????? ??????????? ?????????
???????????? ??????????? ?-???????? ??????? ? d-?????????? ????? ??????.
??????? ?????????? ?????? ??????????? ????????? ???? ?????????????????????, ?? ??????????? ???-????? ????????????????? ?????? (II), ?????????? ??? ????????? ???????????
?????????. ??? ???? ?????????? ???????? ????? ????? ? ????????????? ??????? ????????????????????? ????????? ? ????????? 446-550 ??, ??? ????? ????????? ??? ???.
?????????????
????? ???????? ????????????? ????????????????? ?????????????????? ?????? ???
?? ?????????????? ??????????? ????????????? ??????????? ?????????? ? ????????? ??????????? ? ?????????????? ?????????? ??? ?? ?????????????? ??????????? ?????????????
???????????????.
?????? ??????????
1. El-Far M.A., Pimstone N.R. Selective in Vivo Tumor Localization of Uroporphyrin Isomer I
in Mouse Mammary Carcinoma: Superiority over Other Porphyrins in a Comparative Study // Cancer
Research. 1986. Vol. 46. ? 9. P. 4390-4395.
2. Winkelman J. The Distribution of Tetraphenylporphinesulfonate in the Tumor-bearing Rat //
Cancer Research. 1962. Vol. 22. ? 5. Part 1. P. 589-596.
3. Musser D.A., Wagner J.M., Datta-Gupta N. Distribution of Tetraphenylporphinesulfonate and
Tetracarboxyphenylporphine in Tumor-Bearing Mice // Journal of the National Cancer Institute. 1978.
Vol. 61. ? 6. P. 1397-1403.
4. Berenbaum M.C., Akande S.L., Bonnett R. et al. Meso-Tetra(hydroxyphenyl)porphyrins, a
new class of potent tumour photosensitisers with favourable selectivity // British Journal of Cancer.
1986. Vol. 54. ? 5. P.717-725.
5. Bonnett R., McGarvey D.J., Harriman A. et al. Photophysical properties of mesotetraphenylporphyrin and some meso-tetra(hydroxyphenyl)porphyrins // Photochemistry and
Photobiology. 1988. Vol. 48. ? 3. P. 271-276.
6. ??? ?., ?????? ?.?. ????????? ???????? ? ????????. ?.: ???, 1979. ?. 2. 150 ?.
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Systeme durch Sauerstoff: Die Bildung aktiver, diffusionsfдhiger Sauerstoffmolekьle durch
Sensibilisierung // Naturwissenschaften. 1931. Vol. 19. ? 52. P. 1043.
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?.?. ???????. ???????????? ? ??????????? ????????? ????????????????? ?????? (II) ? ???????? ?????????
8. Kautsky H. Energie-Umwandlung an Grenzflдchen, VII. Mitteil.: H. Kautsky, H. de Bruijn, R.
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Zustandes des Sauerstoff-Molekьls // Chemische Berichte. 1933. Vol. 66. ? 10. P. 1588-1600.
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Molecular and Electonic Structure
of Benzoporphyrins with Iron (II)
at the Ground Spin State
Pavel O. Krasnov
Siberian State Technological University,
82 Mira, Krasnoyarsk, 660049, Russia
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041, Russia
Molecular and electronic structure of mono-, di-, tri- and tetrabenzoporphyrins with iron (II) was
carried out by quantum-chemical method of density functional theory B3LYP/6-31G(p,d). It was shown
that triplet electronic spin state is a ground state for them. The energy of quantum yield of this state
for all compounds excluding cis-configuration of iron-dibenzoporphyrin is enough to singlet oxygen
formation. The smallest wavelength in adsorption spectra of examined structures has a place in the
interval of 446-550 nm. These facts are preferable for practice use of iron-benzoporphyrin derivatives
for photodynamic therapy of cancer diseases.
Keywords: photodynamic therapy, photosensitizers, porphyrins, quantum-chemical calculations.
# 30 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 31-35
~~~
??? 661.177:62-63
????? ???????????????
?????????? ????????
?? ????????????? ?????
?.?. ???????????,?*, ?.?. ???????,
?.?. ????????, ?.?. ???????????,
?.?. ???????????, ?.?. ??????????, ?.?. ?????????
?
???????? ????? ? ?????????? ?????????? ?? ???,
??????, 660036, ??????????, ?????????????, 50, ???. 24
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
Received 24.12.2013, received in revised form 14.01.2014, accepted 10.02.2014
???????? ??????????? ??????? ????????-??????????????? ????????????? ?????????????
?????? ?????????. ?????????? ????????????? ?????????? ?????????? ? ??????????? ??????
????????????? ?????? ? ???????? ?? ????????? ????? (97,4 ± 3,2 ? 112,9 ± 3,5 ??????????????,
????????????????? ?????).
???????? ?????: ??????????, ????????, ???????????? ?????, ?????????????, ?????
????????????? ??????, ?????????????????? ????, ????????????????? ????, ?????????
?????, ??????.
??????????? ??????????????? ????????????? ????? ? ?????????? ? ?????????? ????????????? ??????? ?????????? ? ?????????????????? ????????????, ????????? ?????????? ?????????? ????????. ???????? ?????? ???? ???????? ???? ?????????????? ???????? (??????, ??????? ? ??.), ???? ??????????? (???????? ????????, ????????? ? ??.).
????????-?????????????? ???????? ??????????? ????????? ????????? ???????????????
???????? ???????? ?????????? ?? ????????? ? ??????????????? ? ????? ??????? ????????? (? ???????? 5-????????????????????? ? ??????????? (4-??????????????) ???????
? ?? ????? [1, 2]) ?? ????????? ? ?????????? ????????. ?????????????? ?????????????
????????? ????????? ? ?? ?????? ???????? ????????????? ??????? ? ???????? (2,5-????????????, ????????? ????? 119) [3, 4] ? ????????? ???????? (??????????????, ?????????????).
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: veta@icct.ru
# 31 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????? ????? ??????????????? ?????????? ???????? ?? ????????????? ?????
?????????? ?? ?????? ?????????, ?????? ?????????? ???????? ?????????????????????? ????????? ????????? ?????????, ?????? ???????? ???????????????. ??????? ????????, ??? ????????????? ??????????? ????????, ?? ??????? ????????? ?????????
???????? ??????????, ????? ???? ??????? ????????? ???????, ?? ??????? ????? ???????? 5-????????????????????? [5]. ???????? ??????????? ??????? 2-?????????????????
(???????????????? ????) ?????? ?????????????? ????????????? ?????? ??? 130 °C ???
????????? ?????????? ? ??????????????? ????????????? ? ?????????? ??? ????????? ?????
(?? = 110) [6].
??????- ? ????????????????? ????? ??????????? ?????????????? ??????? ????????????????? ? ? ???????? ???????????????? ?????????? ??? ?????- ? ???????????? [7], ??? ?
?????????????????? [8].
???? ????????? ?????? ??????????? ? ??????? ??????????? ? ?????????? ?????? ????????????? ?????? ? ????????? ?? ????????? ?????.
????????????????? ?????
? ?????? ???????????? ???????????? ????? (98 % ????????? ????????, Acros Organics),
???????, ?????- ? ???????????? ???????????? «???».
??? ??????????? ?????????? ????? ? ???????? ??????????? ????? ?????????????? ??????
??-80-3 ?????????? 0,768 ?/?? ? ???????? ????? ?????????? ????????????? ? 14,8 %, ????????????? ? 19,8 %, ??? ?????????????????? ??????????, ??????????????, ??????, ????????
? ??????.
?????????????????? ???? ????????????? ?? ???????? [7]. ???????????? ??????????
????????????? ?????? ? ???????????? (20 ? 37 ? ??????????????) ???????? ? ??????????
????? ??????? 250 ??, ?????????? ???????? ?????????????. ??????????, ??? ?????????????, ????????? ???????????? ?????????? ?????????? ????? (15?17 ?). ????? ????? ?????????
?? ??????? ???? ?? 50 0?. ????? ??????????? ????????? ???????????? ???????? ?????????
????????? ??? 30 ? ???????????? ? ?????????? ?????????? ? ??????? 1 ?. ?? ??????????
???????? ??????????? ????? ????????? ????? ??? ???????? ??????? ????????????? ??????,
?????? ??? ????????? ?????? ? ?????????? ??? ?????????? ?????????. ?????????? ????????? ?????? ?????????????????? ?????. ????? ??????????????????? ????? 45?55 % ?? ??????, ?????????????????? ????? 70?80 %. ?????????? ???????? ??????? ? ???????????????
????????? ?? ????? 95 %, ?? ?????? ??? ? ???.
????????????? ????????????? ?????? ????????? ????????? ? ????????? ??????????
???????, ??????? ????????? ? ???????? ? ????????? ? ???????? ????????????? ? ???????????? ???????? ? ??????? ??? ?????????? ????????????. ? ?????? ????????? 2 ?? ????????
????????????? ?????? (25 ???. %) ? ???????? ? ????????? ????????? ??????? (0,02 ????/?).
???????? ????????? ?? 180?200 °C ? ??????? 40 ???, ??????????? ? ??????? 2 ? ? ?????????
?? ????????? ??????????? ? ??????? 1 ?.
????????????? ?????????? ?????????? ????????? ???????? ???-?? (???????????-??????????? Agilent 7890a ? ????????????? ?????????? Agilent 5975?) ? ??? (?????????????? Bruker Avance III 600 MHz) ?????? ????????????? ??????????? ?????????????
???????? ?????? ?? ???. ????????? ????? ????????? ?????????? ??????? ? ??????????????
# 32 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????? ????? ??????????????? ?????????? ???????? ?? ????????????? ?????
??????? ????????? ????????????????? ??????? ?? ????????????? ????????? ??? ???????????
?????????? ?????, ?????? Waukesha CFR F1/F2 (???).
?????????? ? ??????????
??????????? ????????-??????????????? ????????????? ????????????? ?????? ???????? ?????????? ??????????? ?????????????: ??-??????, ??? ?????????? ? ???????????
???????, ??????????? ? ???????? ????????? ???????? ??? ???????????? ????? 100 °C [9],
??-??????, ?????????????? ?, ???????, ?????????????????? ?????????????. ??? ??????????? ???? ??????????? ????? ????????? ?????????? ???????????, ???????????????? ?
???????????? ???????????? ???????. ???, ??? 130?150 °C ?????? ????????????????? ?????
? ???????? ??????? ????????? 30?50 ???. % [6], ??? ?????? ? ??????????? ?????????????
????????????? [7].
???? ??????????? ??????????? ????????? ?????????????????? ????? ??????
????????-?????????????? ??????????????? ??????? ??? 180?200 °C. ??????????? ??????
????????? ????????? 35 % ? ????? ???????? ? ???? ?????????? ?????. ??????? ????????,
??? ?????? ??????, ??????????, ??????????? ????? ?????????? ????????????? ??????? ????????????????? ?????? ????? ??????????????????, ??? ???? ????????? ? ????????????.
??????? ??????????? ?????????? ?????????????????? ? ??????????????????? ??????
? ???????? ??????????????? ??????????? ???????. ????????? ????? ?????? ????????? ?? ???????? ?????????? ????? ?? ????????? ? ???????, ??????????? ???????? ????? ????? ???????
??????????? ? ???????? ? ????????? ?????? ???????? ?? ?????????
??? = (???-? * (m ? + m?) ? ???m?) / m ? ,
??? ?? ? ? ??? ? ????????? ????? ???????????? ???????? ? ??????? ??????????????, ???-? ?
????????? ????? ???????? ???????? ? ???????, m ? ? m? ? ????? ???????????? ???????? ? ???????.
? ????. 1 ???????????? ?????????? ??????????. ?????????? ????????? ?????????? ?????
??????? ????????? ? ????????????? ??????? (115,7 [10]) ? ???????? ???????? ????????????. ????????? ????? ?????????????????? ? ??????????????????? ?????? ????? ????????
97,4 ± 3,2 ? 112,9 ± 3,5 ??????????????.
?????????? ???????? ????????? ????? ?????? ?????? ? ?? ????? ???????? ????? ???????????? ?? ???? ??????????????? ??????????? ???????. ??????????? ????? ???????? ??????-
??????? 1. ?????????? ??????????? ????????? ????? (??) ??????????????????
??????????????????? (???) ??????, ? ????? ??????? ????????????????? ???????
????????
?????, ?
?????, ??
???
58,87
60,0
77,8 ± 0,5
97,4 ± 3,2
???
53,55
55,0
79,6 ± 0,5
112,9 ± 3,5
43,5
50
78,8 ± 0,6
113,9 ± 4,2
?? 500 ??
?? 500 ??
74,4 ± 0,5
74,4 ± 0,5
??????
??????
????????
?? ????????
# 33 #
?? ????????
(???)
?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????? ????? ??????????????? ?????????? ???????? ?? ????????????? ?????
?????? ????????, ?? ??? ???????? ? ???????? ?????????? ????????? ????????: ???????????
??????? ??????????? ? ?????????? ?????? ????????????? ?????? ?????????? 170 ? 180 °C
??????????????. ????? ???????, ?????????? ?????????? ????? ???? ????????? ???????? ???
???????? ?????????? ???????????? ???????? ?????? ?? ????????? ????? ? ???????????????
?????????????, ?.?. ? ??????????? «??????? ?????».
?????? ???????????? ??????????? ????? ??????????????? ???????????? ?? ?????????? ????????? ??????, ????? ? 13-03-00754.
?????? ?????????? ???????? ??? ?.?. ???????? ?? ?????????? ????????? ????????? ?????.
?????? ??????????
1. ?????????? ?.?., ?????? ?.?., ???????? ?.?., ???????? ?.?. ???????????? ?????????
????????-?????????????? ???????????? ????????? ? ??????????? ???????? ??? ?????????
???????????? // ????? ????????????? ?????. 2002. ? 2. ?. 5 ? 15.
2. ?????????? ?.?., ?????? ?.?., ????????? ?.?., ??????? ?.?., ????????????? ?.?.
???????????? ????????? ????????-?????????????? ???????????? ???????? ? ??????????? ???????? ??? ????????? ???????????? ? ????????? ???????? // ????? ????????????? ?????.
2002. ? 3. ?. 61 ? 69.
3. Roman-Leshkov Y., Barret C.J., Liu Z.Y., Dumesic J.A. Production of Dimethylfuran for
Liquid Fuels from Biomass-derived Carbohydrate // Nature. 2007. Vol. 447. P. 982-986.
4. Alonso D.M., Bond J.Q., Dumesic J.A. Catalytic conversion of biomass to biofuels // Green
Chem. 2010. V. 12. P. 1493?1513.
5. ??????????? ?.?., ??????? ?.?., ???????? ?.?. ?????????????? ?? ???????????????
????? // ?????????? ???????. ??????? ???. 2009. ?. 79. ? 7. ?. 595- 604.
6. Lange J.-P., Evert van der Heide, Jeroen van Buijtenen, Price R. Furfural ? A Promising
Platform for Lignocellulosic Biofuels // ChemSusChem. 2012. 5. 150 ? 166.
7. L. von Wissell, Tollens B. XXXIII. Ueber den Furfur- oder Furalkohol und einige Derivate
desselben // Justus Liebigs Annalen der Chemie. 1893. V. 272. Iss. 3. P. 291?306.
8. Zanetti J.E. Alpha Furfuryl Ethers // J. Am. Chem. Soc. 1927. 49 (4), P. 1065?1067.
9. ???????, ?.?., ????????? ?.?., ???????? ?.?. ??????????? ??????? ? ????????????
??????? // ?????? ?????. 1999. ?. 68. ? 1. ?. 80 ? 93.
10. ?????? ?.?., ????? ?.?., ???????? ?.?. ???????????? ??????????????? ????????.
?.: ?????, 1981. 224 ?.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????? ????? ??????????????? ?????????? ???????? ?? ????????????? ?????
New Gasoline Components
of High Octane Number Made
of Plant Raw Materials
Valery E Tarabankoa,b,
Mikhail Yu. Chernyak , Andrey A. Morozova,
Konstantin L. Kaygorodova, Yury N. Bezborodovb,
Nina F. Orlovskayab and Ivan V. Nadeykinb
a
Institute of Chemistry and Chemical Technology SB RAS
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041, Russia
a
The possibility of the acid-catalyzed furfuryl alcohol alkylation with butanol is demonstrated.
Preparative quantity of butyl furfuryl ether and propyl furfuryl ether are obtained and their research
octane numbers are measured (97,4 ± 3,2 ? 112,9 ± 3,5, correspondingly).
Keywords: biofuels, furfural, furfuryl alcohol, hemicelluloses, furfuryl ethers, propyl furfuryl ether,
butyl furfuryl ether, octane number, gasoline.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 36-41
~~~
??? 547.564.2 + 547.584
????????? ? ???????? ????? ??????????
2-????????- 5-???????-4,6?????????????????? ???????
?.?. ??????*, ?.?. ?????????,
?.?. ?????????, ?.?. ???????
?
????????? ???????????????
??????????????? ???????????,
??????, 660049, ??????????, ??. ????, 82,
?
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50/24
Received 04.06.2013, received in revised form 12.09.2013, accepted 22.12.2013
????????? ?????????? ?????????? ?????????????????? ??????? ? ????????????????????????.
????????????? ? ???????????????? ???????? ???? ?????????? 2-????????- 5-???????-4,6?????????????????? ???????, ?? ?? ?????? ???????? ??????????????? ?????????????
? ????????? ???? ? ???????????????? ????????. ??????? ???1?-?????????????
???????????, ??? ? ???????? ????-d6 ??? ?????????? ????????? ????????? ? ????????
?????.
???????? ?????: ?????????, ??????????, ????????????? ?????????????, ???????????
???????, ???-?????????????, ??????????.
???????????? ??????? ???? ???????? ????????????? ????????????? (I), ??????????
????????????? ??????????? ? ????-?????????? ?? ????????? ? ????????????? ??????
[1-3]. ??? ????????????? ???? ????????????? ?? ????????????? ???????????? (II) ? ??????? ??????? ??????????????? ???????????? (???. 1) [4].
? ?????? ????????? ????????????? ???????, ?????????? ???????????????????? ??????????, ????? ??????????? ????? ????????????? ???????????? [5].
??????? ????? ????????? ?????? ????? ????????? ????? ??????????? ?????????????
?????????????? ???????? ????????, ?????????? ??????????? ?????? ?????? ?????????????, ? ???????? ?? ???????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: tovbis@bk.ru, natali_fedorova_a@mail.ru
# 36 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ????????? ? ???????? ????? ?????????? 2-????????- 5-???????-4,6?
OH
OH
ROOC
COOR
ROOC
COOR
H2
H 2O
Pd / C
H 3C
H 3C
CH3
I
CH 3
II
NO
NH 2
R = Me, Et, Pr, Bu
???. 1
????????????????? ?????
1. ??????
?????????
????????
?????
??????????
2-????????-5-???????-4,6?????????????????? ??????? ? ????????? ???????? ??????????????
???????? ????-?????????? (-H, -Br, -Cl, -CH3) ????????? ?????????????????? ???????
???????? ??? ?????????? ??????????? ????? ?????????????????? ??????? ? ???????????????? ????????? ? ????????? ?????? ? ??????? 24 ? ?? ???????? [6].
?????????? ????????? ?????????????????? ??????? ????????? ?????????? ? ????????????????????????. ??? ????? ?????????? 0,25 ????? ?????????? ????? ? 2 ?? ???????????
????????? ??????, ????????? 0,25 ????? ??????????????????????? ? ????????? 0,5 ????? ????????? ?????????????????? ??????? ? 0,5 ?? ????. ?????????? ????? ??????????? 6-48 ?
(? ??????????? ?? ???????????) ??? 18-20 °?. ?? ??? ????? ??????? ????? ???? ?? ??????????
?? ????????. ???????? ???? ???????? ??????????? ??????????? ??????????? ????? ?? ??????????. ??????????? ????-??????? ????????? ???????? ???????? ????? ??????????????,
????????????????????? ?? ???????, ?????? ? ??????? ??? Na2SO4. ??? ????????? ????????
?????????????? ? ????????? ???? ?????????? ???? ?????????? ? ??????????? ??????????
???? ? ?????????? ???????????? ??????? ???????? (1:3).
???????? 2-????????-5-???????-4,6-?????????????????? ???????
????? ??????? 6 ?. ????? 0,071 ? (74 %), ??????-?????? ?????????. ? ??-??????? ?
??????? ??????? ??? ????????? ?????????? ?????????????? ?? ????? ????? 248 ? 397 ??
(? = 20260 ? 17480). ? ??-??????? ???????????? ??? ??????? ?????? ??????????, ???????????
??? ????????? ????????? ???????????? ??????, ? ??????? 1627 ? 1648 ??-1. ????-??????, m/z
(I???., %): 119(6) C6H5NCO; 91 (11) C6H5N; 77 (19) C6H5; 51 (7) C4H3; 39 (18) C3H3. ?????? ??? 1?
?, ?.?.: 2.24 ? (3H, CH3), 2.45 ? (3H, CH3), 7.10 ? (2H????.), 7.35 ? (4H????.), 7.65 ? (4H????.), 10.38 ??.?
(2H, 2-NH), 14.19 ? (H, NOH).
??(?-??????????) 2-????????-5-???????-4,6-?????????????????? ???????
????? ??????? 24 ?. ????? 0,036 ? (32 %), ??????-?????? ?????????. ??-?????? ? ???????
?????., ?? (?): 255 ? 397 (35160 ? 25840). ? ??-??????? ????? ???????????? ??? ?????? ??????????
???????????? ????? ? ??????? 1602 ? 1651 ??-1. ????-??????, m/z (I???., %): 153(7) ClC6H4NCO; 125
(12) ClC6H4N; 111 (11) ClC6H4; 76 (7) C6H4; 50 (32) C4H2; 38 (47) C3H2.. ?????? ??? 1?, ?, ?.?.: 2.24 ?
(3H, CH3), 2.43 c (3H, CH3), 7.41 ? (4H????.), 7.68 ? (4H????.), 10.54 ??.? (2H, 2-NH), 14.26 c (H, NOH).
# 37 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ????????? ? ???????? ????? ?????????? 2-????????- 5-???????-4,6?
O
O
O
RHN
O
NHR
O
1) KOH, (C 2H 5OH), ????
ДМСО
O
OH
O
RHN
NHR
2) HCl, H 2O
H3C
H3C
CH3
CH3
NO
NOH
R=C6H5, ?п -C6H4Cl, ?п -C6H4Br,
?п -C6H4CH3
???. 2
??(?-??????????) 2-????????-5-???????-4,6-?????????????????? ???????
????? ??????? 48 ?. ????? 0,054 ? (37 %), ??????-?????? ?????????. ??-?????? ? ??????? ?????., ?? (?):257 ? 397 (38428 ? 29476). ? ??-??????? ???????????? ??? ?????? ??????????
???????????? ????? ? ??????? 1603 ? 1650 ??-1. ????-??????, m/z (I???., %): 197 (19), 199 (19)
BrC6H4NCO; 169 (100), 171 (97) BrC6H4N; 90 (28) C6H4N; 76 (8) C6H4; 50 (45) C4H2; 38 (93) C3H2..
?????? ??? 1?, ?, ?.?.: 2.23 ? (3H, CH3), 2.44 c (3H, CH3), 7.54 ? (4H????.), 7.63 ? (4H????.), 10.54 ??.?
(2H, 2-NH), 14.27 c (H, NOH).
??(?-????????) 2-????????-5-???????-4,6-?????????????????? ???????
????? ??????? 24 ?. ????? 0,071 ? (68 %), ??????-?????? ?????????. ??-?????? ? ???????
?????., ?? (?): 252 ? 397 (26000 ? 22900). ? ??-??????? ????? ?????????? ????? ????????????
??? ??????????? ?????? ?????????? ???????????? ????? ? ??????? 1605 ? 1644 ??-1. ??????????, m/z (I???., %): 133 (5) CH3C6H4NCO; 105 (90) CH3C6H4N; 91 (9) CH3C6H4; 65 (10) CH3C4H2; 53
(8) CH3C3H2; 41 (6) CH3C2H2. ?????? ??? 1?, ?, ?.?.: 2.24 ? (6H, 2-CH3), 2.27 ? (3H, CH3), 2.42 c
(3H, CH3), 7.14 ? (4H????.), 7.53 ? (4H????.), 10.28 ??.? (2H, 2-NH), 14.15 c (H, NOH).
2. ??????? ?????? ??? 1?, ??, ??- ? ????-????????
??????? ??? 1? ???????? ?? ??????? Bruker Avance III 600 (600.13 ???) ? ????? ????-d6
(???????????? ???????????? ????? ????????????? ??????????? ?? ???).
????-??????? ?????????????? ?? ??????? Finnigan MAT 8200.
??-??????? ?????????? ?? ???????????????? «Helios» Omega ? ?????????? ?????????
190-1100 ??, ??????????????? ???????? 0,3-3 ?, ? ????????? ??????? 1 ??.
??-??????? ???????? ?? ??-?????????? ????? «SpecTRA TECH» ?????? «InspectIR» ??
???? «?? ?????» ? ???????????????? «Impact 400».
?????????? ? ??????????
??? ????????? 2-????????-5-???????-4,6-?????????????????? ??????? ???? ????????
??????? ?? ???????, ?????????? ?? ???. 2. ??? ?????????????? ???????? ???? ???????? ????# 38 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ????????? ? ???????? ????? ?????????? 2-????????- 5-???????-4,6?
???????, ?????? ?? ??????? ????????? ? ????????????????? ?????. ??? ?????, ??? ???????
???????? ????? ???????????? ????? ????????????? ?????????????? ???????? ??????????.
???????????? ???? ? ????-???????? ?? ?????????? ??-?? ???????? ?? ??????? ?? ?????????.
? ??-???????? ?????????? ??????? ???????? ?? ???? ???????? ??????? ?????? ?????????? ???????????? ????? ? ??????? 1602 ? 1651 ??-1. ?????????, ??? ??? ?????????? ??????????? ??????? ?????? ?????????? ???????????? ?????? ????????? ? ??????? ???????
??????, ??? ?????? ?????????? ???????????? ?????? ??? ??????????????? ?????? ??????????? ??????? (1650-1675 ? 1725-1740 ??-1) [2], ??? ??????????? ? ??????? ??-????????????? ???
???????????? ????? ??????? ?????? ? ?????? [7].
? ??-??????? ? ??????? ??????? ??? ????????? ??????????, ??????????? ??? ??????????????, ?? ?????? ???? 248 ? 397 ?? (? = 20260 ? 17480 ??????????????).
? ??? 1?-???????? ???? ?????????? ???????????? ??????? ???????? ????????? ?????
?????????????? ?????? ? ??????? 2,23-2,45 ?.?., ??????? ???????? ????????? ????? ? ???????
7,10-7,68 ?.?., ??????? ???????? ??????????? ? ??????? 10,38-10,54 ?.?. ? ??????? «??????»
???????? ? ??????? 14,15-14,27 ?.?. ????????? ???????? ? ??????? ????? ??????? ???? ?????
????????? ???, ??? ??? ????????? ????????? ? ???????? ?????. ????? ???? ????????, ???
????????????? ????????????? ?? ?????????????? ???????? ????????? ? ???????? ?????
????????? ? ???????????????? ????? [2, 3].
??? ????? ??????????????, ?????????? ?????????????? ? ???????????? ???????? ?
???????? ????? ???? ??? ????, ??? ??????? ????????? ????? ? ???1?-??????? «???????»,
?. ?. ???? ??? ??????? ? ?????????? ??????????????. ??? ?????? ??????????? ???, ??? ???? ??
????????? ????? ?????????????? ?????? ????????????? ? ???-????????? ?? ????????? ? ???????? ??????, ? ?????? ??????????? ? ????-?????????, ??????? ????????? ?????? ?????????? ????????????????. ??????????? ?????????? ???????????? ? ????-???????????????????
???????????? ?? ???. 3.
??? ?????? ?? ??????????????? ???? ?????????????? ? ????????? 2-????????-5-???????4,6-?????????????????? ??????? ???????? ??? 1?-??????, ?????????? ? ????-d6 (???. 4).
? ??? 1?-??????? ????? ??????? ???????? ????????? ????? ?????????????? ?????? ?
?????????? ??????? 2,24 ? 2,45 ?.?., ??????? ???????? ????????? ????? ? ?????????? ??????? 7,10-7,65 ?.?., ??????? ???????? ??????????? ? ?????????? ??????? 10,38 ?.?., ?????? ?
??????? 14,19 ?.?. ??????????? ????????? ??????? ???????? ??????.
???. 3
# 39 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ????????? ? ???????? ????? ?????????? 2-????????- 5-???????-4,6?
???. 4. ??? 1?-?????? ????????? 2-????????-5-???????-4,6-?????????????????? ???????
????? ???????, ? ?????????? ???????????? ??????? ???????? ????? ??????????? ????????? 2-????????-5-???????-4,6-?????????????????? ???????. ???????? ?? ???????? ?
?????????????? ??????? ??? 1?, ??, ??-????????????? ? ????-????????????? ? ????????, ??? ? ???????? ????-d6 ??? ???? ?????????? ??????????? ?????????? ?????????????-??????????????????? ????????? ??????? ? ??????? ????????? ?????????.
?????? ????????? ? ?????? ????????? ???????????? ??????????? ? ????? ??.
?????? ??????????
1. ?????? ?.?., ?????? ?.?., ?????? ?.?. ?????? ?????????????? ??????????? ???????????-?????????????? ?????????? ? ???????? // ?????? ???????????? ?????. 1978, 14. 2375-2380.
2. ????? ?.?., ????????? ?.?., ?????? ?.?. ??????????? ???????????????-????????????
????-?????????????? // ?????? ???????????? ?????. 2007. 43. 545-548.
3. Alemasov Yu.A., Slaschinin D.G., Tovbis M.S., Kirik S.D. X-Ray Diffraction and
Spectroscopic Veriication of Dimerization in Hexasubstituted Para-Nitrosophenols // Journal of
Molecular Structure, 2011. 985. 184-190.
4. ???????? ?.?., ?????? ?.?., ???? ?.?., ????? ?.?., ????????? ?.?. ??????????????
???????????? ????????????? ?-?????????????? // ?????? ???????????? ?????. 2010. 46.
527-529.
5. Eiden F., Leister H.P., Mayer D. 5-Aminoacetamido-4,6-dimethyl-2-hydroxy-isophtals?urediethylester: Synthese und Untersuchung antiarrhythmischer Eigenschaften // Arzneimittel-Forschung.
1983. 33. 101-105.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ????????? ? ???????? ????? ?????????? 2-????????- 5-???????-4,6?
6. Besthorn E., Garden E. Ueber die Einwirkung von Acetondicarbonsдureester auf Anilin //
Chemische Berichte. 1903. 33. 3439-3443.
7. ????????? ?.?. ?? ??????? ???????? ??????? ???????????? ??????????. ??????????
????????? // ??? ????? ?.?. ??????????. ?., 2012. 54?.
Preparation and Properties of new Arylamides
of 2-Hydroxy-5-Nitroso-4,6-Dimethylisophtalic Acid
Natalia A. Komara, Dimitri G. Slaschinina,
Ivan V. Petersonb and Mikhail S. Tovbisa
a
Siberian State Technological University,
82 Mira, Krasnoyarsk, 660049 Russia
b
Institute of Chemistry and Chemical Technology
Siberian Branch of the Russian Academy of Sciences
50/24 Akademgorodok, Krasnoyarsk, 660036 Russia
The cyclization of arylamides acetonedicarboxylate with isonitrosoacetylacetone was carried out.
Arylamides of potassium salts of 2-hydroxy-5-nitroso-4,6- dimethylisophtalic acid were synthesized
and characterized. Relevant nitrosophenols in a free form were preparated from these salts and
their properties were investigated. 1H NMR spectroscopy showed that DMSO-d6 solutions of these
compounds are entirely in the oxime form.
Keywords: arylamides, cyclization, persubstituted nitrosophenols, isophtalic acid, NMR spectroscopy,
tautomerism.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 42-53
~~~
??? 661.183:665.7.032.5
????????? ?????????? ?????????
?????????? ???????????? ?????????? ?????
? ???????????? ????????
?.?. ?????????,?*, ?.?. ???????,
?.?. ???????, ?.?. ?????????,?
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
?
???????? ????? ? ?????????? ?????????? ?? ???,
??????, 660036, ??????????, ????????????? 50, ???. 24
Received 10.11.2013, received in revised form 09.12.2013, accepted 04.02.2014
??????? ?????????????? ??????????? ????????? ????????? ???????????????? ??????????,
????? ?????, ????????? ? ??????? ??? ???????? ??????? ??????????? ??????, ??????????? ?
????????????????? ????????. ??????????? ???????????? ???????? ????????? ??????????
?????????. ??? ???? ????? ????????? ????? ??????????? ?????? ??????????? ??????? ?????????
???????????? ?????????? ????????? ? ??????? ???????? ???????????? ? ?? 2000?2900 ?2/?.
???????? ?????: ?????????? ???????, ?????????, ????????, ????? ?????, ?????????, ??????,
?????????? ?????????, ???????? ?????????.
????????
???????? ?????????? ????????? (???) ????????? ????? ??????? ??????????? ?????????? ?????? ???????????? ? ????????? ??????????????? ????????? ?????????? ? ?????? ? ???????????? ??????. ??????????? ?????????? ???????? ?????????? ?????????? ? ???????? ????????? ??? ?????????????, ?????????????, ??????????? ??? ????????????? ? ?????? ????????
?????, ???????-?????????? ??????????? ?????????? ? ?.?. [1, 2]. ????????????? ???????????
??? ? ??????? ????????????? ????????????? ? ?????????????? ?????????? ??? ???????????
???????????? ? ??????????????? ??????, ??????????? ???????????? ???????? ??????????? ?
????????? 0,1-103 ?2/? ? ??????? ??? ?? ???????? ?? ????? ??????, ? ????? ??????? ??????????? ???? ????????? ????????, ?????????? ???????, ???????, ??????? ???????, ?????????, ??????????? ? ?????? ????????? [1-3].
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru
# 42 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
? ????????? ????? ????????? ??????? ???????????? ???????? ?????????? ??????????
?????????? ????? 1 ??? ? ? ??? [1, 2]. ?????????? ??????? ???????????? ? ?????????? ???????????? ??? ???????????? ??? ????, ??? ??? ?? ????????? ????? ?????????????? ????? ????
?????????????????? ?????: ????????? [4, 5], ???????? ? ????? ???? [6, 7], ????????? ????
???????????????????? ??????? [8], ???? [2], ?????????? ????????? [9], ?????? ? ???????????? ???????????? [10], ? ????? ????????????????? ???????????? ? ??????? ?????? [11].
??? ????????? ???, ??????????? ? ???????? ??????????? ? ????????? ?????????????,
?????? ???????????? ?????? ?????????? ??? ?????????? ????????? [1, 2]. ????????? ??? ?
?????????????? ?????????? ????????? ???????? ????????? ??????: ?????????? ????? (?????????, ?????????, ????? ? ??.); ??????? (?????????????? ??? ??????? ?????????? ??? ??????????? 550?1000 °?; ????????? (?????????????? ? ??????????? ??????????, CO2 ??? ????????
???? ??? 700?1000 °?).
????????? ??? ??????? ??????????????? ????????? ???????? ?? ???????? ? ????????
???????? ?????????? ??????? ? ??????????? ????????????? ? ???????? ????? ??? ? ??????????? ????????????? ??????????. ????????????? ????????? ????? ? ??? ?????????????? ???
????????? ????????-???????? ??? ????????????-????????????????? ????????????? (ZnCl2,
Al2O3, H3PO4, ????????? ??? ?????? ???????? ???????? ? ??.) [1, 2, 12]. ???????????? ?????????? ????????????? ????????????? ??????????, ??????????? ?? ?????????? ???????? ????????, ??????? ????????, ??????? ? ?????? ??????????? ??? ????????????? ???????????? ?
????????? ??? ????????????, ??? ???????, ???? 700 °?. ? ????? ?????????? ??? ? ????????
???????? ??????????.
??? ???????????? ????????????? ??? ?????????? ?????? ?? ?? ??????????? ? ?????????? ???????????????, ????? ??? ???????? ???????? ???????????, ????? ? ?????? ???, ????????????? ??? ?? ????????.
? ?????? ???????????? ?????? ?? ???????????? ???????? ?????????? ??????????, ?????????? ?????????? ???????????? ????????? ????? ?????????? ?????????????????? ?????:
??????????, ????? ?????, ???????????? ????????.
1. ???????? ?????????? ????????? ?? ??????????
???????? ?????????, ?????????????? ????????????? ?????????? ? ???????????? ?????????? ?????????, ???????? ?? ?????? ??????????? ???????????, ?????????? ????? ???????????? ?????? ????????? ??????? ????? ??? ??2 ??????????? ???????????? ????????????. ????????????? ???????????? ?????? ????????? ?????????? ??????????????????? ? ??
???????? ?????????? ????????? ?????????? ???????? ???????????? ?????????? ????????? ??
?? ?????? [7, 13]. ??? ????????? ?????????? ????????? ? ???????? ?????????????? ???????????????? ????????????? ???????? ?????????? ????????? ????????? ?????????? ????? ?
??????? ???????????. ??? ???? ?????????? ?????? ????? 50 % ?? ????????? ???? ????????? ??
???? ??? ?????????.
??????? ???????? ? ???, ??? ?????????????????? ?????????? ??????????? ?????????
(????????, HClO4 ??? HNO3) ??????????? ??? ??????????? ??????????? ??? ???????????
?????????? ????????? [14-16].
# 43 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
? ?????? ?????? ??? ?????????? ????? ???????? ????????? ??? ?? ?????????? ? ???????????? ?????????? ????? ? ?????????? ? ??????????? ???????? ?? ?????????? ???????????
? ??????????? ??????????? ?????????. ??????????? ??????? ??????? ?????????? ??????????? ???????????? ????????? ? ???????? (HNO3, H2SO4, LiOH, NaOH, KOH) ??????????
????????? ????????????? ?????? ? ??????? ?? ?????????? ?????????????? ? ???????????
???????? ???????? ?????????? ?????????? (???), ?????????? ??????????? ?????????? ???????????????? ???????? [16, 17].
??? ???????????? ?????????? ?????????? ???? ???????????? ?????? ?????????????
?????????, ??????????-????????????????, ???, ????, ??? ? ?????-???????????????.
??????????? ?????????????? ???????? ???????????? ?? ??????? ????????? ????? ??? 77 ? ?
????????? ??2 ??? 273 ?.
???????????, ??? ??????????????? ?????????? ??????????? ?????????? ?????? ???????
? ?????? ?????? ??????????? ???????? ?? ?????? ? ?????????. ????????????? ??????? ??????? ???????? ?????????????? ????????? ? ???????????? ?? 1000 ?2/?, ?????? ?????????? ?
?????????????? ?????????????? ??? ?? ????????. ??????? ??????? ????????? ??????????
?????? ?????? ? ??????? ??????, ?????????????? ?? ?????? ??????????? ? ??????????? ??????????? ????? ?????????? ???? ??? ?????????? ?? ????????. ??????????????? (?????????
?????) ?????????????? ??????????? ??????????? ????????? ??? 900 °? ???????? ? ??????????? ??? ? ???????? ???????? ??????????.
???, ?????????? ?????????? ?????????? ?????????? ???????????? ?????????, ?????
???????? ????????????? ?????????. ????? ??? ? ?? 0,133 ?? 0,253 ??3/?. ?????? ????????
??????????? ?? 0,7 ?? 2,5 ??, ? ?? ??????? ?????? 0,94 ?? (???. 1).
????????????????? ? ???????????????? ???????? ????? ??????? ??????????? ??????? ?? ???? ? 71 %. ???????, ??? ??? ??????????? ???????????? ????????? ??? ????????
?????????? ????? 60 %. ????? ??? ?? ????????????????? ???????????? ????????? ????????? ????????? 84 % ?? ???? ????????? ?????????, ????? ??? ? ???????????? ???????? ??????????? ????????? ???????? ?? 30?50 % ????? ????????? ?????????. ??????? ????? ???????????,
?
?
?
? ??
????? ???, ??3/?
0.3
0.2
0.1
0.0
0
8
16
24
?????? ??? (?)
32
40
???. 1. ????????????? ???????? ?? ???????? ? ???????? ?????????? ?????????, ??????????
??????????????? ????????????????? ?????? ?????? ? ??????? ?????? ????????? (?? ?????? ??
????????? N2 ??? 77 ?)
# 44 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
??????? 1. ?????????? ?????????????? ???????? ???, ?????????? ?????????? ?????????? ?
??????????? ??????? (??????????? ????????? 800 °?)
????????
???????????, ?2/?
235
????????? ?????
???, ??3/?
0,15
????????/NaOH
1174
0,76
0,25
2,6
????????/KOH
3240
1,77
0,20
2,2
???????
????????/LiOH
????? ????????,
??3/?
0,10
??????? ??????
???, ??
1,0
??? ????????????? ?????? ?????? ???????? ???????? ????????? ????????? ?? ??????? ?????????? ? ??????????????? ?????? ??????????? ?????????.
??? ?????????? ????? ??????? ??????? ???????????? ?????????? ?????????? ??????????? ???????? ????????? ?????????? ???? ????????????? ?????? ? ??????? ? ???????????
??????????? ?????, ?????? ? ?????. ? ?????????? ??????????? ???????????? ???????? ????????????????? ???????????, ??????????? ?????????? ?????????????? ?????????? ?????????? ?????????? ? ???????? ????????? ? ????????????? ??????, ? ????? ? ????????? ????????
?????????.
???????????, ??? ???????????? ??????????? ??????????? ?????????? ? ???? LiOH <
NaOH < KOH. ??????????? ?????? ???????? ?????????? ?????????? ????????? ?????????? ???????????? Li, Na, K (???????????, ??????????? ?????????, ??????????? ?????),
??????????? ???????? ???????????? ?????????? ????????? ? ??????? ???????? ????????????.
???????? ???????????? ???????? ???????? ??????????? ??????????? ????????? ?????????? ??? ????????? ????????? ? ??????????? ?????????? ????? (???????? ???????? ???????????
????????? ????? 3000 ?2/?, ????? ??? ? 1,77 ??3/?, ??????? ?????? ??? ? 2,2 ??). ??? ?????????
????????? ? ??????????? ?????????? ?????? ???????? ??????????? ?????????? ??????????
?????????? ????????? 1500 ?2/?, ? ??? ??????? ????????? ?????/???????? ? 240 ?2/?, ??? ??????? ??????? ??? 2,6 ? 1,0 ?? ?????????????? (????. 1).
????? ???????, ? ?????????? ??????????? ???????????? ??????????? ?????? ????????
?????????? ?????????? ????????? ?????????? ???????????? ????????? ? ???????? (???????????, ??????????? ?????????, ??????????? ?????), ??????????? ???????? ???????? ?????????? ????????? ? ??????? ???????? ????????????. ?? ????????? ???? ?????? ???????????
????? ??????? ????????? ??? ?? ?????????? ? ???????? ???????????? ?? 240 ?? 3000 ?2/? ?
??????? ???????? ??? ?? 1,0 ?? 2,6 ??.
2. ???????? ?????????? ????????? ?? ????? ?????
?????????????????????? ????? ???? (??) ? ???????????? ??????? ? ????????? ???????? ???????? ??? ????????? ???????? ?????????? ??????????. ??? ????? ?????? ??????????
?????? ???????? ????????? ????? ?????, ??????????? ???????? ??? ? ?????? ????????
????????????? ?????????? [18-20]. ????? ??? ????? ????????? ??????? ????????????? ?
??????? ????????????????? ????? [21], ??? ?????? ????????? ?? ????????????? ? ?????????????????? ?????????.
# 45 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
? ?????? ?? ??????? ????? ????? ???????????? (???) ? ?????????? (????) ????????????? ??????? ???????????? ???????? ????????? ?????????? ??????????, ?????????? ??????? ???????? ?????????.
??????? ????????? ????????? ??????????? ????????? ??????? ?????????? ????????????? ?? ??????? 1-2 ?? ?? ? ??????????? ????? ??? ??????, ???????????? ? ??????? ????, ? ??????? ??????????? 1:1-1:7. ????????? ????? ????????? ? ????????? ???????? ? ????????? Ar.
????????????? ????? ??????? ?????????? ?? ????????? 5 °?/??? ?? ????????? ???????????
?? 600-800 °? ? ??????????? ?????????????? ????????? ? ??????? 1 ?. ?????????????? ???????? ????? ????????? ?? ?????????????? ???????? ?????? ?? ??????????? ???? ??? 105 °?.
?????????????? ???????? ????????? ??? (???????? ??????????? S???, ????? ????? ???
V??? ? ??????? ??????? ???) ????????????? ??????? ??? ?? ????????? ????? ??? 77 ?. ??????????? ???????? ?????????? ??? ?? ????????? ? ???????? ?????????? ??? 77 ? ? ???????? ?2 6,5 ??? ????? ??????????????? ?????????? ???????? ??? ???????? ??? ???????????
300 °? ? ??????? 2 ?. ????????? ???????? ???????????? ?? ????????? ??????? ???????????
5 °? /??? ?? 400 °?.
?????????? ??????-??????????? ???????????? ????????? ????????? ????? ????? KOH
? NaOH ??? 600 °? ????????, ??? ???????? ??????????? ? ????????? ????? ??? ??????? ??
??????? ???????????? ?????? ? ?? ?????????? ? ???????? ?????. ???????? ??????????? ?
????? ??? ?????????????? ???????? ??? ????????? ????????? ??? ??????????? ?????
?????/??? 1:5 (S??? = 1565 ? 2/?, V = 0,78 ??3/?). ??? ?????????????? ??? ? NaOH ??????????
??????????? ???????????, ?????? ?????????? S??? ? V??? ????????? ???? (1240 ? 2/? ? 0,56 ?3/?
??????????????).
??????????? ??????????? ?????????? ? ??? ????????? ????. ?????? ??? ?????????
???? ???????? ??? ? ????????? ????? ?????? ???????? ???????????? ? ????????? ??????? ???: 1273 ?2/? ? 0,611 ??3/?; 808 ?2/? ? 0,32 ??3/? ?????????????? ??? ??? ? NaOH.
???????????, ??? ? ??????????? ??????????? ????????? ? 600 ?? 800 °? ? ??????????
????????? ????????????? ?????? ????? ????? ??? ? ???????? ??????????? ??? ??????????. ?? ???. 2 ???????????? ?????????, ?????????? ??????????? S??? ?? ??????? ????
?????????? ??? ???, ?????????? ?????????? ????? ??? ? NaOH, ?????? ? ????????? ??????????? 1:1 ? 1:7.
??? ???? ?????? ??/?????? ?????????? ?????????? S??? ? ?????? ??????????? ?? 1:1 ??
1:5, ??? ???? ??? ???????? ???/??? ? ????/??? ??? ???????? ????????? ??????????? ???????? ? 2680 ? 2250 ?2/? ??????????????. ? ??????????? ???????? ??? ?????, ???????????????? NaOH, ???????? ??????????? ?????????? 1259 ?2/?. ??????????? ?????????? ??????????
???????? ? ????? ?????? ?? ??????????? 1:7 ???????? ???????? ???????? ???????? ??????????? ???.
???????? ???????? ??????????? ? ?????????? ?????????? ??????????, ?????????? ?? ??,
?????????? ?? ??????? ??????????? ??????????, ? ????????? ? ???????? (????. 2). ???????????, ??? ?????????? ???????? S???, V??? ? ???????? ??????? ??? ??? ?? ?? ???????? ? ?????
??????????? ??????? ?? ????????. ??? ????? ?? ?????? ? ????. 2, ? ??????????? ???????? ??????????? ? ?????? ?????? ??? ?????????? ??????????? ??????? ?? ????????. ????????????
???????? (2,99 % ???.) ???????? ??? ??? ??? ??????????? ?????/??? = 1:5.
# 46 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
3000
2500
S???, ?2/?
2000
1500
1000
500
??? + ???
???? + ???
0
1:1
??? + Na??
1:3
1:5
??????????? ??/??????
1:7
???. 2. ??????????? ???????? ??????????? ???, ?????????? ? ????????? ?????? ??? 800 °?, ??
????????? ??/??????
??????? 2. ?????????????? ???, ?????????? ???????? ?????????? ????? ????? ? ????????? ??????
??? 800 °?
???????
???/???
???????????
?????/??????
1:3
????????
???????????, ?2/?
2134
????? ???,
??3/?
0,92
??????? ???,
??
1,98
??????? ?2, %
????.
2,58
???/???
1:5
2680
2,12
3,00
2,99
???/Na??
1:5
1259
0,72
2,55
1,35
????/???
1:3
2003
0,86
2,76
2,32
????/???
1:5
2250
1,45
2,92
2,64
???????????, ??? ?????????????? ????? ????? ??? 800 °? ? ??????????? ??? ???????????? ?????? ???????? ??????????? ??? ?? ????????? ? Na??.
????? ???????, ??????????????? ????????? ????? ????? ? ??????????? ???????????
???????? ???????? ????????? ???????? ???????????? ?????????? ??????????-???????? ????????? ? ??????? ???????? ???????????? (?? 2700 ?2/?) ? ???????????? ??????? ??? (1,5?
2,1 ??3/?). ??? ???? ???????? ???????????? ??????????? ???????? ?? ???????? (?? 3 % ???.)
???????? ???, ?????????? ??? ????????? ?????? ???? ? ???.
3. ???????????? ?????????? ?????????,
?????????? ???????? ?????????? ????????? ???????
???????????? ???????? ?????????? ?????????? (???) ????? ????????????? ??? ????
?? ????????????? ???????? ?????????? ??????? ????????????? ? ??????????? ?????????.
?????? ??????? ??? ???????? ????????????? ????????, ??? ??????? ?????????? ???????
????? ???????? ? ????????? <1,0 ??. ??????? ????? ??? ???????????? ??????????? ????????? ??????????? ? ??????????? ??????? ????????????????? ?????, ? ????? ??????? ???
# 47 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
???????????-??????? ????????, ??? ?????? ????????? ??? ????????????? ? ?????????????????? ????????? [21].
?????? ???????????? ??????? ????????? ??? ? ?????????????? ??????????? ?????????
?????????????? ??? ????????? ????????????? ?????????? ??????????. ??? ?? ????????????? ????? ???? ???????????? ???????? ?????????, ?????????????? ???????? ?????????????
????????? [22].
? ?????? ??????? ??????? ??????? ???????? ????????? ?? ???????????? ???????? ????????? ? ??????????? ??????? ?????????? ??????????, ?????????? ?? ????????? ?????? ? ???????????? ???????.
? ???????? ????????? ????? ???????????? ????????-????? ?????? (??????? 0,25-1,0 ??)
????????? ?????? (??), ????????? ????? (??) ? ??????????? ?????? ????????????? ???.
??????? ??? ???????? ?? ????????? ????????: ???????????? ????? ?????? ? ?????????? ?????, ?????? ? ???????? ????????? 1:1 ? 1:4, ????????? ? ?????????????? ?????????
???????? ? ???? ?????? ?? ????????? ??????? 5 °?/??? ?? ??????????? 800 °? ? ???????????
??? ???????? ??????????? ? ??????? 1 ?. ????? ????????????????? ??????? ????????? ??
????????? ???????????, ?????????? ? ???????? 0,5 ? HCl ? ???????????????? ????? ?? ??????????? ????? ? ?????????? ? ????????? ????? ??? ??????????? 105-110 °? ?? ???????????
????. ????? ??? ????????? 5-8 ???. % ? ??????? ?? ???????? ?????????.
? ?????????? ??????????? ???????????? ???? ???????????, ??? ???????? ???????? ??????????? (S??.) ? ??????????? ???????? ?????????? ??? ???????????? ???????? ???????????? ????????? ? ?????????? ?????????/??????. ???????? ????????? S??. ??? ????????
??????? ????? ?????????/??? ?????????????? ???????, ??????????????? ? ????. 3. ? ????
?????????????? ????????? ???????????????? ???????? ???????????? ???????????? ?????????, ??????? ??? ????????, ??? ???? ?????????? ??? ? ?????.
?? ?????? ? ????. 3 ???????, ??? ???????? ??????????? ???, ?????????? ?? ????????? ??????, ??? ????? ???? ?????? ? ????? ?? 1 ?? 4 ????????????? ????? ??????? ? ? 880 ??
2050 ?2/?, ????? ??? ?? ????????? ????? ? ? 820 ?? 1348 ?2/?. ???????? ?????????? ? ????????-
??????? 3. ?????????????? ???????? ?????????? ??????????, ?????????? ??????????????? ?????
????????? ?????? ? ????? ? ??? ??? 800 °? ? ?? ??????????? ??????? ?? ?2
?????.
???????, ?2,
??3/?
(???. %)
214 (1,91)
?????????
?????????/
???
????????
???????????,
S??., ?2/?
?????????
????? ???,
V???/
?????
????????,
V?????, ??3/?
???????
?????? ???
D, ??
??
1:1
880
0,42
0,31
2,19
??
1:2
963
0,48
0,33
2,14
248 (2,21)
??
1:3
1338
0,69
0,40
2,08
264 (2,35)
??
1:4
2050
1,05
0,24
2,16
242 (2,16)
??
1:1
822
0,47
0,27
1,97
192 (1,71)
??
1:2
1005
0,53
0,31
2,15
228 (2,04)
??
1:3
1100
0,51
0,34
2,16
247 (2,21)
??
1:4
1348
0,70
0,37
2,09
232 (2,07)
???????
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?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
800
500
700
4
?
3/
?600
?,
??
?
? 500
?
?
?
?
?
? 400
?
?
?
?
?
? 300
?
?
3
2
1
4
450
?
3/ 400
??
,?
?? 350
?
?
?
?
? 300
?
?
?
?
? 250
?
?
? 200
?
?
200
3
2
1
150
100
100
0
0,2
0,4
0,6
0,8
1
0
0,2
0,4
0,6
P/P0
0,8
1
?/?0
?
?
???. 3. ???????? ????????? ????? (77 ?) ?? ???????? ???, ?????????? ??????????????? ??????
??/??? (?) ? ??/??? (?) ? ????????? ???????????? ????????? : ??? (1 ? 1:1; 2 ? 1:2; 3 ? 1:3; 4 ? 1:4)
?????? ?????????? ????????? ??? ???????????? ??????, ????????, ?????????? ? ??????????
?????????????? ??????? ???????????? ? ???????????, ??????????? ?? ?????? ????????????. ? ?????????? ?????? S?? ??????????????? ???????? ?? ????????? ????? ?? ?????????
116 ?2/?, ? ?? ????????? ?????? ? 378 ?2/?.
??????????? ???????? ???????? ???, ?????????? ?? ????????? ?????? ? ?????, ????????, ??????? ? ????????? ?????????? ???????? ????????? ?????? ? ?????.
??? ??????? ?? ?????????? ??????, ????????? ?????????? ?????? ? ????? ?????? ??
???????? ???????????, ????? ? ?????? ??? ? ???????? ???. ????? ??????? ???????? ?????? ??? ??? ??? ?? ????? (0,70 ??3/?) ? ?????? (1,05 ??3/?) ?????????? ??? ?????????????
????????? ????????? ?????????/??? = 1:4, ??? ???? ??????? ???????? ??? ?? ?????????
2,1?2,2 ??.
???????? ????????? ????? ?? ???????? ???, ?????????? ??????????????? ?????? ???
? ?????????? ?????? ? ????? (???. 3), ?? ????? ? ???? ????????????? ????????? I ????, ???
??????????????? ? ???????? ????????????? ???????? ???????????? ?????????? ??????????
[23].
??????? ???????? ??????????? ? ???????????? ???? ???????? ? ?????????? ?????????? ?????????? ????????? ????????????? ?? ? ???????? ??????????? ??????????? ?????????????????
?????, ? ????????? ???????? [3]. ??? ???????? ??????????? ???????????? (????. 3), ???????????
?????????? ?? ???????? ? ???????? ??????????? ? ???????????????? ????????. ????????????
??????????? ??????? ?? ???????? (264 ??3/?) ????? ?????????? ?????????, ?????????? ?? ????????? ??????, ???? ???????? ? ??????? ?????????? > 50 % ?? ?????? ?????? ???. ??????????
?????? ??? ? ?????????? ???????? ? ?????? ?????????? ??? ? ????? ???????? ? ????????
?????????? ?????????????? ????????, ????????, ?? ???? ????????? ????????? ??? ????????? ?
????? ??????? ????? [23].
? ?????????? ??????????? ???????????? ???????????, ??? ??? ???????????? ???????????? ?????? ????????? ?????? (??????, ?????) ? ?????????? ????? ?????????? ????????????
?????????? ????????? ? ??????? ???????? ???????????? (?2000 ?2/?) ? ??????? ???????? ???
2,0?2,2 ??.
# 49 #
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?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
?????????????? ??????????? ?????? ????????? ????? ?????????????????? ????? [24]
??? ?? ?????????? ???????????? ??????????? ? ???????????? ????????? ?????? ?????????
? ??????????? ????????????? ?????????? ?????????? ??????????. ??? ???????????? ???????????? ??????? ? ???????????? ????????? ????? ????????? ? ???????? ?????????? ? ??????????????? ????????? [25].
???????? ???, ???, ???, ??? ? ??????????????? ??????? ??????????? ???????????
??????????????? ??????????? ????????????????? ???????? ???? ???????????? ??????? (?)
? ??? ?????? ? ???????????? (??), ? ????? ????????? ? ???????? ?????????? ???????? ?????
(??) [26].
??????????, ??? ?????????????? ??????? ???? ? ??????????????????? ??????????????? ???????? ??????? ???????? ? ??????????? ????????????? ? ????????? ???? ? ? ????????? ??????????????? ??????????? ? ??????????? ??????????? ??????? ??? ??????????????? ????????????. ????????? ????????? ??????????? ? ?????????? ??????? ???????????
?????????? d002, ?????????? ??????? ????????????, ????? ????? ? ??????????? ? ????????????
???????? ??????? ?? ???????????????.
??????? 2 % ??????? ???? ? ??????? ???????? ? ????????? ?????? ????????? ????????
?????????? ?? ?????? ??? ??? 193 °?, ???????, ????????, ????????????? ?????????? ????????????? ????. ??? ???? ????????? ??????????? ?????? ????????? ???????????? ??????????
(???) ? ??????????? ???????? ?????????? ? ?????????? ??? 230 ? 370 °?.
??????? ??????? ???? ? ??????? ? ????? ? ? ?? ???????????? ??????? ??????????? ??
??????????? ????????? ???? ???????? ??? ???????????? ??????? ? ???????? ???????.
????????? ??????? ????? ??????? ? ???????? 2 % ??????? ???? ??? ???????? ???????
40 °?/??? ?? ???????? ??????????? 800 °? ?????????????? ????????? ?????? ???, ???????????? ??????????? ??? ???????? ??????????? ? ????????????? ?????????? ?? ???????????? ?????? (??) ? ???? ?? ????????? ? ??? ?? ??????? (????. 4).
??? ???????? ??????? 90 °?/??? ?????????? ????? ??? ?? ???????, ??????????? 2 %
?u, ? ??? ????? ? ??????????? ?? ????????? ? ??????? ??? ?? ?????????????????? ??-
??????? 4. ?????????????? ???????? ????? ?? ??????? ? ????? ? ? ?? (1:1), ?????????? ??????????
????? ??? 800 °?
?????????
???????
?????????
?????
?????????, ?
V???????, °?/
???
2
-»-
40
-»-
31,2
370
233
918
? + 2 % ?u
24,1
120
71
458
? ? ??
-»-
-»-
27,6
250
137
529
? ? ?? +2 %
?u
?
-»-
-»13,9
341
134
798
?
? ? ??
? ? ?? +2 %
?u
0,5
-»-
90
-»-
-»-
-»-
?????, %
SBET, ?2/?
??, ??/?
???, ??/?
15,1
631
232
1056
14,1
739
137
727
18,6
620,5
126
951
# 50 #
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?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
?????? ? ? ?+??. ??? ???? ??????????? ?????????? ???????? ? ??????? ???????????
????????.
?????????? ????????? ?????????? ???? ? ??????? ????????????, ????????? ???
???? ????????????????? ??????? ????????? ???????????? ????? ? ???????????? ????????, ??? ??????????? ??????? ????? ???, ??? ???????? ??????????? ? ??????????? ??????????.
? ?????????? ??????????? ???????????? ??????????? ?????? ??????? ???????????????
? ?????????????? ???????????? ??????? ? ??? ?????? ? ???????????, ?????????????? ????????? ?? ???? ???????????? ??????? ??? ? ??????? 18-19 % ???. ? ???????? ????????????
620 ?2/?.
?????? ??????????
1. Marsh H., Rodriguez-Reinoso F. Activated Carbon. Elsevier, 2006. 537 p.
2. ?????????, ?.?. ???????? ???????. ??-? ???????? ?? ???, ???????????,
1995. 518 ?.
3. Carbon Materials for Advanced Technologies. Ed. T.D. Burchell. Elsevier, 1999. 540 p.
4. Shafizaden, F. Introduction to pyrolysis of biomass // J. Anal. Appl. Pyrol. 1982. V. 3. P. 283-305.
5. Sanchez, A.R., Elguezabal A.A., Saenz L.T., CO2 activation of char from wood waste //
Carbon. 2001. V. 39. P. 1367-1377.
6. ??????? ?.?., ???????? ?.?., ????? ?.?. ? ??. ??????????????? ?????? ???????????
??????????? ????? ?????? ??? ????????? ???????, ??????-???? ? ????? ?????????? ?
????????? ??????????. ???????????, 2005. 219 ?.
7. ???????, ?.?. ??????????? ?????????? ?????????????????? ?????????? ?????????.
?????????? ?? ?????? ??????????? ???? // ???. ????. 1997. ? 11. ?. 31-35.
8. Gonzales J.C., Gonzales M.T., Molina-Sabo M. et al.Porosity of activated carbons prepared
from different lignocellulosic materials // Carbon. 1995. V. 38. P. 1175-1177.
9. Helleur R., Popovic N., Ikira M. et al. Characterization and potential application pyrolytic
char from ablative pyrolysis of used tires // J. Anal. Appl. Pyrolysis. 2001. V. 58-59. P. 813-824.
10. ????????? ?.?., ????????? ?.?., ??????? ?.?. ? ??. ?????????????? ????????????
???????? ????????? ?????????? ?? ?????? ??????????????? ? ???????????? ???????? // ?????
???????? ???????. 1995. ? 3. ?. 62-68.
11. Sorum L., Gronli M.G., Hustad J.E. Pyrolysis characteristics and kinetics of municipal solid
wastes // Fuel. 2001. V. 80. P. 1217-1227.
12. Bansal R.C., Donnet J.B., Stoeckli F. Active carbon. Marcel Dekker Inc, New York. 1988.
P. 121-129.
13. ???????? ?.?., ?????????? ?.?., ????????? ?.?. ???????? ???? ? ???????? ???????
????????? ?????????? ????????? // ???? ? ?????. 1995. ? 10. ?. 13-19.
14. ???????? ?.?., ????????? ?.?.,. ??????? ?.?., ????????? ?.?. ??????? ???????????????
?????????? ??????????? ?? ???????? ????????? ?? ?????????? ????? // ????? ????????
???????. 2000. ? 1. ?. 45-54.
15. Lyubchik S.B., Benoit R., Beguin F. Influence of chemical modification of anthracite on the
porosity of the resulting activated carbons // Carbon. 2002. V. 40. P. 1287-1294.
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?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
16. ???????? ?.?., ????? M.?., ???????? ?.?. ? ??. ????????? ???????? ??????????
?????????? ???????????????? ???????? ? ??????????????? ?????????? ????????????
?????????? // ????? ? ????????? ??????????? ????????. 2005. ? 4. C. 521-529.
17. Mikova N.M., Chesnokov N.V., Kuznetsov B.N. Study of High Porous Carbons Prepared by
the Alkaline Activation of Anthracites //Journal of Siberian Federal University. Chemistry. 2009. V.2,
N 1. p. 3-10.
18. Marsh H., Heintz E.A., Rodrigues-Reinoso F. Introduction to carbon technologies. ? Alicante:
Universidad, 1997. 696 p.
19. Carbon nanotechnology. Ed. L. Dai. Elsevier, 2006. 733 p.
20. ??????? ?.?., ????????? ?.?., ???????? ?.?., ????????? ?.?., ???????? ?.?., ????????
?.?. ???????????? ???????? ????????? ?????? ???? ??? ????????? ? ??????????? ????? //
????? ???????? ???????. 2009. ?. 5. ?. 51-55.
21. Mota J.B. Adsorbed natural gas technology. in Recent advances in adsorp-tion processes for
environmental protection and security. Ed. by J.P. Mota, S.B. Lyubchik. Springer: 2006. 192 p.
22. Carrot P.J.M., Ribeiro Carrot M.M.L., Mourao P.A.M. Pore size control in activated carbons
obtained by pyrolysis under different conditions of chemically impregnated cork. // J. Anal. Appl.
Pyrolysis. 2006. V. 73. P. 120?127.
23. ???? C., ???? ?. ?????????, ???????? ???????????. ?: ???, 1984. 306 ?.
24. ??????? ?.?., ????????? ?.?., ????????? ?.?., ???????? ?.?. ???????? ?????? ??????
???? ? ???????? ??????? // ?????????????? ??????. 2005. ? 1-2. ?. 45 ? 49.
25. ??????? ?.?., ??????? ?.?., ???????? ?.?., ??????? ?.?., ????????? ?.?., ????????
?.?. ?????????? ?? ??????? ? ????????? ???????? ??????? // ????? ???????? ???????. 2007.
?2. ?. 62-67.
26. Simonova V.V., Shendrik T.G., Chesnokov N.V., Kuznetsov B.N. Influence of Copper Acetate
on the Thermochemical Transformations of Hydrolytic Lignin and its Mixtures with Oil Slimes //
Journal of Siberian Federal University, Chemistry. 2008. N3. P. 215-224.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ??????? ????????? ?????????? ????????? ?????????? ???????????? ?????????? ??????
Synthesis of Carbon Sorbents
by Chemical Modification
of Fossil Coals and Plant Biomass
Nicolay V. Chesnokova,b, Nadezhda M. Mikovab,
Ivan P. Ivanovb and Boris N. Kuznetsova,b
a
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
b
Institute of Chemistry and Chemical Technology SB RAS,
50-24 Academgorodok, Krasnoyarsk, 660036, Russia
Main features of thermal activation of chemically modified abthracites, lignites, wood and lignin were
studied at variation of the chemical agent nature, process temperature and time. The formation of
porous structure of carbon products was studied. Optimum conditions of porous carbon synthesis
which ensure obtaining of products with the high specific surface area (to 2000?2900 m2/g) were
selected for all types of studied raw materials.
Keywords: carbon sorbent, synthesis, anthracite, lignite, wood, lignin, chemical activation, porous
structure.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 54-62
~~~
??? 547,51+547,562+547,563+547,565
????????????? 1-?????????????
??????????? ??????
?.?. ????????? a, ?.?. ????????a,
?.?. ???????? *, ?.?. ???????????a, ?.?. ???????a,?*
a
???????? ????? ? ?????????? ?????????? ?? ???,
??????, 660036, ??????????, ?????????????, 50, ???. 24
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
a
Received 17.12.2013, received in revised form 28.12.2013, accepted 10.02.2014
?????????????? ?????????? ??????? ? 1-????????????? ? ??????????? 1-??????????????,
? ????? ??????? 1-???????????? ? ??????????????? ? ??????????????? ??????? ???????? ?
????????? ????- ? ???????????????.
???????? ?????: ?????????????, ??????, ?????????.
????? ??????????????????? ??????? ???????? ??????? ??????????, ?????????? ???????? ????????????? ??????? ? ????-????????? ? ?????????? ??????. ?????
???????????????-???????????? ??????, ??????? ???????????? ???????????????, ?????
??????????? ? ???????? ?????????????? ?????????? ??????????, ???????? ? ???????? ?
?????? [1]. ??????? ????????????????? ??????????? ???????, ?????????? ???????? ????????????? ??????? ? ????- ? ????-??????????, ? ???????????, ??? ? ????????? ???????
????????? ?????? ???????? ??????? ????-??????????????? [2]. ???????????? ???????
????????????? ?????????????????? ??? ??????????? ?????? ????????? ????????, ??? ???????????? ?????? 2,6-??(1-?????????)-4-??????????, 2,4-??(1-?????????)-6-??????????,
3,5-??(1-?????????)-2-????????????? [3].
???????? ????????? ???????? ????????? 6-[3-(1-?????????)-4-????????????]-2-?????????
???????, ?????????????? ????????? ?????????, ???????????? ? ?????? ????????? ????????????? ??????????, ????????????? ? ????????????????? ???????? ??? ??????????? ????????
?????? ??????? ???? [4].
? ??????????? ???????????? ??????? ????????????????? ??????? [5, 6] ??????? ?????????????? ??????????? ?????? ? 1-????????????? ? ????????? ????????. ??????? [7] ????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: Ivan.Peterson.Krsk@gmail.com
# 54 #
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?.?. ????????? , ?.?. ????????? ????????????? 1-????????????? ??????????? ??????
??? ????????? ??????? ? ??????????? ?????? ????????? ???????????????????? ??????? (?
??? ????? 4-?????????????????) ??????????????? ??????? ? 1-????????????? ? ???????????
1-??????????????. ???????? ?????? ????????? 3-(1-?????????)-4- ??????????????????? ??????????? 4-??????????????????? ? 1-????????????? ? ???????? ??????? ? ??????????? ?????? ???????????? ???? [8].
?????????? ? ??????????
? ????????? ?????? ???????? ??????????? ??????? 4-??????????????????? ? 1-????????????? ? ??????????? 1-?????????????? ??? 210 °? ??? ???????????? ? ???????????? ????- ???
??????????????? ???????????, ?? ? ??????? ??????????? 1-??????????????, ??? ?? ?????
???????????? [7]. ??????????? ????????? ? ???????????? ?????????????? 3-(1-?????????)-4??????????????????? (1) ??????? ? ????????????? [8]. ???? ??????? ?? ?????????? 1, ?????
3(1-?????????)-4-??????????????????? (1?). ?? ?????? 1? ???????????????? ??????? ??? ?????????? ? ??????????????? ??????? ??????? 2-(1-?????????)-?????????????? (3) ? ?????????????????? ?????? ???????????? ? ??????? 90 %. ??? ?? ?????????? 3 ?????????? ? ???
?????????????? 4-??????????????? ? 1-??????????????? ??? ?????????? ? ??????? ????????
??????? ? ??????? 30 % (???. 1).
????? [9] ?????????? ?? ????????????? ?????? 1-????????????? ? ???????????????
??????? ??? ????????? ??????????? ? ???????????? 4-(1-?????????)?????? ? ???????
79 %. ?? ?????, ??? ??? ?????????????? ?????? ? ???????? 1-???????????? ? ???? ???????? ??????? ????????? ???????? 2,4-??(1-?????????)????? (4?, 70 %) (???. 2). ???????
????????? ?????????? 4? ???????? ?????? ? 1-????????????? ? ??????????? ??????????????????? ???????? ? ???????? ???????????? ? ????? ? ???? 2- ? 4- , 2,6-?? ? 2,4,6-???(1?????????)???????? ? ????????????? ?????? ?????? ? ??????? ? ???????? 1,4-9,8 %
[10].
? ?????? [2] ????????????? ???????????? ? ???????? ?????????????? ?????? ???? ???[2????????-3-(1-?????????)-5-??????????]??????, ??? ????????????? ?????? ???????????????
???????. ??? ???????? ?????????? ???????? ?????????? «??????? 2246», ? ??????? ????????????? ?????? ???????? ?? ?????????????. ?? ?????????? 4? ???????????? ? ?????????????? ???? ??????? ???[2-????????-3,5-??(1-?????????)?????]????? 5 (???. 2). ? ??? ?
????????? ?????? ???????? ?? ?????????????. ??? ?????? ????????????? ??????? ????????? ???-????????????? ??????? ????????? ????????????? ?????????? ? ????- ? ??????????????.
OH
OH
1-OHAd, R2
1-BrAd
OH
R1
Ad
OH
OH
Ad
???????
????????.
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', CF3COOH
H3C
C
O
C
H3C
O
1 (R1=Ad, R2=H);
2 (R2=R1=Ad)
H3C
C
NOH
1a
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# 55 #
HN
3
C
O
CH3
HN
C
O
CH3
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?.?. ????????? , ?.?. ????????? ????????????? 1-????????????? ??????????? ??????
R
OH
OH
OH
R1 1-OHAd R
CF3COOH
Ad
R1
R2
4a (R=H, R1=R2=Ad);
4? (R=R1=CH3; R2=Ad)
Ad
CH2O
Ad
OH
OH
Ad
Ad
4a
Ad
5
???. 2. ????? ??????? ?????????? 4?, 4? ? 5
???. 3. ????? ??????? ?????????? 6?-?
OR
OR
1-OHAd
H2SO4,
CH3COOH
R1
R2
4?: R=H; R1=R2=Ad
R1 7: R=CH3; R1=I; R2=Ad
???. 4. ????? ??????? ?????????? 4? ? 7
????- ? ????-????????????? ? ?? ??????? ????? ??????????????? ??? ????????? ??????????? ? 1-????????????? ? ??????????????? ??????? (???. 3). 2,6-???????? ????? ?????????
? 1-????????????? ? ???? ?? ???????? ? ???????????? 2,6-???????-4-(1-?????????)?????? 4?
? ??????? 92 % (???. 2), ? ?? ????? ??? ??? ?????????????? ??? ? 1-??????????????? ??? ?????????? ?????????? 4? ?????????? ? 50%-??? ??????? [11].
??????? ???? [12] ????????? ????? ?????? ????????? 2-(1-?????????)-4-?????????? ?
?????????? ?????? ????????? 2-(1-?????????)-4-??????????? ? ???? ?????? ?????? ????;
??? ?????????? ???????? ?????????????? ?????????? ? ??????? ?????????. ?????????? ??
4-?????????? ??????????????? ? 1-????????????? ??? ????????? ??????????? ? ????? ???????? ? ?????? ?????? ??????? 2-(1-?????????)-4-????????? (7, ???. 4). ????? ?? ??????????,
??? 2,4-??(1-?????????)????? 4? ???????? ??????? ????????? ? ??? ?????????? ???????
4-(1-?????????)?????? ? 1-????????????? ? ????? ?????? ? ???????? ?????? [13] ??? ????????? ???????????, ?? ????? ??? ?????????? ?? 53 % (???. 4).
????? ???????, ????????? ????????????? ???? ??????? ?????????????, ????? ????????????? ?????????????????? ??????????? ????????????? ???????.
# 56 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????? , ?.?. ????????? ????????????? 1-????????????? ??????????? ??????
????????????????? ?????
??????? ??? ?????????????? ?? ???????????? «Bruker Avance III 600» (1H ? 600,13 ???,
13
C ? 150,90 ???) ????????????? ????????????? ?????? ????????????? ??????????? ?? ???).
?????????? ??????? ????????? ?? ??????? «Flash EA 1112TM».
3-(1-?????????)-4-?????????????????? (1)
4-?????????????????? (0,272 ?, 2 ?????) ????????? ? 1-????????????? (0,152 ?, 1 ?????) ?
1-??????????????? (0,02 ?, 0,1 ?????) ? ????????? ? ????????? ??? ??????????? 210 °? ? ??????? 10 ?. ??????????? ??????????? ????? ?????????? ? ??????? ? ?????? ? ????, ?????? ??????? ?????. ??????? ??????????????????? ?? ???????. ????? 0,222 ?, 82 %. ?. ??. 182-184 °?
(183-185 °? [8]).
?????? ??? 1? (CDCl3, ?, ?.?.): 7,93 (?, 3J=2,2, 1H, H3); 7,74 (??, 3J=8,3, 2,2, 1H, H5); 6,76 (?,
3
J=8,25, 1H, H6); 6,10 (?, 1H, OH), 2,59 (?, 3H, Ac-CH3); 2,17 (?, 6H, Ad-H?); 2,12 (?, 3H, Ad-H?);
1,83-1,79 (?, 6H, Ad-H?).
13
C (?, ?.?.): 197,6 (Ac-CO); 159,7 (C1); 136,4 (C2); 130,9 (C4); 128,1 (C3); 128,1 (C5); 116,6 (C6);
40,3 (Ad-C?); 36,7(Ad-C?); 36,5(Ad-C?); 28,7 (Ad-C?); 26,2 (Ac-CH3).
????? 3-(1-?????????)-4-??????????????????? (1?)
? 3-(1-?????????)-4-??????????????????? (0,270 ?, 1 ?????) ? 2,5 ?? ?????-??????????
???????? ????????????? ?????????????? (1,75 ? NH 2OH-HCl ?? 5 ?? ???? ? 20 ?? ???????) ??
?????? ????????? 20%-??? ??????? NaOH ?? ??????????? ???????, ??????????? ????? 1 ?
? ???????? ? ????, ?????? ??????, ????? 0,27 ?, 95 %. ?. ??. 204 °? (????.).
?????? ??? 1? (????-d6, ?, ?.?.): 10,76 (??.?., 1H, NOH), 7,41 (?, 3J=1,9, 1H, H3), 7,22 (??,
3
J=8,3, 1,9, 1H, H5), 6,72 (?, 3J=8,3, 1H, H6), 3,22 (??.?., 1H, OH), 2,04 (?, 3H, Ac-CH3), 2,03 (?, 6H,
Ad-H?), 1,99 (?, 3H, Ad-H?), 1,68 (?, 6H, Ad-H?).
13
C (?, ?.?.): 157,1 (C1), 153,2 (C-NOH), 135,5 (C2), 127,9 (C4), 116,3 (C6), 124,5 (C5), 123,8 (C3),
40,2 (Ad-C?), 36,9 (Ad-C?), 36,5 (Ad-C?), 28,7 (Ad-C?), 11,7 (Ad-C?).
?????????? (2) ???????? ??????????.
3,5-??(1-?????????)-4-?????????????????? (2)
??????? ?? 4-??????????????????? (0,136 ?, 1 ?????), 1-???????????? (0,304 ?, 2 ?????)
? 1-?????????????? (0,03 ?, 0,15 ?????) ??? ?????????? ??? 210 °? ? ??????? 15 ?. ?????
0,307 ?, 76 %. ?. ??. 206-208 °?. ???????, %: ? 83,25; ? 8,77, ?28?36?2. ?????????, %: ? 83,37;
? 8,98,
?????? ??? 1? (CDCl3, ?, ?.?.): 7,82 (?, 2H, H3-H5), 5,91 (??.?., 1H, OH), 2,58 (?, 3H, Ac-CH3),
2,18 (?, 6H, Ad-H?), 1,85-1,82 (?, 6H, Ad-H?), 2,17 (?, 3H, Ad-H?).
13
C (?, ?.?.): 197,6 (Ac-CO); 159,1 (C1); 136,3 (C2); 129,0 (C4); 125,9 (C3, C5); 42,0 (Ad-C?); 36,6
(Ad-C?); 35,4 (Ad-C?); 27,8 (Ad-C?); 26,2 (Ac-CH3).
2-(1-?????????)-4-???????????????? (3) (??????????????? ???????)
?. ??????? ?????? (0,5 ?, 1,8 ?????) ? 1,5 ?? ??????????????? ??????? ???????? ?????????? ? 0,76 ?? ??????? CF3COOH, ??????????? ????? ??? ??????? 30 ???. ????? ????????
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?.?. ????????? , ?.?. ????????? ????????????? 1-????????????? ??????????? ??????
??? ???????? CF3COOH ??????? ????????? ?????, ?????? ? ?????????????????????. ?????
0,45 ?, 90 %. ?. ??. 195-196 °? (??????). ?????? ??? 1? (??????-d6, ?, ?.?.): 8,88 (??.?., 1H, NH),
8,11 (??.?., 1H, OH), 7,41 (??, 3J=8,49, 2,49, 1H, H5), 7,21 (?, 3J=2,49, 1H, H3), 6,72 (?, 3J=8,49, 1H,
H6), 2,20 (?, 3H, CH3), 2,18 (?, 6H, Ad-H?), 1,81-1,79 (?, 6H, Ad-H?), 2,04 (?, 3H, Ad-H?).
13
C (?, ?.?.): 168,5(Ac), 152,4 (C1), 135,5 (C2), 124,1 (C3), 118,4 (C5), 115,6 (C6), 40,2 (Ad-C?), 36,4
(Ad-C?), 36,3 (Ad-C?), 22,7 (Ad-C?).
?. 1-????????????? (0,430 ?, 2 ?????) ? ?????????????? (0,755 ?, 5?????) ???????? ? 5 ??
??????? ???????? ??????? ? ????????? ?????? ? ??????? 2 ?. ?????????, ???????? ? ????, ?????? ????????? ????? ?? ??????????? ???????, ??????. ?????????? ?????????????? (???????
?????????? 100-160 ?), ?????? ??????-??????????? ??????? ??????? 0,170 ?, 30 %. ?. ??. 195196 °?. ???????, %: ? 75,68, ? 8,08, N 4,93 C18H23NO2 ?????????, %: ? 75,75, ? 8,12, N 4,81,
?????? ??? 1? (??????-d6, ?, ?.?.): 8,88 (??.?., 1H, NH), 8,11 (??.?., 1H, OH), 7,41 (??,
3
J=8,49, 2,49, 1H, H5), 7,21 (?, 3J=2,49, 1H, H3), 6,72 (?, 3J=8,49, 1H, H6), 2,20 (?, 3H, CH3), 2,18 (?,
6H, Ad-H?), 1,81-1,79 (?, 6H, Ad-H?), 2,04 (?, 3H, Ad-H?).
13
C (?, ?.?.): 168,5 (Ac), 152,4 (C1), 135,5 (C2), 124,1 (C3), 118,4 (C5), 115,6 (C6), 40,2 (Ad-C?), 36,4
(Ad-C?), 36,3 (Ad-C?), 22,7 (Ad-C?).
2,4-??(1-?????????)????? (4?)
?. ? ???????? ?????? (0,094 ?, 1 ?????) ? 3 ?? ??????????????? ??????? ??? ????????????? ???????? 1-??????????? (0,380 ?, 2,5 ?????) ? ??????????? ??? 30 °? ? ??????? 24 ?.
? ????? ???????? 15 ?? ????. ?????? ?????????????, ??????? ????????? ????, ????????.
????? 0,254 ? (70 %). ?. ??. 305-306 °? [10].
?. ? ???????? 4-(1-?????????)?????? (0,228 ?, 1 ??????) ? 1-???????????? (0,152 ?, 1?????)
? 1,5 ?? ??????? ???????? ??????? ??????????? 0,3 ?? ????????????????? ?????? ??????? ?
??????????? ??? 30 °? ? ??????? 24 ?. ? ????? ???????? ???? ?? ????? ? ????????????? ??????, ??????? ????????? ????, ????????. ????? 0,192 ? (53 %). ?. ??. 305-306 °?.
?????? ??? 1? (CDCl3, ?, ?.?.): 7,26 (?, 3J=2,3, 1H, H3), 7,07(??, 3J=8,2, 2,3, 1H, H5), 6,63 (?,
3
J=8,2, 1H, H6), 4,62 (?,1H, OH), 2,17 (?, 6H, Ad-H?), 2,12 (?, 6H, Ad-H?), 1,92 (?, 6H, Ad-H?), 1,82
(?, 6H, Ad-H?), 1,80-1,75 (?, 6H, Ad-H?).
??? 13C (?, ?.?.): 151,8 (C1), 143,4 (C4), 135,4 (C2), 123,3 (C3), 122,8 (C5), 116,1 (C6), 43,4 (Ad-C?),
40,5 (Ad-C?), 36,9 (Ad-C?), 36,8 (Ad-C?), 36,7 (Ad-C?), 35,8 (Ad-C?), 28,9 (Ad-C?).
???[2-????????-3,5-??(1-?????????)?????]????? (5)
? ????? 2,4-??(1-?????????)?????? (1,01 ?, 5 ?????), 2 ?? ????, 0,01 ?? ????????????????? ?????? ???????, 0,01 ? ??????????????????? ? 6 ?? ??????? ??? ?????????? ?? 80-85 °?
? ????????????? ??????????? 1,4 ?? ????????? ? ??????? 30 ???. ????? ????????? ?????
?????????? ??????? ???????? ???????????????, ????????? ????????? ??????????? ????,
??????? ? ?????? ?? ???????. ????? 2,98 ? (87 %). ?. ??. 270-271 °?. ???????, %: ? 86,38; ? 9,35,
?53?68?2 ?????????, %: ? 86,44; ? 9,29.
?????? ??? 1? (CDCl3, ?, ?.?.): 7,16 (?, 3J=2,0, 2H, H4); 7,15 (?, 3J=2,0, 2H, H6); 3,96 (?, 2H,
CH2); 2,14 (?,12H, Ad-H?); 2,12 (?, 12H, Ad-H?); 2,12 (?, 6H, Ad-H?); 1,81-1,77(?, 12H, Ad-H?); 1,81
(?, 12H, Ad-H?); 1,92 (?, 6H, Ad-H?).
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?.?. ????????? , ?.?. ????????? ????????????? 1-????????????? ??????????? ??????
??? 13C: 150,4 (C2); 143,3 (C3); 135,7 (C5); 125,6 (C1); 124,4 (C6); 122,0 (C4); o???-Ad: 40,8 (AdC?); 36,8 (Ad-C?); 28,7 (Ad-C?); ????-Ad: 43,3 (Ad-C?); 36,7 (Ad-C?); 28,7 (Ad-C?).
2,6-???????-4-(1-?????????)????? (4?)
? ???????? 2,6-????????????? (0,242 ?, 2 ?????) ? 2,5 ?? ??????????????? ??????? ???
????????????? ???????? 1-??????????? (0,304 ?, 2?????), ????????? ??? ????????? ??????????? ? ??????? 48 ?. ? ????? ???????? 15 ?? ????, ?????? ?????????????, ??????? ?????????
????, ????????. ????? 0,470 ? (92 %). ?. ??. 160,5-161 °? (161 °? [11]).
?????? ??? 1? (CDCl3, ?, ?.?.): 7,00 (?, 2H, H3-H5), 4,48 (??.?., 1H, OH), 2,28 (?, 6H, CH3),
2,11 (?, 3H, Ad-H?), 1,91 (?, 6H, Ad-H?), 1,81-1,77 (?, 6H, Ad-H?).
??? 13C: 150,0 (C1), 143,4 (C4), 125,1 (C3, C5), 122,2 (C2,C6), 43,3 (Ad-C?), 36,8 (Ad-C?), 35,4
(Ad-C?), 28,9 (Ad-C?), 16,1 (CH3).
?????????? (6?-?) ???????? ??????????.
2-????-4-(1-?????????)?????(6?)
??????? ?? 2-?????????? (0,173 ?, 1 ?????) ? 1-???????????? (0,152 ?, 1 ?????) ? 2 ?? ??????????????? ???????. ????? 0,246 ? (80 %). ? ??. 108-109 °? (107-108 °? [14]).
?????? ??? 1? (CDCl3, ?, ?.?.): 7,44 (?, 3J=2,31, 1H, H3), 7,23 (??, 3J=8,54, 2,31, 1H, H5), 6,99 (?,
J=8,54, 1H, H6), 5,19 (??.?., 1H, OH), 2,12 (?, 3H, Ad-H?), 1,88 (?, 6H, Ad-H?), 1,81-1,76 (?, 6H, Ad-H?).
??? 13C: 149,7 (C1); 145,3 (C4); 128,3 (C3); 125,6 (C5); 115,4 (C5); 110,0 (C2); 43,1 (Ad-C?); 36,5
(Ad-C?); 35,7 (Ad-C?); 28,7 (Ad-C?).
3
2-????-4-(1-?????????)????? (6?)
??????? ?? 2-?????????? (0,129 ?, 1 ?????) ? 1-???????????? (0,152 ?, 1 ?????) ? 2 ??
??????????????? ???????. ????? 0,180 ? (76 %). ?. ??. 110-111 °?. ???????, %: ? 73,14; ? 7,32,
?16?19?l?. ?????????, %: ? 73,10; ? 7,23.
?????? ??? 1? (CDCl3, ?, ?.?.): 7,45 (?, 3J=1,74,1H, H3), 7,25 (??, 3J=8,46, 2,27, 1H, H5), 7,04
3
(?, J=8,71, 1H, H6), 5,38 (??.?., 1H, OH), 2,12 (?, 3H, Ad-H?), 1,89 (?, 6H, Ad-H?), 1,81-1,76 (?, 6H,
Ad-H?).
??? 13C: 148,9 (C1), 145,1 (C4), 125,6 (C3), 125,0 (C5), 119,5 (C2), 115,7 (C6), 43,3 (Ad-C?), 36,7
(Ad-C?), 35,8 (Ad-C?), 29,0 (Ad-C?).
2-????-4-(1-?????????)????? (6?)
??????? ?? 2-?????????? (0,112 ?, 1 ?????) ? 1-???????????? (0,152 ?, 1?????) ? 2 ??
??????????????? ???????. ????? 0,172 ? (70 %). ?. ?? 144-145 °?. ???????, %: ? 78,10; ? 7,64,
?16?19F?. ?????????, %: ? 78,05; ? 7,72.
?????? ??? 1? (CDCl3, ?, ?.?.): 7,10 (??, 3J=12,96, 2,25, 1H, H3), 7,04 (???, 3J=8,57, 2,25, 0,86,
1H, H5), 6,96 (??, 3J=9,21, 8,57, 1H, H6), 4,43 (??.?., 1H, OH), 2,12 (?, 3H, Ad-H?), 1,88 (?, 6H, AdH?), 1,81-1,76 (?, 6H, Ad-H?).
??? 13C: 150,7 (J HF=235,6, C 2); 144,9 (J HF=4,9, C 4); 140,7 (J HF=13,4, C1); 120,7 (J HF=3,7,
C 6 ); 116,4(J HF=1,9, C5) 112,1 (J HF=18,2, C3); 43,2 (Ad-C?); 36,5 (Ad-C?); 35,6 (Ad-C?); 28,8
(Ad-C?).
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?.?. ????????? , ?.?. ????????? ????????????? 1-????????????? ??????????? ??????
2-(1-?????????)-5-????????? (6?)
??????? ?? 3-?????????? (0,173 ?, 1 ?????) ? 1-???????????? (0,152 ?, 1 ?????) ? 2 ??
??????????????? ???????. ????? 0,295 ? (96 %). ?. ??.112-114 °?. ???????, %: ? 62,63; ? 6,27,
?16?19BrO. ?????????, %: ? 62,54; ? 6,24.
?????? ??? 1? (CDCl3, ?, ?.?.): 8,79 (?, OH), 7,09 (?, 3J=8,40, 1H, H3), 7,15 (?, 3J=2,19, 1H, H6),
6,97 (??, 3J=8,40, 2,12, 1H, H4), 2,15 (?, 6H, Ad-H?), 1,80 (?, 9H, Ad-H?, Ad-H?).
??? 13C: 155,0 (C1), 135,5 (C2), 128,3 (C3), 123,6 (C4), 119,5 (C6), 119,2 (C5), 40,2 (Ad-C?), 36,8
(Ad-C?), 36,3 (Ad-C?), 28,8 (Ad-C?).
2-(1-?????????)-5-???????? (6?)
??????? ?? 3-????????? (0,220 ?, 1 ?????) ? 1-???????????? (0,152 ?, 1 ?????) ? 2 ?? ??????????????? ???????. ????? 0,202 ? (57 %). ?.??. 127 °?. ???????, %: ? 54,30; ? 5,46, ?16?19JO.
?????????, %: ? 54,24; ? 5,40.
?????? ??? 1H (CDCl3, ?, ?.?.): 7,25(??, 3J=8,41, 1,74, 1H, H4), 7,02 (?, 3J=1,58, 1H, H6), 6,95 (?,
3
J=8,38, 1H, H3), 4,57 (??.?., 1H, OH), 2,10 (?, 9H, Ad-H?, Ad-H?), 1,80 (?, 6H, Ad-H?).
??? 13C: 155,1 (C1); 136,3 (C2); 129,7 (C4); 128,6 (C3); 125,2 (C6); 90,4 (C5); 40,2 (Ad-C?); 36,8
(Ad-C?); 36,5 (Ad-C?); 28,7 (Ad-C?).
2-????-4-(1-?????????)?????? (6?)
??????? ?? 2-??????????? (0,126 ?, 1 ?????) ? 1-???????????? (0,152 ?, 1 ?????) ? 2 ??
??????????????? ???????. ????? 0,161 ? (62 %). ?. ??. 114-115 °?. ???????, %: ? 78,52; ? 8,16,
?17?21FO. ?????????, %: ? 78,43; ? 8,13.
?????? ??? 1H (CDCl3, ?, ?.?.): 7,11 (???, 3J=8,71, 2,33, 2,09, 1H, H5), 7,07 (??, 3J=13,75, 2,33,
1H, H3), 6,88 (??, 3J=8,84, 8,71, 1H, H6), 3,85 (?, 3H, OCH3), 2,11 (?, 6H, Ad-H?), 1,84 (?, 3H, Ad-H?),
1,81-1,78 (?, 6H, Ad-H?).
??? 13C: 152,9 (J HF=244,0, C2); 145,0 (J HF=11,2, C1); 144,9 (J HF=5,58, C4); 120,0 (J HF=3,5, C6);
112,9 (C5); 112,9 (J HF=16,8, C3) 56,2 (OCH3); 43,1 (Ad-C?); 36,6 (Ad-C?); 35,5 (Ad-C?); 28,8 (AdC?).
2-(1-?????????)-5-?????????? (6?)
??????? ?? 3-?????????? (0,234 ?, 1?????) ? 1-???????????? (0,152 ?, 1 ?????) ? 2 ?? ??????????????? ???????. ????? 0,132 ? (36,4 %). ?. ??. 151-152 °?. ???????, %: ? 55,39; ? 5,75,
?17?21J?. ?????????, %: ? 55,45; ? 5,74.
?????? ??? 1H (CDCl3, ?, ?.?.): 7,26 (??, 3J=8,25, 1,69, 1H, H4), 7,15 (?, 3J=1,69, 1H,
H6), 6,93 (?, 3J=8,25, 1H, H3), 3,83 (?, 3H, OCH3), 2,05 (?, 9H, Ad-H? Ad-H?), 1,78 (?, 6H,
Ad-H?).
??? 13C: 159,4 (C1); 138,3 (C4); 129,5 (C2); 128,1 (C3); 120,6 (C6); 90,7 (C5); 55,2 (OCH3); 40,2
(Ad-C?); 37,8 (Ad-C?); 37,1 (Ad-C?); 28,9 (Ad-C?).
2-(1-?????????)-4-????????? (7)
4-????????? ? ?????????? 0,261 ?, 1,14 ????? ????????? ? 1-????????????? (0,173 ?,
1,14?????) ? 1,5 ?? ??????? ???????? ??????? ??? ????????? ??????????? ? ????? ???????# 60 #
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???? 0,6 ?? ????????????????? ?????? ???????. ??????????? 4 ??? ??? ????????? ??????????? ? ????? ?????????? ??????????? ????? ?????????? ?????, ??????? ???????????????,
????????? ????? ? ?????. ????? 0,380 ? (91,5 %). ?.??. 124-125є? (??????). ???????, %: C 55,52;
H 5,70, C17H21IO. ?????????, % : ? 55,45; ? 5,74.
??? 1H: (CDCl3, ?, ?.?.): 1,82 (?, 6?); 2,11 (?, 9?); 3,85 (3?, ???3); 6,67 (?, 1?, ?6; J=8,4 ??);
7,50 (??, 3J=2,29, 1H, ?5); 7,51 (?, 3J=2,29, 1H, H3).
??? 13C: 158,6 (C1); 141,1 (C4); 135,5 (C3); 135,3 (C5); 113,8 (C6); 83,6 (C2); 54,9 (OCH3); 40,2
(Ad-C?); 37,0 (Ad-C?); 36,8 (Ad-C?); 28,8 (Ad-C?).
?????? ??????????
1. ????????? ?.?. ????????? ?????????????. ??????????? ??????????? ?
?????????????. ?., ?????, 1998, 149 ?.
2. ????????? ?.?., ???????? ?.?., ??????? ?.?., ?????? ?.?. ?????????????????
?????????? ???????????????? // ???????? ? ???????. 2002. ?. 43. 2. ?. 205-208.
3. ???. ?? 246014, ?????. 10. 09. 2012; ???. ?? 246016, ?????. 10.09.2012; ??????? ?.?.,
?? ???? ???, ????????? ?.?., ???????? ?.?., ??? ??? ????? ???, ??????? ?.?., ????????
?.?., ??????? ?.?., ????????? ?.?. ??????????? ??????????????? ??? ?????????????????
?????????? ????????????? ??? ????????? ??????????? ?????? ????????? ???????? //
???????????????? ? ??????????. 2013. ? 4, ?. 18-21; ??????? ?.?., ?? ???? ???, ?????????
?.?., ???????? ?.?., ??? ??? ????? ???, ??????? ?.?., ????? ?.?., ???????? ?.?.,
??????? ?.?., ????????? ?.?. ?????? ???????????? ?????????? ????????????????????
??????????? ???????????? ? ??????????? ??? ??????????? ?????? ????????? ????????//
???????????????? ? ??????????. 2013. ? 9. ?. 24-28.
4. Carpentier B., Bernadon J.-M., Eustache J., Millois C., Martin B., Michel S. Brahan Shroot.
Synthesis, Structure-Affinity Relationships and Biological Activities of Ligands Binding to Retinoic
Acid Receptor Subtypes // J. Med. Chem., 1995, 38, 4993; ???. WO 2007/125542, ?????. 08.11.2007;
CN 101955417, ?????. 26.01.2011.
5. ????????? ?.?., ???????? ?.?., ???????? ?.?.. ????????????????? 1- ? 2-????????
1-????????????? ? ??????????????? ??????? // ????. 2007. ?. 43. ? 5. ?. 783-784.
6. ????????? ?.?., ???????? ?.?., ????? ?.?., ??????? ?.?., ?????????? ?.?.
??????????????????? ??????????? ??????? ? ?? ??????????? // ????. ?????. ???. 2008. 81.
? 3. ?. 524-525.
7. ????????? ?.?., ???????? ?.?., ??????? ?.?. ?????????????? ??????? ?
1-????????????? ? ??????????? 1-?????????????? // ???. ??. ???. ???. 2013. 5. ?. 1294-1296.
8. Wang N., Wang R., Shi X., Zou G. Ion-exchange-resin-catalyzed adamantylation of phenol
derivatives with adamantanols: Developing a clean process for synthesis of 2-(1-adamantyl)-4bromophenol, a key intermediate of adapalene // Beilstein J. Org. Chem. 2012. 8. P. 227-233.
9. ???????? ?.?., ???????? ?.?., ???????? ?.?. ?? ????????????? ?????????????
?????????? 1-????????????? // ????. 2007. 43. 4. ?. 540-544.
10. ????? ?.?., ???????????? ?.?., ??????? ?.?. ?????????????? ?????? ?
1-??????????????? ? ??????????? ??????????????????? ????????. // ????. 1988. 24. 9.
?. 1922-1925.
# 61 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????? , ?.?. ????????? ????????????? 1-????????????? ??????????? ??????
11. ?????? ?.?., ???????? ?.?.. ?????? ??????????????????? ?????????? ? ????????????
// ???? ??. ?.?. ?????????? 1981. ?. 26. ? 5. ?. 593-595.
12. ????????? ?.?., ???????? ?.?., ???????? ?.?., ??????? ?.?. ???????????????????
?????? 2-(1-?????????)-4-?????????? ? 2-(1-?????????)-4-??????????? ? ?????????????
????????? ??????? ????????? // ???.-????. ????. 2013. ?. 47. ? 4. ?. 133-134.
13. ???????-????????? // ?????? ???????????? ? ???????????? ?????: ???. ? ???. / ???
???. ?. ?. ????????. ?.: ?????, 1968, ?. 780.
14. ?????? ?.?., ???????? ?.?., ????????? ?.?., ????? ?.?., ?????? ?.?. ????? ??????
??????? ????????? ??????????? ? ???? ?????????? ? ?????????????????? // ????? ? ??????????? ????????? / ??? ???. ?.?. ??????????. ???, 1975. ?. 121-140.
Alkylation of Derivatives Phenol
with Adamantan-1-ol
William A. Sokolenko ?,
Nadezhda M. Svirskaya?, Ivan V. Peterson?*,
Alexander A. Kondrasenko? and Anatoliy I. Rubaylo?,b
a
Institute of Chemistry and Chemical Technology SB RAS,
50-24 Academgorodok, Krasnoyarsk, 660036 Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
The interaction of phenol derivatives with adamantan-1-ol and 1-bromoadamantane as well as the
reaction of halogenophenols with adamantan-1-ol in trifluoroacetic acid was investigated. Reaction
of substituted phenols with 1-adamantanol in the presence of 1-bromoadamantane as well as the
reaction of halogenophenols with 1-adamantanol in trifluoroacetic acid leads to products of monoand dialkylation.
Keywords: alkylation, phenols, adamantane.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 63-70
~~~
??? 54.05
?????? ????????? ?? ????
???????????? ????????
? ??????? ??????????? ?????-?????????
?.?. ???????????,?,
?.?. ???????????, ?.?. ?????????,?*
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
?
???????? ????? ? ?????????? ?????????? ?? ???,
??????, 660036, ??????????, ?????????????, 50, ???. 24
Received 12.06.2013, received in revised form 08.09.2013, accepted 12.01.2014
?????????? «???????» ????? ????????? ?? ???? ???????????? ???????? ? ??????? ???????????
?????-?????????, ?????????? ?????? ?????????????? ???? ?????????? ???????? ? ?????
«???????? ??????? ? ???? ? ?????????????? ???????????» ? ?????? ???????? ?????????
NaOH. ??????????? ?????? ??????? ??????????????, ?????????????? ??????? ?????
???????????? ???????? (56 % ???.) ? ??????????? ?????-????????? 97,5 % ???.
???????? ?????: ???, ??????????????, ???????? ????????, ???????? ???????, ??????????????
???????????, ???????? ?????????, ?????-?????????.
????????
? ????????? ????? ?????? ??? ????????? ????????? ?????? ????????? ??????? ? ?????????? ????? ??????. ?????? ???????????????? ???????????????? ?????? ??? ???????????? ????????? ????? ???????? ?????? ??????????? ???????? ? ?????? ???????? ???????,
?????? ???????? ???????????? ? ??. ????????? ???????? ? ???????? ?????????? [1], ?????????? [2] ???????? ? ?? ????????????? [3]. ????????? ???????????? ? ???????????? ??????
? ?????????? ??????????? ? ?????????? ???????, ??????, ???????, ???????, ??????????? ?????????? ? ?????? ?????????????? ????????? [4-6]. ????????? ?????? ???????????? ????????? ? ??????????? ?????????? ? ?????? ?????????? ????? ??????? ????????????? ??????
??? ? ????????? ??????? ?? ??????????, ???????????? ?????????? ???? ? ?????. ??? ??????????? ????? ?????????????? ????? ??????????????, ????? ??????? ??? ?????????? ?????. ??????????????? ????????????? ?????, ???????????? ?????????? ?????????? ?????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru
# 63 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????????? ?????? ????????? ?? ???? ???????????? ???????? ? ??????? ????????????
????????? ???????? ?? ??????? ?????????????? ???????????????????? ????? ????????????
??????? ?????????? ? ???????????? ?????????? ??? ?????????? ???????? [7].
????? ?? ????????????? ???????? ????????? ??????????? ?????????????? ????????
????????????? ?????????????? ????????????? ????? ? ?????????????? ????????? ????????. ?
?????? [8] ????????, ??? ?? ?????? ????????? ????? ????????????????? ?????????? ?????? ?????????? ?????????????, ??????????? ?????, ???????? ??????????, ??????? ? ????????? ????????? ??????????????? ????? ???????? ? ??????? 32,5 % ???????, ?????????? 97,5 % ???.
?????-?????????. ??????? ??????????? ????????? ?????????????????? ???????????????????? ????????? ?? ?????????? ????? ????????? ? ???? ?????? ? ????? ???????? ??????? ? ????????? ???????? ? ??????????? ??????????????? ???????????? [9]. ?????????, ????????????
??? ?????????? ???????????, ???????? ??????????, ?????? ??????????????? ????????????
??????????????? ? ????????? ?? ????? 97 % ?????-?????????.
?????????? ??????? ???????? ?????????? ?????????? ?????? ? ????? ?? ?????????????
????????? ????- ? ?????????????? ????????????????? ??????? ??? ????????? ???????????? ???????? ? ??????? ??????????? ?????-?????????.
? ?????? ?????? ?????? ???????????? ?????????? ????? ????????? ?? ???? ????????????
???????? ? ??????? ??????????? ?????-?????????. ?? ??????? ?? ?????? ??????????????
???? ? ????? «???????? ??????? ? ???????? ???????? ? ???? ? ?????????????? ???????????» ?
????????? ??????????????? ???????????? ????????.
???? ???????????? ???????? ? ??????????? ??????? ????????????? ????????? ?????? ?
?????????? ???????????? ??????? ?????????????? ????, ???????????? ???????? ??????????? ???????, ?????????? ?? ????? 97 % ?????-?????????.
????????????????? ?????
? ???????? ????????? ????? ???????????? ??? ?????????????? ???? 10330-76. ?????????? ???????? ??????????? ? ???? ?????????? ( % ???): ????????? ? 78,1, ????????????? ? 19,5,
?????? ? 2,4, ?????? ? 2,9, ????????????? ???????? ? 1,6, ???? ? 0,2. ??? ?????? ????? ???,
??????????? ?? ???? ?????? ?? 50-100 ??.
?????????????? ???? ???????????? ? 2-???????? ?????, ?????????? ???????? ?????????????. ? ????? ????????? 50 ? ????, ???????????? ?? ???? ?????? 50-100 ??, ????????
150 ?? ??????? ???????? ???????, 280 ?? ????, 100 ?? 15%-???? ????????? ????????, 25?50 ??
10%-???? ??????? ???????? ?????? ??????? ? ????????? ?? ??????? ??????? ???? ? ???????
2 ?. ??????????? ??????????? ????? ? ????? ??? ??????? ?????????? 96 °C. ????? ???????
???? ???????? ????????? ? ??????????? ????? ??????????? ??? 0,5 ? ??? ??????????? ???????. ?? ????? ??????? ?? ????????? ???? ?????????? ??????????? ????????????? ??????????? ?????. ?? ????????? ????????? ?????????? ??????? ??????????? ????? ????????? ?
??????? ????????. ??????????? ??????? ????????? ????????? ?? ??????? ???????????????? ????? ?? ??????????? ????????? ???, ???????? ? ?? ??????? ????????? ??????????
????????? ???????????????.
??????????????? ???????????? ???????? ????????? ????????? ???????: ? ??????
??????? 1,5 ?, ?????????? ????????, ????????? ??????????? ???????, ??????? ?? ??????? ??????? ?? ????????? 60?70 % ???. ????????? ?????? ??????? ?????????? ?????? ??
# 64 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????????? ?????? ????????? ?? ???? ???????????? ???????? ? ??????? ????????????
??????? ??? ???????? ???????????? ? ??????????? ???????? 10, 15 ? 20 % (??????????? 12)
? ?????????? ???????????? ? ??????? 1 ?. ????????? ??????????? ???????? ????????? ?????????? 70?75 °C ? ?????????? ????????? ? ??????? 1 ? ?? 20?22 °C. ????? ???????????
??????? ???????????????, ????????? ????????? ?? ??????? ????? ? ?????????? ??? ????????? ???????????.
??-??????? ???????? ???? ? ????????? ??? ?????????????? ? ??????????????? ????????
? ??????????? ????? ??-???????????? Vector ? 22 (????? Bruker) ? ??????? ???? ???? 4004000 ???1. ??????? ??? ?????? ???????? ? ???? ???????? ? KBr (3 ?? ??????? / 300 ?? KBr).
??????????? ??????????????? ???????? ?? ????????? ??????????? ?????????? ??1000 HITACHI (??????) ? ?????????? ??????????? 15 kV ? ? ??????????? ?? 100 ?? 10 000
???? ? ??????????? 30 ??.
??????????????? ?????? ???????? ? ?????????????? ?????????????? ?????????????
????-3 ?? Cu K? ????????????????????? ????????? (? = 0,154 ??). ???????? ???????? ??????????? ??????? ???????????? ??????????????? ??????????? ???? ?????????? 1 ????/???.
?????? ????????? ? ????????? ??????????? ????? 2? ?? 5,00 ?? 50,00 ????.
?????? ??????????????? X ???????? ????????? ???????????? ?? ?????????
X
SK
,
SK S A
??? SK, SA ? ?????????????? ??????? ????? ??????????? ????????????? ????? ?? ??????????????? ? ???????? ???????? ????????? [10].
??????????? ???????? ???? ?????-?????????, ?? ?????????????, ???????? ???? ???????,
?? ???????????? ? ?????? ???????, ???????? ???? ??????????? ????, ??????? ? ????????????
???????? ????????? ?? ???? 595-79 [11].
?????????? ? ??????????
?????? ??????? ?????????????? ???? ?????????, ?????????? 27 % ???????? ??????? ?
3,5 % ????????? ???????? ??? ???????? ??????????? ? ???????????? ??????????????? ????????????. ? ????. 1, 2 ????????? ?????? ? ??????? ???????????? ?????? ??????? ? ????????
?? ????? ? ?????? ???????????? ???????? ??? ??????????? ?????????????? 96 °C ? ???????????? 10 ? 15.
??? ??????? ?? ?????? ? ????. 1 ? 2, ???? ???????????? ?????? ??????? ? ???????? ??
0,25 ?? 0,50 % ???. ????? ?????? ?? ????? ???????????? ????????, ??????? ??????????
??????? 1. ??????????? ?????? ? ??????? ???????? ?????????????? ???? ?? ???????????? ??????
??????? ? ???????? ??? ??????????? 10, %
???????????? H2SO4
0,25
0,35
0,50
????? ???????????? ????????*
79,1
75,0
72,5
?????????? ?????-?????????
79,5
81,7
83,0
?????????? ??????????? ???????
1,3
0,6
0,2
* ? ?? ????? ????????? ?????? ????.
# 65 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????????? ?????? ????????? ?? ???? ???????????? ???????? ? ??????? ????????????
??????? 2. ??????????? ?????? ? ??????? ???????? ?????????????? ???? ?? ???????????? ??????
??????? ? ???????? ??? ??????????? 15, %
???????????? H2SO4,
0,25
????? ???????????? ????????*
?????????? ?????-?????????
?????????? ??????????? ???????
0,35
0,50
78,9
74,2
72,0
80,1
82,3
83,6
1,2
0,5
0,1
* ? ?? ????? ????????? ?????? ????.
??????? 3. ??????? ???????????? ?????????? ?????? ?? ????? ??????????????? ???????????? ????????,
?????????? ? ??? ?????-????????? ? ??????? ?? ???????????????
????????????
NaOH, % ???.
????? ????????????
????????, % ???.*
?????????? ??????????????, % ???.
10
63,4
87,8
??????
???????????????
0,63
15
58,3
92,7
0,60
20
56,0
97,5
0,57
* ? ?? ????? ????????? ?????? ????.
72,5?79,1 % ???. ???????? ???? ?????-????????? ? ?????????? ???????? ????? 79,5?83,0 %.
??????????, ??? ?????????? ??????????? ? 11 ?? 15 ?? ????????? ????????????? ??????? ??
????? ???????????? ???????? ? ?????????? ? ??? ?????-?????????.
??????????????? ???????????? ????????, ??????????? ????? ?????????????? ???? ?????? «???????? ??????? ? ???????? ???????? ? ?????? ???????», ????????? ?????????? ??????
????????? ?????????? ?????? ??? ??????????? ????????????? ? ??????? 1 ?. ? ????. 3 ????????? ?????? ? ??????, ?????????? ?????-????????? ? ???????? ??????????????? ? ????????? ????????? ??????????????? ???????? ???????????? ???????? ?? ???? ??? ?????????
???????????? ?????????? ??????.
??-??????? ????????? ???? (???. 1, ?????? 1) ? ???????????? ???????? ?? ???? (?????? 2)
????? ??????. ??????? ??????????? ?????? ? ???, ??? ? ??-??????? ???????????? ????????
??????????? ?????? ?????????? ??? 1511,28 ??-1, ??????????? ??? ????????? ????????? ?????????????? ?????? [12]. ??? ????????? ?? ?????????? ?????????? ??????? ? ???????? ?????????????? ????. ? ??-??????? ?????-????????? (?????? 3) ?? ????????? ? ???????? ?????
? ????????? ??? ?????????????? ??????????? ????????? ???????? ?????? ?????????? ? ??????? 1737 ??-1, ???????? ?????????? C=O-????? ? ????????????? ???????. ????????????
????? ????????? ????????????? ????? ?????????? ? ??????? 1639 ??-1, ??????????????? ????????? ?????????? ?????????????? ??????.
?????? ? ??????? 900 ??-1 ????????????? ????????????? ????????? ?????? ? ???????????
? ????????? ????? C1 ? ??????? ?????????? ??? ?????? ? ???????? ?-??????????? ????????
[12]. ??? ???????????? ? ?????????? ??????????? ????????? ?????????? ???????? ????????????? ?????? ??????, ??????? ?? ???????? ??????? ??????????, ? ????????? ??????????
?????????? D1430/D900 ? ???????? ??????????????? ?? ???????? [13]. ?? ????????? ????????# 66 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????????? ?????? ????????? ?? ???? ???????????? ???????? ? ??????? ????????????
???. 1. ??-???????: 1 ? ???????? ???; 2 ? ??????????? ???????; 3 ? ?????-?????????
????? ????? ??? 897 ??-1 ? ??-???????? ???????????? ???????? (?????? 2) ? ?????-?????????
???????, ??? ?????? ??????????????? ???????????? ???????? (????? 0,63) ????????? ?? 0,57
????? ??? ????????? ??????? ??? ????????? ?????-?????????.
????????, ??? ?????????????? ????????? ????? ??????????? ??? ? ??????? 2? = 1516°, ????????? ? ?????????? ????????????? ????? ?? ?????????? 10 1 ? 101 ???????????????
??????? ????????? [14]. ?? ?????????????? ?????????, ???????????? ??????????? ??????,
???? ??? ???????????, ?? ?????????? ??? ? ??????? 2? = 12°, ????????? ? ?????????? ????????????? ????? ?? ?????????? 101 ??????????????? ??????? ?????-????????? [10].
??? ??????? ?? ??????????? ?? ???. 2 ?????????????, ??? ????????? ???????????? ???????? ?? ???? 10%-??? ?????? ????????? ?????? ??????????? ??? ? ??????? 2? = 15-16°. ?????? ??? ????????? 15 ? 20%-??? ????????? ?????? ???? ??? ????????? ????????, ?? ?????????? ??? ? ??????? 2? = 12°, ??????????? ??? ?????-?????????. ??????????????????? ?????
???????????? ??????? ?????????? ?????-????????? ? ??????????? ???????? ?? ????, ?????????? ????? ????????? 20%-??? ?????? ????????? ?????????? ??????.
? ?????????? ??????????? ???????????? ????????? ???????????? ?????????? ??????
????????? ?? ???? ???????????? ???????? ? ??????? ??????????? ?????-?????????, ?????????? ?????? ??????????? ?????????????? ? ???????????? ????????? ???????????????.
???????????, ??? ?????????????? ???? ?????????? ???????? ? ????? «???????? ??????? ?
????» ? ??????????? ?????? ??????? ????????? ???????? ??????????? ??????? ? ???????
72,0-79,0 %, ?????????? ?? 83 % ?????-?????????. ??????????? ???????? ???????????????
???????????? ???????? ?? ???? ???? ??????????? ???????? ????????? ? ??????? ?? 56 % ?
??????????? ?????-????????? 97,5 %.
??? ??????? ??????????? ?????????, ?????????? ??? ????? ?????????? ??????????????
?????????????? ????, ??? ? ???????????? ????????? ???????????????, ???????????? ?????
# 67 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????????? ?????? ????????? ?? ???? ???????????? ???????? ? ??????? ????????????
???. 2. ?????????????? ???????? ??????????? ?????????, ?????????? ?? ???? ? ????????????
?????????? ?????????? ?????? ????????? ????????????: 1 ? 10 %; 2 ? 15 %; 3 ? 20 %
?????? ??????????? ????? ?????? ????? ? ?? ???????? ??????????? ????????? ?????????????? ?????????. ?? ???. 3 ???? ??????????? ????????? ??????????? ??????????? (???) ???????? ???????????? ????????, ??????????? ?? ???? ? ??????????? 96,7 ?????-?????????.
??? ????? ?? ???. 3, ???? ??????????? ??????? ???????????? ????? ???????, ????????? ?? ????? ????? ? ???????? ????????? ?? 9,5 ?? 15,3 ??? ? ?????????? ?????????
3,7?5,0 ???.
?? ???????? ???????????: ?????????? ?????-????????? ? 97,6 %, ????????? ? 0,08 %, ??????? ????????????? ? 1200, ???????? ???? ?????????????? ? ?????? ??????? ?????? ? 0,28 %,
????????????? ? 130 ?, ???????? ???? ??????????? ???? ? 1,3 % ? ?????????? ???????????
????????? ?????????? ????????? ????????????? ???? 559-79, ?????????????? ? ?????????
??? ?????????? ??????????? [11].
??????????
?????????? ????????????? ?????? ??????????? ???? ? ?????-?????????, ??????????
?????? ??????????? ?????????????? ?????????????? ? ???????????? ????????? ???????????????. ????????, ??? ?????????????? ???? ?????????? ???????? ? ????? «????????
??????? ? ????» ? ??????????? ??????????????? ???????????? ????????? ???????? ??????????? ??????? ? ??????? 72,0 % ???. ? ??????????? ?????-????????? ?? 83,0 % ???.
???????????, ??? ???????? ??????????????? ???????? ?????????????? ???? ???? ??????????? ???????? ????????? ? ??????? ?? 56,0 % ???. ? ??????????? ?????-?????????
97,5 % ???.
? ?????? ???????????? ??????? ????????????? ????????????? ?????? ?????????????
??????????? ?? ???.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????????? ?????? ????????? ?? ???? ???????????? ???????? ? ??????? ????????????
?
?
?
???. 3. ???-??????????? ???????????? ????????, ??????????? 97,6 % ?????-?????????, ???????????
?? ????
?????? ??????????
1. ?????? ?., ??????? ?.?. ?????????: ?????, ???????????????, ??????? / ???. ? ????. ?.:
?????? ????-???, 1988. 512 ?.
2. ??????? ?.?. ?????????? ?????????. ???????????? ?????????? ?????????. ?. II. ?.:
?????? ????-???, 1990. 600 ?.
3. ??????? ?.?. ?????????? ?????????. ???????????? ?????????? ?????????. ?. I. ?.:
?????? ????-???, 1976. 624 ?.
4. Hoenich, N. A. Cellulose for Medical Applications: Past, Present, and Future / N.A. Hoenich //
BioResources. 2006. Vol. 1. ?. 2. P. 270?280.
5. Kamel, S. Pharmaceutical Significance of Cellulose: A Review / S. Kamel, N. Ali, K. Jahangir,
A. El-Gendy // EXPRESS Polymer Letters. 2008. Vol. 2. No.11. P. 758?778.
6. Cellulose Nanocomposites: Processing, Characterization, and Properties / Ed. by K. Oksman,
M. Sain. ? San Diego: American Chemical Society, 2006. 256 p.
7. ???????? ?.?., ?????????? ?.?., ????????? ?.?. ????? ?????????????? ?????? ? ????????? ????????? ? ?????? ?????????? ????????? ?? ???????????? ???????? // ???????? ?
???????. 2008. ?. 49. ? 4. ? 541-551.
# 69 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ??????????? ?????? ????????? ?? ???? ???????????? ???????? ? ??????? ????????????
8. ??? ?.?., ??????????? ?.?. ?????????????? ?????????????? ????????? ?????????? ???????? ? ???????????????? (?????) // ????? ????????????? ?????. 2005. ? 3. ?. 61-73.
9. Kuznetsov B.N., Kuznetsova S.A., Danilov V.A., Yatsenkova O.V., Petrov A.V. Agreen one-step
process of obtaining microcrystalline cellulose by catalytic oxidation of wood // Reac. Kinet. Mech
Cat. 2011, V. 104. ? 2. P. 337-343.
10. ???????? ?.?., ??????? ?.?. ??????????? ?????????? ????????? II ??????????????????? ??????? ??????????? ????????? // ????? ?????????. 1983. ? 2. ?. 10-14.
11. ????????? ?.?., ????????? ?.?. ???????????? ?????? ????????? / ??? ???. ?.?. ?????????. ?.: ?????, 1974.
12. ????????? ?.?., ??????? ?.?., ???????? ?.?. ? ??. ?????? ???????????? ????????? ? ??
???????????: ??????? ???????. ???????: ???-?? ???. ???. ??-??, 2002. 160 ?.
13. O'Connor R.T., Du Pre E., Mitcham D. Application of infrared absorption spectroscopy
to investigations of cotton and modified cottons. Part I. Physical and crystalline modification and
oxidation // Text. Res. J. 1958. Vol. 28. ? 5. P. 382-392.
14. ???????? ?., ???????? ?. ??????????? ??????????? // ????????? ? ?? ???????????.
?. 1: ???. ? ????. / ??? ???. ?. ??????? ? ?. ??????. ?., 1974. ?. 154-182.
Method of Obtaining from Flax
the Cellulosic Product
with High Content of Alfa-Cellulose
Vladimir A. Levdanskya,b,
Alexandr V. Levdanskyb and Boris N. Kuznetsova,b
a
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
b
Institute of Chemistry and Chemical Technology SB RAS,
50-24 Academgorodok, Krasnoyarsk, 660036, Russia
The ?green? method of obtaining from flax the cellulosic product with high content of alpha-cellulose
was developed. It consists of the stages of flax delignification by hydrogen peroxide in the medium
?acetic acid ? water ? sulfuric acid catalyst? and of alkaline treatment by NaOH. Delignification
conditions were selected which allow to obtain with a high yield (56 % mas.) the cellulosic product
containing 97,5 % mas. of alpha-cellulose.
Keywords: flax, delignification, hydrogen peroxide, acetic acid, sulfuric acid catalyst, alkaline
treatment, alpha-cellulose.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 71-78
~~~
??? 615.454.21:547.562.4: 543.422.3:543.544.943.3
?????????? ?????????? ??????????????
????????????? ? ???????????
?.?. ?????????,
?.?. ??????? *, ?.?. ??????????
?
????????? ??????????????? ??????????? ???????????
??????, 634050, ?????, ??. ?????????? ?????, 2
?
??????????? ??????-???????????????? ????????,
??????, 357532, ?????????, ??. ????????, 11
a
Received 07.06.2012, received in revised form 12.11.2012, accepted 08.09.2013
? ?????? ?????????? ???????? ??????? ?????????? ? ?????????? ????????????? ???
?????????????? ??????? ?????????. ??? ???????????? ????????? «???????????»
?????????? ? ????????????? ??????????? ????? ????????????? ? ?????? ???? ????????. ?
???????? ?????????? ??? ?????? ???????? ??????? ????? ????????????????? (III), ?????????
?????? ??????? ?????????? ?? ????????? ? ?????????????? ????????. ?????????? ??????
??????????? ?????????? ???????? ????????? ????? ????????????????? (III) ?? ?????????
??????????, ?????? ?????????? ?????? ??????????? ?????????? ??? ????????????? ?????????
«???????», ??????? ???????? 0,06 ???. ??? ??????????? ?????????? ? ????????????
??????????? ?????????? ? ????????????? ?????????? ?????????????????????? ????????.
????????? ????????????? ???????? ????????, ??? ??? ???????? ???????????, ??? ???
????????? ?????????? ????????? ? ??????????? ?????? ??????????? ????????????? ?????
??? ????????????? ????? ?????. ???????????? ????????? ? ???????? ?? 97,25 ?? 102,75 %.
????????????? ??????????? ??????????? ?????????????? ???????? ?????????? 0,62 %.
???????? ???????? ???????? ?????????????? ? ????????????? ??????? ??????????
?????????? ? ????????????? ?? 0,035 ?? 0,065 ? (r = 0,99930).
???????? ?????: ?????????, ????????????, ????????????? ? ?????? ???? ????????,
?????????????????.
????????
???????? ?? ?????????????? ????????????????? ? ??????????? ????????????, ?????????????? ???????? ????????? ? ????????? ? ????????? ? ??????????? ???????? ?????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: krasnov.37@mail.ru
# 71 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????? ?????????? ?????????????? ????????????? ? ???????????
??????????. ?????? ???????? ? ???? ????? ?????? ???????????????-???????????? ??????,
? ????????? ?????????, ??? 4-?????-2,6-???????????????? [3, 5], ??????? ????????? ???????????????, ????????????????, ?????????????????, ?????????????????, ????????? ????????????????? ?????????? ? ????????? ? ?????? ???????????? [2]. ??????? ?????????? ?????????? ?????????????? ????? ?????????? ?????????? ?????? ????????????.
???? ????????? ?????? ? ?????????? ??????? ??????????? ?????????? ? ?????????? ????????????? ??? ???????? ????????????? ?????? ???????????.
????????? ? ??????
???????? ???????????? ???????? ?????????? ???????????? ? ???????????, ???????
???????????? ????? ???????????? ?????? ?????, ??????????? ???????, ??????????????? ????? ? ??????? ????????????, ?? ????? ?????????? ??? ???????????? ?????????. ? ?????? ?????? ????????????? ?????? ??? ???????????? ? ??????????? ??????????? ?-2. ? ?????? ?????
???????????? ??????? ??????????? ??????? (???) ??????????, ??????????????? ? ?????????
????? ???? ???????? ?????? ?????????? ????????? ???. ??????? ???? ? ??? ??????????
???? ?????????? ?????????? ????????? ???????? 99,8 % ? ??????????? ?????????? ????????
(?-??????? ? 2-?????????-4-???????????).
??? ????????????? ??????????? ?????????? ? ????????????? ???????????? ?????
????????????? ? ?????? ???? (???) ????????. ??? ????????? ? ?????????? ???? ???????? ??????? ????????????? ??? ??????????? ????? 20 °? ? ???????????? ???????? ?????????? ??????? ? ?????????????? ????????? ????????? ?????: «??????? ????-??-??»
? «??????? ????-??-?» (??????), «??????? ??-254» (?????) ? «TLC Silicagel 60 F254»
(Merck, ????????). ???? ???????????? ? ??????????? ???????? ? ?????????? ????? ???????????? 50 ??, ?????????? 25 ?? ??????????, ??????????? ?? ??????? ???????????.
0,002 ?? ??????????? ???????? (4 ???) ???????? ?? ????? ?????? ????????? TLC Silicagel
60 F254 ???????? 5Ч10 ??. ????? ? ???????? ????????? ???????? 0,004 ?? (4 ???) 0,1%-????
???????? ???????????? ??????? ?????????? ? ??????????. ????????? ? ??????????? ??????? ?????? ?? ??????? ? ??????? 3 ???, ???????? ? ?????? ? ???????? ?????????????
? ?????????????????? ?????????? ???????. ????? ??????????? ??????? ????????????
????? 8,5 ?? ????????? ???????? ?? ??????, ?????????? ?? ??????? ? ??????? 5 ???.
?????????? ?????????? ???????????? ???????????? ??????? «??????????». ? ????????
??????????? ????????????:
1) ?????????? ??????? ????? ????????????;
2) ????? 1%-???? ???????? ????? ????????????????? (III) ? 1%-???? ???????? ????? ?????????? ? ??????????? 4:1.
???????????? ??? ????????????? ? ???????? ??? ????????? ??????????? ????? ?????
??? ? ???.
??????????? ??????????????? ?????????? ? ???????????? ??????????? ?????????? ?
????????????? ????????? ?????????????????????? ???????.
????????????? ???????????? ????????. ???? ???????????? ???????? ? ??????????
????? ???????????? 250 ??, ?????????? 80 ?? ?????? ????????? 95%-????, ????????? ?? ??????? ???? (??????????? ???? 80-85 ??) ? ???????? ????????????? ? ??????? 15 ??? ??? ??# 72 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????? ?????????? ?????????????? ????????????? ? ???????????
??????????? ???????????? (?? ??????? ??????????? ???????????). ????? ????????? ?? ????,
?????????? ? ?????? ????? ???????????? 100 ??. ?????????? ????? ????????? 3 ???? ?? 5
?? ?????? ????????? 95%-????, ?????????? ???????? ????? ?????????? ? ?????? ????? ? ???????? ?? ????? ??? ?? ????????????? ??? ????????? ???????????. ??????? ???????????? ?
??????????? ????? ???????? ?????? «????? ?????», ?????????? ?????? ?????? ?????????.
5 ?? ????????? ?????????? ? ?????? ????? ???????????? 50 ??, ???????? ????? ?? ?????
95%-???? ??????? ???????? ? ???????????? (??????? ?).
????????????? ???????? ??? ??????????. ????? 0,05 ? (?????? ???????) ?????????? ???????? ? ?????? ????? ???????????? 100 ??, ?????????? 50 ?? ?????? ????????? 95%-????,
???????????? ?? ??????? ??????????? ? ???????? ??????? ???????? 95%-??? ?? ????? (??????? ?). 5 ?? ???????? ? ?????????? ? ?????? ????? ???????????? 50 ??, ???????? ???????
???????? 95%-??? ?? ????? ? ???????????? (??????? ?).
?????????? ????????? ????????? ? ? ? ???????? ?? ???????????????? ??-2000-02 (??????) ??? ????????? ?????????? ?=282±2 ?? ? ??????? ? ???????? ???? 1 ??, ????????? ?
???????? ???????? ????????? ????? ???????? 95%-???. ?????????? (?) ?????????? ? ????????????? ? ??????? ????????? ?? ???????
X
A � a0 � 5 � 100 � 50 � P
A0 � 100 � 50 � 5 � 100
A � a0 � P
,
A0 � 100
??? ? ? ?????????? ?????????? ? ?????????????, ?;
A ? ?????????? ????????? ??????????? ???????? ??? ????? ????? 282 ± 2 ??;
A0 ? ?????????? ????????? ???????? ?????????? (???) ??? ????? ????? 282 ± 2 ??;
?0 ? ????? ??????? ??? ??????????, ?;
? ? ?????????? ?????????? ? ??????????? ???????, %.
?????????????? ????????? ?????? ???????????? ????????? ? ??????????? ????????
????????? [1].
?????????? ? ?? ??????????
??? ?????????????? ??????????? ?????????? ? ????????????? ???????????? ????? ???.
???? ??????? ??????? ????????????? ??????-?????????? ? ???????? ??????????? 95:5, ??? ???
???????????? ?????? ??????? ???????? ?????????? ??????????, ??? ????????? ???????? [4] ?
??????????? ?????? ?????????????, ????? ????????? ?? ??????? ?? ??????????? ???????????? ????????. ?????? ??????? ????????? ???? ?? ????????? ???????????? ???????? ?????????
?? ???????? ? ?????? ?????????????.
?????????? ???????? ?? ????????? ??? ????????????? ? ??????????. ????????? ? ??????????? ??????? ????????????? ????? ?????????? ?????????????????? ? ????????? ???????
?????????????. ?????? ????????????? ????????? ?????????? ????????? ????? ????????????,
?????? ? 1%-???? ?????????? ????? ????????????????? ? ????? ?????????? ? ????????????
4:1. ? ?????? ?????? ????? ?????????? ?? ????????????? ??????????? ?????????? ????? ?????????? ? ??????????? ?????? ?????????????, ? ?? ?????? ?????? ? ?????? ????????? ?????
???????????? ????????. ????? ???????, ????????????? ????????? ???????? ????? ????????????????? (III) ????? ???????????? ? ?????????? ????????? ????? ???????????? ? ?????????
# 73 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????? ?????????? ?????????????? ????????????? ? ???????????
????????????? ??????? ?? ????????? ? ?????????????? ????????. ??????? ???????? ???????
????? ????????????????? ??? ?????? ? ???????? ?????????? ??? ??????????? ????????? «???????????» ?????????? ? ????????????? ??????? ???. ????? ????, ??? ?????????? ?????? ??????????? ?????????? ?????? ??????????? ?? ?????????? ????????? ?????. ?????????? ??????
???????????? ? ????. 1, ?? ??????? ???????, ??? ?????????? ?????? ??????????? ??????????
??? ????????????? ????????? «???????» ???? ?????, ??????? ???????? 0,06 ???.
?????? ? ???????????? ??????????? ???? ??????????? ???????? ??????????????? ??????????? ? ???????????? ??????????? ?????????? ? ????????????? ??????? ?????? ?????????????????. ???????????? ???????? ???????? ??????????????, ??? ??? ????????? ?????????? ????????????? ???????? ? ??????????? ?????? ??????????? ????????????? ????? ???
????????????? ????? ????? 282±2 ??. ?? ???. 1 ?????????? ??????? ?????????? ????????
?????????? ? ???????? ?????? ?????????????. ?????? ??????? ?????????? ??????????, ???
?????????? ?????? ????????????? ????? ?? ????????? ??????? ?? ?????????? ??????????
??? ???????? ????? ?????.
????????? ???????? ????????? ???????? ??????????? ????????????? [6, 7]. ??????
????????????? ???????? ???????????? ?? ????????? ???????????: ?????????????, ??????????????, ????????????, ?????????? ? ????????????? ???????. ???????? ??????????????
????????????? ???????? ???????? ? ???? ?????????????, ????????????? ?????????????? ?
?????????????????. ? ?????? ?????? ????????? ????????????? ???????? (????. 2) ?? ????????????? ? ??????????? ?????????? 0,05 ? ??? 10 ????????????. ????????????? ???????????
??????????? ?????????? ?????????? 0,62 %, ??? ??????????????? ? ??????? ??????????????
???????? ? ???????? ?????????????.
???????????? ????????????? ??????? ???????? ? ????????? ???????? ????????????????? ???????????, ?????????? ? ?????????????? ????????????? ???????? [6]. ?????? ???????? ??? ???????? ??????????????? ??????????? ? ???????????? ??????????? ?????????? ?
????????????? ????????????? ? ??????????? ????????? ?????? ?? ???? ??????? ??????????
???????????? ???????? ?? 70 ?? 130 % (????. 3). ?????? ???????????? ????????? ?? ????????
??????????
????????????
??????????? ??
????????? ????????
??????????, ???
??????? ???????????
????? ??????????, %
??????????????????
??????????? (Rf )
?????? ???????????,
???
??????? 1. ?????? ??????????? ?????????? ?? ?????????? ????????? ?????
??????? ????-??-?? (??????)
0,003
0,85±0,02
0,06
??????? ????-??-? (??????)
0,003
0,87±0,02
0,06
??????? ??-254 (?????)
0,011
0,76±0,01
0,22
?????????
TLC Silica gel 60 F254 (Merck,
????????)
0,008
# 74 #
0,80±0,01
0,16
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????? ?????????? ?????????????? ????????????? ? ???????????
???. 1. ??????? ?????????? ?????????? ????????? ?????????? 0,005 % (1) ? ?????? ????????????? (2)
??????? 2. ????????????
?????????????
?????????????
????????
???????????
1
0,3539
?????????? ?????????? ?
????????????, ?
0,05006
2
0,3512
0,04967
3
4
0,3581
0,3482
0,04925
5
0,3565
0,05042
6
0,3564
0,05041
7
0,3506
0,04959
8
0,3535
0,05000
9
0,3553
0,05025
10
0,3524
0,04984
?
?????????? ?????????
0,05065
??????????
??????????
?
???????????????
??????????????
?= 0,05001
S2 = 1,88471*10 -7
S = 0,000434133
Sx = 0,000137285
? = 0,95
?(P,f) = 2,26
?X = 0,00031
X±?? = 0,05014±0,00031
? = 0,62 %
??????????????. ??? ????? ?? ????. 3, ?? ?????????? ? ??????? 100,15 % ? ????????? ? ????????
(100±5) %.
?????????? ???????? ????????????? ??????? ???????? ??????????? ??????????????
??????? ?? ???????????? ??? ?????????? ????????????? ???????? ? ????????????? ????? ?
???????? ????????????? ??????? ????????. ??????????? ?????????? ???????? ???????????? ?? ????????? ??????, ?????????? ??????????????? ???????? ? ??????????? ???????? ?
????????? 70-130 % ?? ??????????? ?????????? ? ????????????, ?.?. ???????? ?? 0,035 ?? 0,065
? ?????????? ? ????????????. ?????????? ???????????? ?? ???. 2. ????????? ????????????
?????????? ?????? ??????????? ?????????? (r), ??????? ? ?????? ?????? ????? 0,99930, ????# 75 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????? ?????????? ?????????????? ????????????? ? ???????????
??????? 3. ?????? ???????????? ???????? ??????????? ?????????? ?????????? ? ?????????????
?????????
??????????
?????????? ?
????????????, ?
??????????
??????? ????????
??????????
?????????????, % ?????????????, %
?????????? ?
(n=3)
????????????, ?
0,03479
99,40
0,03500
0,03505
100,14
100,20
0,03537
101,06
0,04081
102,03
0,04000
0,04110
102,75
102,04
101,35
0,04054
0,04554
101,20
0,04500
0,04498
99,96
100,31
0,04489
99,76
0,05000
100,00
0,05000
0,04967
99,34
99,82
0,05006
100,12
0,05549
100,89
0,05500
0,05468
99,42
100,52
0,05569
101,25
0,05919
98,65
0,06000
0,06007
100,12
99,76
0,06031
100,52
0,06440
99,08
0,06500
0,06321
97,25
98,47
0,06441
99,09
??????? ???????? ????????????? (n=21) = 100,15 % (RSD=1,31)
?????????????
???????????
??????????, %
(RSD)
0,83
0,69
0,78
0,42
0,96
0,99
1,08
????? ????????? ?????????????? ??????? ????? ??? y=6,81786x-0,01271. ??????? ???????? ??
0,035 ?? 0,065 ? ????? ????????????? ??? ????????????? ??????? ????????.
????? ???????, ????????? ?????????????????????? ???????? ??????????? ?????????? ? ????????????? ????????, ??? ?????? ???????? ???????? ????????????, ????????,
?????? ? ????????? ?????????? ?????????? ?????????? ? ????????????? ? ????? ????????????.
??????
1. ????????? ????? ??? ??? ???????????? ????????? «???????????» ?????????? ? ?????????????. ? ???????? ??????? ????????????? ???????????? ????? ??????? ? ??????????? ?
???????? ??????????? 95:5, ??? ?????????? ???????????? ??? ?????? ???????? ??????? ????? ????????????????? (III). ???????? ????????? ???????? ??????? ?????? ?????????????
????? ?? ??????????? ??????????.
2. ??????????? ???????? ??????????????? ??????????? ? ???????????? ??????????? ?????????? ? ????????????? ? ??????? ??-?????????????????. ???????? ??? ?????????? ? ?????, ??? ??? ????????? ?????????? ????????? ? ??????????? ?????? ??????????? ?????????????
????? ??? ????????????? ????? ?????, ? ????????????? ??????????? ??????????? ?????????? ?????????? 0,62 %. ???????????? ????????? ? ???????? ?? 97,25 ?? 102,75 %. ???????? ?????
# 76 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????? ?????????? ?????????????? ????????????? ? ???????????
???. 2. ??????????? ?????????? ????????? ?? ?????????? ?????????? ? ????????? ??????
???????? ?????????????? ? ????????????? ??????? ?????????? ?????????? ? ?????????????
?? 0,035 ?? 0,065 ? (r = 0,99930). ???????? ?????????? ??????????????? ?????? ? ???????????
????????????? ?????? ???????? ??? ??????????? ?????????? «?????????????? ???????????»
? «???????????? ???????????» ????????????? ? ??????????? 0,05 ?.
?????? ??????????
1. ??????????????? ?????????? ????. ???. 1: ????? ?????? ???????. 11-? ???. ?.: ????????, 1987. 336 ?.
2. ?????? ?.?. ????????????????? ? ???????????????? ?????????? 4-?????-2,6?????????????????: ???????. ???. ? ????. ????. ????. ?????, 2009. 23 ?.
3. ??????? ?.?., ??????? ?.?., ???????? ?.?., ???????????? ?.?. ????????? ???????? ??????????: ?????????? ??????? ? ?????????? // ????????. 2011. ? 5. ?. 36-38.
4. ???????????? ?.?. ??????-?????????? ???????? ?????? ???????????????-?????????????
?????? ? ?????????? ?????????? ?????????????? ??? ??????????????? ?????: ???????. ???. ?
????. ????. ????. ??????, 2011. 23 ?.
5. ???????? ?. ?., ????? ?. ?. ????????? ? ????????????? ????????????? // ??????????
?????????? ??????. 2004. ?. 48. ? 3. ?. 21-37.
6. ICH (1995) International Conference on Harmonization of Technical Requirements for
Registration of Pharmaceuticals for Human Use, Guideline for Industry. Text on Validation of Analytical
Procedures (Q2A) [?????????????????]. ? ????? ???????: http://www.fda.gov/downloads/Drugs/
GuidanceComplianceRegulatoryInformation/Guidances/UCM073381.pdf /. ? ????. ? ??????.
7. ICH (1996) International Conference on Harmonization of Technical Requirements for
Registration of Pharmaceuticals for Human Use, Guideline for Industry. Validation of Analytical
Procedures: Methodology (Q2B) [?????????????????]. ? ????? ???????: http://www.fda.gov/
downloads/Drugs/GuidanceComplianceRegulatoryInformation/Guidances/UCM073384.pdf /. ? ????.
? ??????.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ???????? ?????????? ?????????? ?????????????? ????????????? ? ???????????
Development of Standardization Parameters
of Suppositories with Mediborol
Vera A. Shelekhovaa,
Efim A. Krasnova and Eleonora F. Stepanovab
a
Sibirian State Medical University
2 Moscowski Trakt Str., Tomsk, 634050, Russia
b
Pyatigorsk Medical and Pharmaceutical Institute,
11 Kalinin Prospekt, Pyatigorsk, 357532, Russia
In this study methods of analysis of mediborol in rectal suppositories for this drug standardization
are presented. We used the method chromatography in a thin layer of sorbent for establishment
of the parameter «Identification» of mediborol in suppositories. Alkaline solution of potassium
hexacyanoferrate (III) was chosen as the detector, because this reagent is specific in relation to the
drug. A threshold of detectability of mediborol was established with an alkaline solution of potassium
hexacyanoferrate (III) on different plates, and the lowest threshold of detectability was observed when
using plates «Sorbfil», which amounted to 0,06 ?g. We proposed the spectrophotometric method for
the assay and uniformity of content of mediborol in suppositories. The validation data showed that
this technique is specific, because it allows us to determine mediborol among other components of the
dosage form at the analytical wavelength. The accuracy of the method ranged from 97,25 to 102,75 %.
The relative error in the determination of the drug was 0,62 %. The method showed linear response in
the range of the mediborol content in suppositories from 0,035 to 0,065 g (r = 0,99930).
Keywords: mediborol, suppositories, chromatography in a thin layer of sorbent, spectrophotometry.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 79-86
~~~
??? 547.589.+547.26? ??11+616-003.725
?????? ???????????????? ???????? ?????????
??????????????? ?????????????
??????????? ??????? ? ????????????? ???????
? ???????? ?????????? ????????
?.?. ??????*, ?.?. ?????????,
?.?. ??????????, ?.?. ?????????,?
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
?
???????? ????? ? ?????????? ?????????? ?? ???,
??????, 660036, ??????????, ?????????????, 50, ???. 24
Received 15.10.2013, received in revised form 17.11.2013, accepted 16.12.2013
?????????? ????? ?????? ????????? ??????????????? ????? ??????????? ??????? ? ????
?? ???????? ????? ? ????????????? ??????? ? ???????? ?????????? ????????. ??????????
??????????? ??????? ???????????? ?????????????? ?????? ?????????????? ???????????
??????? ? ??????? ????????????, ??????????? ???????? ??????????????? ???????
???????? ? ??????? 47 %.
???????? ?????: ??????????????? ??????? ????????, ??????, ???????????? ???????????
???????, ????????????? ?????, ????????? ???????.
????????
????????????? ?????? ??????????? ???????????? ???????? ??????????, ??????????
?? ????????? ????????, ???????? ? ????????? ????? ??????? ?????????????? ???????????
??????? ????????????? ???????.
?????? ???? ? ???? ??????????? ????????? ????????? ???????????, ??? ?????????????
?????????? ?????????? ???????????. ????????, ??? ??????????? ??????? ???????? ???????
???????? ????????????? ??????????, ? ????????? ?????????????????, ?????????????????,
???????-??????????? (???. 1).
??????????????? ? ????????????????? ?????????? ??????????? ??????? ?????????? ? ?????????? ??????????????????? ?????????. ???????????? ????????, ??? ? ???? ???????
??????????? ??????? ? ?? ??????????? ??????????? ?? ????????????? ???????? ????????? ??-
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru
# 79 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ?????? ???????????????? ???????? ????????? ??????????????? ??????????????
???. 1. ??????? ??????????? ???????
??????????? ?????????, ??????????? ??? ??????? ????????????? ??????????? [1?3]. ??????
?????? ????????????? ??????????? ??????? ? ???? ???????????? ?? ?????????? ??-?? ????????? ???????? ? ????????, ???????? ???????????? ?????.
??????? ????????????? ?????????? ?? ?????? ??????????? ??????? ? ?? ??????????? ?
??????????? ???????? ???????? ???? ??? ??????? ???????? ???????????? ???? ???? ??????????.
??? ???????? ???????????? ???? ????????????? ? ???? ?????????? ??????????? ???
???????? [4?6]:
?) ????????? ?????????? ????????? ? ???????????????? ? ?? ????????????;
?) ??????????? ?????????? ? ???????????? ?????????? ? ????????? ??????????? ??????? ? ?????? ?????????? ? ??????? ? ??????? ????????;
?) ??????????? ???????????? ????????? ????? «????????» ? ???????? ???? ???????????? ???????? ??????? ??????????? ?????????????? ????????? ??????????? ?????. ?????
????????????? ???????? ????????? ??????????????? ???? ????????, ?? ??? ??????, ??????????? ???????????? ?????????. ???? ?????? ????? ?????? ??????????, ???????????? ??? ????
?????? ???????, ??? ?????? ???????????? ???????????? ????.
?????? ????????? ??????????????? ????? ??????????? ??????? ?????? ? ??????? [5]. ??? ???????? ??????? ? ???, ??? ? ??????????????? ??????????????? ????????, ?????????? ???????????? ?????????? ???????????? ??????????????? ??????, ????????????????? ?????????-????????, ????? ???? ??????? ?????????? ?? ?????????-??????
????????? ??????????? ??????? ?? ??????????? ??????? ?????????? N-????????????????
?
N,N-????????????????????????????
?
??????????????????????????????????????? ???????. ? ??????????, ??? ?????????? ??????, ??? ??????? ??? ???????? ????? ?????????? ? ?????? ???????? ????????? ?????????-??????? ?? ?????? ??????????? ???????
(???. 2).
? ??????????? ??????? ??????? ????????? ??????????????? ????? ??????? ??????? ????????????? ???????? ????????????? ???????????????? ?????????? ??????????? ???????, ???
??? n ?????????? ? ????? ??????? ????????? (n = 0,1-33,9 ???. %), ? ????? ??????? ???????????
?????? ?????????-?????? ?? ?????? ?????? ??? ???????????? ????????????? ???????? ? ?????? ??????.
# 80 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ?????? ???????????????? ???????? ????????? ??????????????? ??????????????
???. 2. ??????? ???????????????? ???????? ?????????? ???????? [5]
? ????? ? ?????????????? ????????? ??????????????? ???? ??????????? ??????? ? ??
??????????? ????? ?????????? ?? ??????????? ?????????????? ????????? ?????? ? ??????????????? ????????? ???????? ?????????? ???????.
? ????????? ????? ???????? ??? ??????????????? ??????????? ?????????, ??????? ??????? ?????????? ? ???????? ??? ???????? ??????????????? ???? ????????????? ??????????, ???????????????? ? ?????????? ????? [6]. ????????? ?? ?????? ???? ????????? ?????
???? ???????????? ??? ???????? ? ???????? ???????????? ????? [7]. ? ???????? ?????? ???????? ???? ??? ?????? ????????????? ?????. ????????????? ????? ???????? ??????????
???????????? ??????????, ????????? ?????????? ? ???????? ???????? ????????????? ?????????? ? ??????????? ????????????????, ?? ????????? ??? ?????????, ????????? ? ????, ??
????? ????? ? ??????.
? ?????? ?????? ?????? ????????????? ???????? ????? ?????? ??????? ???????????????
????? ???????????? ??????????? ??????? ????? ???????????? ?????????????? ?????? ??
?????????????? ? ???????? ?????????? ????????.
????????????????? ?????
??????????? ??????? ???? ????????????? ?? ?????????? ???? ???????? [8]. ? ???????????? ???????? ?????? ????????? ???????? ? ???????? ?????????? ?????????? ??????? ??????
(??????? ????????? ????????? ? ???????????? ?????? ???????). ????????? ???????? ? ???????
? ??????? 7 ? ??? 0 °?. ?????????? ??????????? ??????? ???????? ? ????? ???? ? ???????????? ??????? ???????. ?????????????? ?????? ?????????. ??????????? ??????? ??????? ?? ?????????? ????? ??????????? ?? ???????? ????????, ???????????? ??????? ????????.
??? ??????? ?? ???????????? ???????? ??????????? ??????? ?????????? ? ????????? ????.
????????? ???? ????? ????????? ?????????? ??????. ????? ????????? ???? ?????????? ?
??????????? ??????? ????????? ???????? ??????? ? ???????? ????????. ??????????? ???????
???????? ?? ???????? ?????. ????? ??????????? ??????? ?????????? 47 %.
# 81 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ?????? ???????????????? ???????? ????????? ??????????????? ??????????????
? ??????????? ???? ???????? ????? ??????? ???????????? ?????????? ??????? ????????? (7 ?) ? ???????????????? ???????? ????????? ? ???????.
????????????? ?????????? ??????? ????????? ?????????? ??????????? ???????????
??????? ? ????????? ????????? ? ?????????? ????? ?? ????????? ? ???????. ? ??????????
???????? ???????????? 6?7 ????? ????????? ????????? ?? ???? ??????????? ???????. ? ?????????? ????? ????? ????????? ??????? ????????? ?? 20?30 ???. ????? ??????????? ???????
???????? 55 %.
????? ????????? ? ??????? ??????? ???????????? ?????? ??????? ??????????? ???????
? ???????????? ????????? 250?252 °?.
???????????? ??????????? ??????? ????????????? ?? ??????????? ??????? ? ?????????????? ? ????????? ???????? ?? ???????? [9].
??? ????????? ??????? ???????????? ?????????????? ?????? (???) ??????????????
??????????? ??????? ??????? ????????? ????????? ????? ?? ???????????? ??? ?????
????????? ?????????????? ????????? ??????? ?? ?????? ??????????????? ? ?? ??????
???????? [10].
???????????? ??? ??????????????? ?? ?????? ???????-??????? ???????????? ?
?????-?????????-?????????? ???????? ??? 0 °?. ? ?????????? ??????? ???????? ???????,
??????? ???????? ???????? ????????????? ? ??????. ? ??? ??-??????? ???????????? ?????? ?????????? ??? 1714 ? 1176 ??-1, ??????????????? ????????? ?????????? ?????? ?=?
? ??? ??????? ??????. ????? ????, ???????????? ?????? ?????????? 1603 ? 1489 ??-1,
??????????????? ????????? ?????????? ???-?????? ??????????? ??????, ? ????? ?????
??????????? ??? ????????????? ?????? ??????? ?????? ??? 710 ??-1, ??????????????? ?????????????? ?????????????? ?????????? ???-?????? ????? [11]. ? ??-??????? ????? ?????????? ??????? ?????? ??????????, ??????????????? ????????? ?????????? ????????????? ?????? ? ??????????? ??????.
???????????? ??? ??????????????? ?? ?????? ???????? ????????? ? ????? ???????. ?
???????? ????????????? ????????? ???????????? ???????. ????????? ??? ? ??????? ??????????? ????????? ?????????????? ? ??????? ??? 0 °?, ? ??????????? ?????????? ???????????
?? ?????????. ? ??-??????? ????? ?????????? ??????????? ?????? ??????????, ??????????????? ????????? ?????????? ????????????? ?????? ? ??????????? ??????.
?? ????????? ???? ????????????????? ?????? ??? ?????? ????? ? ???, ??? ????????????
??? ?????????????? ??????????? ??????? ????????????? ????????? ?? ?????? ????????
???????. ? ???? ?????? ??? ????????? ? ????????.
???? ????????? ??????? ?????? ????????????? ??????? ??????????????? ??????????
?????? ?????? ????????????? ????????????? ?????, ????????? ?????????? ??? ? ?????? ?????? ??????????? ? ???????????? ??????????????? ????????????? ?????????: ?????????????
????? ??????????? ? ???????????? ?????????????, ? ???????????? ? ? ????.
??? ???????? ??????? ???????? ?????????????? ?????? ? ?????????? ?????????????
??????????? ??????? ? ????? ?????????????, ??? ?????????? ????, ??????????, ?????????????, ??????? ???????? ? ??????, ??? ??????????? ??????????? ???????????? ??????????? ???? ?????????? ?????????????? ????????????? ? ??? ????????????? ?????????????.
# 82 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????, ?.?. ????????? ?????? ???????????????? ???????? ????????? ??????????????? ??????????????
???. 3. ????? ???????????? ?????????????? ?????? ?????????????? ??????????? ???????
???? ??? ????????? ????? ???????????? ?????????????? ?????? ? ???????? ?????????? ????????, ??????? ????????? ?????? ???????? ????????????? ????????????? ???????? ?
????????? (???. 3).
????? ????, ???? ????? ????????? ???????????? ??????????? ????????????? ? ???? ???????????? ????????????, ??? ????????? ????????? ?????????????? ?????? ? ?????? ?? ??????
????.
? ???????? ????????????? ?????????? ???????? ???? ??????? ?????? ???????????? ?
???????? ?????????? ???????? [12] ?????????????????????????? (?????) ? ??????????????????????? (????). ? ???????? ???????????? ????, ?????????? ???????????? ???????????
???????, ???????????? ????????? ???????, ?????? ? ??????.
????????????? ????? (???? 10779?78) ??? ?????????? ?????????? ? ??? ??????? ?????? ?? 0,5 % ????????? 3 ???? ??????????? ??????????? ??????? ? ??????? 1 ? ??? 40 °?.
? ???????????? ?????????? ????? ???????????? 50 ??, ?????????? ????????, ??? ??????????? 0 °? ? ????????? ?????? ???????? ?????? ??????? ?????????????? ??????, ????? ?????? ??????? ?????????? ?????? ? ??????????? ?????????? ???????? ?? ?????? ????????????
??????????????? ????.
? ????? ???????? ??? ??????????? ????????????? ????????? ????? ??????? ???????
????????????? ??????????? ??????? ? ???????????? ????????????. ????????????? ?????????? 2 ?. ???????????? ???? ????????, ?????? ???? 2 ???? ?????????????? ?????????? ??????, ???????????????? ???????????? ??????? ???????? 1:10 ?? ?? = 7 ? ?????? ????????????
? ??????. ???????? ?????? ???????????????, ????????? ????????, ?????? ?? ???????.
??-??????? ????????? ???????? ? ?????????????? ???????????????? Vektor-22 (Bruker)
? ??????? ???? ???? 400?4000 ??-1. ??????? ??? ???????????? (2 ??) ?????????????? ? ??????? KBr. ????????? ???????????? ?????????? ???????, ???????? ????? ???????? OPUS,
?????? 5.0.
?????????? ? ??????????
??? ??????????? ???????? ????????????? ??????? ???????????? ?????? ??? ???????????? ? ????????????, ??????????? ??????????? ?????????. ??????? ??????????? ???????????? ??????????? ??????? : ????????????? ????? ???????? ?? 1:5 ?? 1:10 (?? ??????? ?? ????
???????????? ????? ?????????????? ??????). ???????????? ?????????????? ?????? ? ????
??????????? ?? 4 ?? 6 %. ??????? ??????????? ????????? ?????? : ??? ?? ???? ?????? ????
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?.?. ?????, ?.?. ????????? ?????? ???????????????? ???????? ????????? ??????????????? ??????????????
?????????? ? ?????? 1,5. ??????? ??????????? ??????????? ?????????? ???????? : ???????????? ??????????? ??????? ?? ???? ?????? ?????????? ?????????? ? ?????? 0,70.
???????, ??? ???????????? ?????????????? ?????? ????? ????? ??? ??????? ??????????? ???????????? ????? ?????????????? ?????? : ???????????? ??????????? ??????? 5:1. ???
??????? ?????????? ????????????? ??????? ???????????? ?? ??????????.
??????? ???????? ??? ????????????? ?????????? ??????????????? ???????? ????? ???
????????????? ???????????? [13]. ???????? ??????????? ???????? ??????????, ?? ????????????? ? ????? ???????????? ????????????. ?????? ?? ????????? ????????????? ????????
??????, ??? ????????????? ???????? ??? ??????? ?????????? ????? ???????????????? ????????. ? ??????? ???? ? ?????? ??????? ???????????? ??????????? ?? ???????.
??????????? ???????????? ???????????? ??? ?????????????? ?????? ? ?????? ????, ??????? ?????????? 4 %. ???? ???????????? ???????? ? ?????? ???? ????????? ??? ????????,
?? ??? ???????? ? ?????????? (??????? ??????, ???????????, ???????????? ????) ??????????
??????? ?????????? ???????????, ??? ??? ??????? ???????? ? ??????.
???? ???????????, ??? ???????????? ?????????????? ?????? ????? ????? ? ?????? ????????????? ? ???????? ???????????? ?????????? ???????? ?????, ? ? ???????? ????????????
???? ? ???????????? ??? ???????. ??? ????????????? ? ???????? ???????????? ??????????
???????? ???? ????????????? ????? ?? ??????? ??????????? ?? ? ????? ?? ??????????????
?????????????.
?????????? ????? ???????????????? ???????? ??? ??????? ??? ????????????? ? ???????? ???????????? ?????????? ???????? ?????, ? ? ???????? ???????????? ???? ? ??????? ?
???????? 47,5 %.
??? ?????????????? ????, ??? ???????????? ?????????????? ?????? ?????????????? ??????????? ??????? ????? ????? ? ??????? ??????????????? ????????, ???????????? ?????
??-?????????????. ? ??-???????? ??????????? ? ???? ????????????? ???????? ???????????? ??? ?????? ??????????, ??????????????? ??????? ????????????? ?????: ?????? ?????????? ??? 1799 ??-1, ??????????????? ????????? ?????????? ????? ?=?, ? ??????????? ?????? ??? 1143 ??-1, ??????????????? ????????? ?????????? ???????? ????? ???, ????????? ??
???? ????????????????? ????????????? ????????? ??? = ? (??) ? ????? ?????????????
?????? [11]. ? ??-??????? ??????????? ??????? ??? ?????? ?????????? ???????????. ??????
?????????? ??? 1705 ??-1, ??????????? ??? ????????? ????????? ????-??????, ? ?????? ?????????? ??? 1631 ??-1, ??????????? ??? ????????? ????????? ??????? ???????-?????????? ?????
??????????? ???????, ????? ???????????? ? ? ??-??????? ?????????????? ????????.
??? ????? ??????? ?????????????? ??????? ????????????? ????? ? ??????????????? ???????? ???????? ??? ???????? ????????, ??????? ?????? ????????? ??? ?????. ???????? ???????? ????????? ? 10%-??? ?????? ???????? ?????????? ?????? ??? ??????????? 70 °? ?
??????? 0,5 ?. ??????????? ????? ???????????????? ???????????? ????????? ??????? ??????? ??? ????????? ??????????? ? ??????? ???????, ?????? ??????????? ??? ? ??????. ???
? ??????????????, ? ??-???????? ??????????????? ????????? ?? ??????????? ?????? ?????????? ??? 1799,5, 1143 ??-1, ??????????????? ??????? ????????????? ????? ????? ????????????? ??????? ? ???????? ??????????? ???????. ?????? ?????????? ??? 1705 ? 1631 ??-1
????? ???????????.
# 84 #
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???????? ???????? ??????????????? ????? ??????????? ??????? ? ???? ?? ???????? ????? ?
????????????? ???????. ??????? ??????????? ??????? ?????????? ?????? ???????: ???????????? ?????????????? ?????? ? ?????? ???? 4 %; ??????????? ????????????? ????? : ???????????? ??????????? ??????? 5:1; ??????????? ?????????? ???????? ? ??????????????????????????; ???????????? ???? ? ???????????, ??????; ??????????? ??????? 0 °?.
? ????????? ???????? ??????? ???????????????, ???????? ????????????? ?????????????? ??????????? ??????? ????????????? ????? ? ??????? 45?47,5 %.
??????
??????? ??? ????????? ???????????????? ????????? ??????????? ??????? ? ????????????? ??????? ???????????? ??????? ???????????? ?????????????? ?????? ?? ?????????????? ? ???????? ?????????? ????????.
?????????? ??????????? ? ???????????? ?????????, ??? ??????? ???????????? ?????????????? ?????? ?????????????? ??????????? ??????? ???????? ? ??????????? ????????,
?????????? ???????????? ? ????.
?????? ??????????? ??? ?????? ??????? ??????????? ?????????? ???????? ? ??????????????????????????.
??????? ???????????? ????, ?????????????? ?????????? ????????? ???????, ? ???????????, ??????.
? ??????????? ???????? ??????? ??????? ??????????????? ????????????? ?????, ???????? ????????????? ?????????????? ??????????? ??????? ? ??????? 45?47,5 %.
?????? ??????????
1. Lee Kuo-Hsiung, Morris-Natschke Susan L. Recent advances in the discovery and development
of plant-derived natural products and their analogs as anti-HIV agents. // Pure and Appl. Chem. 1999.
V. 71. N. 6. C. 1045-1051.
2. ????????? ?.?., ??????? ?.?., ????? ?.?., ??????? ?.?., ????????? ?.?. ??????? ? ???
???????????. ????? ? ????????????? ?????????? // ????? ? ????????? ??????????? ????????.
2005. ? 13. ?. 1-30.
3. ??????? ?.?., ?????? ?.?., ???? ?.?., ?????????? ?.?., ?????? ?.?., ??????? ?.?., ???????? ?.?., ?????????? ?.?. ??????????? ??????? ? ?? ????????????? ??????????? ? ????????????? ???????????????? ??? ???????????? ???????? // ?????? ??????????? ? ????????????????? ????????. 2005. ? 4. ?. 53-59.
4. ?? ???? ???, ?????? ?.?., ?????????? ?.?., ?????-????????? ?.?. ? ??. ??????
??????????? ??????? ?? ???????? ? ???????????? ?? ????????????? ? ??????? ??????? //
??????. ?????. 1998. ?. 24. ? 10. ?. 787-793.
5. ?????? ?? 2253657. ?????????? ??????????????? ??????????? ?????????????? ?
?????? ?? ????????? / ???????? ?. ?., ?????? ?.?., ??????? ?.?., ????????, ????? ?.?. ?????.
10.06. 2005.
6. ???????? ?.?. ???????? ??????-?????????????? ??????????. ?.: ???????????,
2006. ?. 36.
# 85 #
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?.?. ?????, ?.?. ????????? ?????? ???????????????? ???????? ????????? ??????????????? ??????????????
7. ?????? ?.?. ????????????? ????? ? ??? ???????????. ?.: ???-?? ???????? ????
????, 1960. ?. 1. 552 ?.
8. ????? ?.?., ???????? ?.?. ?????? ????????? ??????????? ???????. ?????? ?? ?
2333916, 2008, ?? ? 27.
9. ???????? ?.?., ???????? ?.?., ???????? ?.?., ??????? ?.?. ?????? ???????????
??????????? ???????, ?????????? ?????????????? ????????? // ????? ??????. ????. 2002.
? 4. ?. 276-283.
10. ???????-????????? ?.?. ?????? ???????????? ? ???????????? ?????. ?: ?????, 1969.
233 ?.
11. ???????????? ?., ??????? ?., ?????? ?. ?????????????????? ????????????? ???????????? ??????????. ?.: ???, 1974. 164 ?.
12. ????????? ???????. ?????, ???????????? ? ?????????? / ??? ???. ?.?. ???????. ?.:
?????. 1991. 159 ?.
13. ???????? ?.?., ???? ?.?. ???????????? ?????? ? ?????????? ????????. ?.: ?????,
1982. 184 ?.
Synthesis of Water-Soluble Polyester
by Interaction of Betulonic Acid Chloride
with Polyvinyl Alcohol in Conditions
of Interphase Catalysis
Tamara I. Kogaya, Nadezhda M. Svirskayab,
Natalia M. Ivanchenkob and Boris N. Kuznetsova,b
a
Siberian Federal University
79 Svobodny, Krasnoyrsk, 660041, Russia
b
Institute of Chemistry and Chemical Technology SB RAS,
50-24 Akademgorodok, Krasnoyrsk, 660036, Russia
New method of water soluble ester of betulonic acid and polyvinyl alcohol synthesis in conditions of
interphase catalysis was developed. Betulonic acid chloride was used for polyvinyl alcohol acetylation.
Optimal conditions of betulonic acid chloride interaction with polyvinyl alcohol and effective phasetransfer catalysts were found which make it possible to obtain the soluble ester with yield to 47 %.
Keywords: water soluble polyester, synthesis, betulonic acid chloride, polyvinyl alcohol, interphase
catalysis.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 87-99
~~~
??? 544.472.2; 547.458.8
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?.?. ???????, ?.?. ??????,
?. ???????-???????,?, ?. ??????, ?.?. ?????????
?
???????? ???????? ??. ?.?. ????????? ?? ???,
??????, 630090, ???????????, ??. ??. ???????????, 5,
?
???????? ????? ???????????????? ??????????
???????, 33608, ??????, ?. ?????, ????,
????? ??????? ????????, 87
?
??????????? ?????
???????, 33405, ??????, ?????. ?? ?? ??????????, 1, 351
?
????????????? ??????????????? ??????????? ???????????,
??????, 630092, ???????????, ??. ?. ??????, 20
?
???????? ????? ????? ?????????? ??? ????????,
????????, 220141, ?????, ??. ?. ???????, 36
Received 26.12.2013, received in revised form 18.01.2014, accepted 10.02.2014
??????? ????????? ????????????, ??????????????? ??? ??????????? ????????? ?
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?????, ???????? ?? ?????? ???????????????? ??????????? ????????? «???????-4» ???????
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? ???????? ????????? ??????????? ?????????????? ???????????????????? ?????????
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???????? ??????? ? 5-????????????????????? ? ????????????? ???????? ?? 46 ?
22 %. ????????? ??????????? ???????????? ?????????? ? ???????????? ?????????????
????????, ??? ???????? ????????????? ???????? ???????????, ??????????????
??? 200 °?.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: gromov_n_v@inbox.ru
# 87 #
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????????
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5-?????????????????????.
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???????? ?????? ?????????? ??????????????, ???????? ? ????????????? ?????????? ????? ????????? ????????? ?????????? ??????? ?? ??????????????? ????????????? ????? [1].
???????????????? ???????? ?????????????? ????????????? ?????? ?? ?????? ??? ??????????
? ????????? ??????????????, ?? ? ??? ???????????? ??????????????? ? ?????????????? ??????????? ?????: ??? ?????????? platform molecules, ?.?. ??????? ???????-????????, ? ??????
??????? ? ???? ?? ???????????, ????? ??? 5-????????????????????? (5-???), ??????????,
???????????, 2,5-????????????????? ??????? ? ??. [2-12]. ????? ????, ??????????? ???????? ? ?? ????????????? ? ?????????????? ? ?????????? ????????? ?????????? ???????? ??????????? ???????, ????????? ??????????? ? ????????? ??????????? ????, ??????????? ???
??????????? ??????????? ????? [2-12]. ???????? ??????????? ???????????????? ????????
???????? ?????????, ?????????? ??????? ????? ????????? 60 % [13-14]. ? ?????????? ???????
?????????? ????????? ??????? ????????? platform molecules ?? ????????? ????? ?????????
? ????????? ???????? ? ? ??????????? ????????? ????? ????????????? (?????????? ? ?????????????) [15-19]. ????????? ???????? ? ?????? ????? ?????????????? ???????? ????????????? ???????? ????????? ?????? ????????? ????????????, ? ????? ??????? ????????? ?????????. ?????? ?????????? ????????? ?????? ??? ????????? ???????? ? ?????????? ??????
?????? ???????????? ? ?????????? ????????, ??????????? ???????????? ??????? ???????????? ??????? ??????? ? ???????? ????????? ? ????????? ???????????? ?? ??????????? ?????.
????????????? ??????? ????????? ????????????? ??? ????????? ????????? ???????? ??????
????????? ????????.
????????????? ???????????? ????????? ????? ???????????? ?? ??????? ?????? ??????? ????????? ????????????? ????????? ????????????, ????? ??? ?????? ? ???????????????? ??????? ???????, ???????? ? ????????, ????????, ?????????????? ??????, ??????????,
??? ?????????? ????????? ????????? ???????????? ?????????? [20-23]. ????????, ?. ???? ?
???????? ???????? ????????? ???????? ???? ??????? ????????? ?????????????. ?????????????? ?????????? ??????????????? ???? ? ????????? ??? ????????? ?????????? ?????? ????????? ?????????????, ? ?????? ??????? ? ??????????? ??????????????? ??????????? ?????????
????????? 40 % [21, 22]. ????? ????????, ??? ?????? ?????????????????? ?????????? ???????? ?? ????????? ???????????? ??????????.
???????? ???????????????? ??????? ?????????? ??????????? ?????????? ??????????
???????? ????????? ?????? ????????, ??????????? ??????? ?? ??????????? ???????????? [2026]. ??????? ????????? ????? ?????? ???????? (???????????, ????? ???????? ? ????????????
?????? ???????) ????????? ???????????? ??????? ?? ???????? ?????????? ?????????????.
????????, ?????????? ??????????? ????????????? ????? ? ????? ?????????? ??????????? ??
??????????? ????????? ?, ??? ?????????, ? ????? ?????????? ?????????????. ?????? ??? ?????
??????? ???????????? ?????????? ?????????? ???????? ?????????????? ????? ??-?? ???# 88 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
?????? ????????? ????????? ???????? [23]. ????????????? ???????????? ?????????, ? ?????????????, ? ???????????? ?????????????? ????? ?????? ???????????? ?? ???? ?? ?????????????
?????????? ? ????????? ????????? ?????????, ??????? ????????? ? ??????? ??????????????? ????????.
???????? ???????? ???????????? ????? ????? ?????????? ????????? ????????????? ??
?????? ???????????????? ????????????? ??????????? ????????? ????? «???????» [27-28]. ????????? ????? ?????????? ???????? ??????????? ???????? ???????? ???????? ????????????
? ?????????? ??? ?????????????, ? ????????? ??????? ????????? ? ?????????????? ? ??????
??????????? ?????????????? ??? ????????? ???????????? ????????? [29-33]. ?????? ?????? ??????????? ?????????? ????????????? ?????????? ????????? ??? ??????? ??????????? ???? ??????????? ?????????, ??? ??? ?????????? ????????? ????? ??????? ?? ??????????
??????? ?????????? ????? ?????????? ??????????.
????? ?????? ?????? ???? ?????????? ?? ?????? ????????????? ???????????????? ??????????? ????????? ????? «???????» («???????-4») ??????????, ?????????????? ? ??????????? ?? ????????? ? ??????????? ?????????????? ???????????? ?????????? (??????? ?
5-???) ??????? ????????? ????????????? ????????? ?????????. ??? ????????? ?????????????, ?????????? ?????????? ??????????, ???????? ????? ??????????? ??????? ????????????? «????????-4», ??????????? ?????????? ? ????????? ???????? ?????????????? ????????
?????????????, ? ?? ?????????????? ????????? ? ???????? ????????? ??????????? ?????????????? ?????????.
????????? ? ??????
? ?????? ?????? ??? ??????????????? ??????? ? ???????? ?????????? ???? ??????? ?????????????? ????????? ?????????? ???????? ????? «???»: H2SO4 (???????), NaOH (Panreac),
????????? (??????? < 0,10 ??, ??? «??????», ?????-?????????), 5-?????????????????????, D-???????? (Sigma-Aldrich), D-??????? (Sigma-Aldrich), D-??????? («??????», ??????),
D-?????????? (Alfa Aesar), ??????????? ??????? (Acros Organics). ????? (99,998 %, ???? 1015770, OAO «?????????», ???????????, ??????) ????????? ? ???????? ????????? ???? ? ????????.
????, ????????? ?? ????????? Milli-Q, (Millipore, ???????), ?????????????? ??? ????????????? ???? ?????????.
????????? ????????? ????????? ? ??????????? ???????? «?????????-4?» (??? «?????????», ?. ???????????, ??????). ??????? ?????????: ????? ???????? 1300 ??, ????? ?????????
50 ?, ????? ????? 200 ?, ??????? ????? 10 ??, ????????? ??????? ??? 75 g, ????? ?????????
10 ???.
????????? ??????? ?????? ????????? ????????? ? ??????? ??????????? ??????????
«??????-5» (??? «??????-?», ?. ??????, ??????), ??????????? ???????? ???????????. ??????? ??????? ?????? ????????? ?????????? ??? ??????? ??????? ??????????? ???????? ???????? ?? ????????? ????? 100 ??????, ??????????? ?? ????????????????.
??????????????? ?????? (???) ???????? ????????? ?? ????????????? Bruker D8 (????????) ? ?????????????? ????????? CuK? (? = 1.5418 ?) ??? ???????????? ?? ?????? ? ?????????? 0.05° ? ????????? 2? ?? 10 ?? 40°. ?????????????? ???????????? ?? ????????? ???? (101,
10?, 021, 002, 040 ? ???????? ?????????) ? ?????? 2?, ???????: 15,2 16,8, 20,6 22,7 34,1 ? 21,5
# 89 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
?????????????? [34]. ??????? ??????????????? ????????? ???????????? ??? ????????? ????? ???????? ????? ??????????????? ????????? ? ????????? ??????? ???? ?????.
??????????? ????????? ?????????????? ????????? ????????? ???????? ???????? ????
16932-82 (??????) ??? ??????????? 103±2 °?.
??????? ?????????????? ????????? ?????????? ????????????? ????????? ?? ????????????? ????????????? ??????????? ????????? «C??????-4» (???????? ??????? ??????????? ?????????????, ?. ????) ????? ????????????? ? ????????????????? ????????? ??????
??????? ?? ????????, ????????????? ? ?????????????? ?????????? ?????? [23]. ??????? 1 ?
«C???????-4» ? 15 ?? ????????? H2SO4 ???????? ? ?????, ?????????? ???????? ?????????????, ??????? ????????? ?? ????????? ??????????? ?????????????. ??????????? ???????????? ? ??????? 10 ?. ?????????? ??????? ???????? ?? ?????? ??????? ???????????, ????????? ??????? ????? ?? ??????????? ???????? ?? ????????? ??? ? ?????? ?? ???????. ???
???????? ????? ???????????? ????????????? ????? ??????? ???????????? ? ??????????????? ????? ??? 190 °? ? ??????????? ????????????? ? ??????? 3 ?, ????? ???? ????? ????????
?? ??????????? pH, ?????? ??? 150 °?.
?????????? ?????????????? ???????? ??????????? ?? ????????? ????????? N2 ??? 77 ?
?? ????????? ASAP-2400 (Micrometritics, ???). ??? ??????? ?????????????? ????????????
? ??????? ??? 130?150 °C. ??????? ??????????? ???????????? ?? ?????? ??? ? ?????????
STSA, ? ????? ????????????? ??????? (? ???????? ????????? ???????????? ????? Cabot BP
280). ????????????? ??? ?? ??????? ????????? ?? ????????? ???????? ???????? QSDFT ?
NLDFT.
???????????? ??????? ????????? ?????: ?????????, ?????????, ????????????? ? ??????????? ? ?? ??????????? ?????????? ????????????? ?????????? ????????-???????? ??????????? ??????????? ?????? [27, 28]. ??? ????? ?????????? ???????? (0,5 ?) ?????????????? ?
20 ?? 0,2 ? ???????? ?????????? ?????? ? ??????????? ? ??????? ????, ????? ???????????????. ?? ???????? ???????? ???????? 5 ??, ??????? ????????? ? 25 ?? 0,1 ? HCl, ??? ????????????? ?????????????????? ??????. ?????????? ??????? ????????????? ??????? ??????????
0,2 ? ????????? NaOH ?? ?????????????? ????????? ???-02 («???????», ??????). ?????????
??? ???????????? ?????????, ? ?????????? ?????????. ?????????? ????????? ????? ?? ??????????? ?????????? ?? ??????? ????? ??????????? ??????, ??????????????? ?? ????????
????????? ? ?????????? ?????????? ????????.
???????? ????????? ????????? ??? ??????????? 180 °C ? ???????? ?????? 1 MPa ? ????????? ???????? ???????? (Autoclave Engineers, USA) ??? ??????????? ????????????? (1500
??/???) ???????????? ???????? ???? ????????? ? ????????? ????????. ?????????? ????????? ? ???????????? ?????????? 10 ?/?. ??????? ????????? ? ???????????? ???????? ? ???????, ????????? 45 ?? ????, ??????? ?????????, ????????? ??????? 6 ??? ? ???????? ??????
??????????? ?????. ????? ?????????? ??????????? 180 є? (????? ?????????? ???? ??????????? ?????????? ???????? 30 ???.) ???????? ??????? ?????. ? ???? ??????? ?? ?????????
???????????? (????? 1, 2, 3 ? 5 ?) ???????? ????? ??????????? ????? ??? ???????.
?????? ????????? ??????????? ????? ????????? ??????? ???? ?? ????????????
Shimadzu Prominence LC-20, ????????????? ??????????????????? ? ??????????????? ??????????? ? ???????? Rezex RPM-Monosaccharide Pb2+ (Phenomenex, 300 ?? * 7,8 ??), ?????# 90 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
????????????? ??? 70 °C. ???????????????? ???? (Milli-Q) ?????????????? ? ???????? ???????
? ?????????? ?? ????????? 0,6 ??/???.
?????????? ? ??????????
????????? ???????? ???????? ????????????? ???????, ????????? ?-1,4-????????????
???????, ?? ???????? ????????????? ?? 20000. ????? ??????????? ?????????? ?????????? ????????? ?????????? ??????, ??????? ????????? ???????????? ????? ?????????????????????? ????????, ? ??????? ? ?????????? ??????????? ?????? ?? ??????????? ?
?????????? ??????? ???????? (????????????? ?????? ?? 220 ??) ??????????? ???????? ???????. ????????? ??????????????? ????????? ????????? ????????? ?????????? ??????????,
????????????? ? ????, ??? ?????????? ?? ??????????? [16]. ? ???????? ??????????? ?????????
??????? ????????? ? ?????? ??????? ?????????? ????????? ?? ??????????????? ?????????, ??? ???? ????????? ???????? ??????? ??????? ?????????? ???????? (??????????? 200 єC
? ????, ??????? ???????????? ????????? ????????????? ? ?????????? ?????). ?????? ??????????????? ???????????? ????????? ?????????, ??????????? ??????????????? ?????????,
????????? ??????? ????????? ????? ??????? ??????????????? ????????? ?/??? ??????? ??????????? ? ??????? ?????????????? ????????????? ??????? ????????????? ????????? [16].
? ?????? ?????? ???? ???????????? ???????????????????? ????????? ??? ?????????????.
?????? ?????? ????????? ?? ?????? ????????????????? ???????????? ???????? (43±4) ???
(????. 1). ??????? ??????????????? ??????? ???? ????????? ?? ??????????? ????????????????
??????? ????????? 92 % (???. 1). ?????????? ? ???????? ????????? ???????????? ?????????
???? ???????? ? ?????????? ?????????? ???????????? ?????????????. ?????? ????? 1-10, 110,
012 ? 200 ?????????? ?? 1,5 ?? 2,7° ?? 2?, ??? ????????????? ??? ?? ??????? ??????? [29, 30]
?? 3 ?? 6 ??. ?????? ???? 004 ????? 0,7°, ??? ????????????? ??????? 13 ??. ????? ???????,
??????? ????? ????????? ????? ? ??????????? 001.
???????????? ????????? ???????????????????? ????????? ???? ????????? ? ??????????? ???????? ? ??????? 10 ???. ???????????? ???????? ????? ???????????? ????????? ??????? ?????????? ??????????? ???????? ?????????? ??????? ?????? ?? 5±4 ???. ?? ?????????????? ??????? ??????????? ?????????? ? ?????????? ????????????? ????? 1-10, 110, 012,
200 ? 004, ??????????? ??? ??????????????? ????????? ?????????, ? ????????? ?????????
???? ??? 2?, ?????? 21,5° (???. 1). ?? ???? ????????????? ??????? ??????? ????? ????????????
??????? ?? ?????????????? ??????? ?? ??????, ????????? ? ?????? ????? (???????? ????????? ????????? «????????????????» ????????, ??? ?? ????? 3 ??). ??????? ???????????????
??????? 1. ????????? ?????????: ??????? ?????? ?????? ? ?????????? ??????????? ????
?
?/?
??????? ?????????
<d>*, ???
????????? W, %
???????????
??????? ????
1
????????? ????????????????????
43±4
5,70
0,943
2
?????????, ?????????? ? ???????????
????????
5±4
3,52
0,965
* <d> ? ??????? ?????? ?????? ?????????.
# 91 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
?????????????????
10
15
20
25
30
35
40
???. 1. ?????????????? ???????????????????? ????????? ?? (1) ? ????? (2) ??????? ? ???????????
????????
???????, ????????? ?? ???????? [34], ????????? ????? 30 %. ????? ???????, ????? ?????????
???????????????????? ????????? ????? ???????? ???????????.
????????, ??? ????????, ? ??? ????? ? ?????????, ???????? ? ????? ??????? ???????????
????, ?????????? ??????? ????? ????????? ?????????? ??????? ????????, ????? ???????????? ????? ? ????? ??????? ????????? ?, ??? ?????????, ??????? ?????? ???????? ?????????.
??? ??????????? ????????? ?????????? ???????? ????????? ? ???????? ???????????????????? ? ???????? ????????? ???? ????????? ??????????? ????????? ?? ??????????? ???????? (???? 16932-82). ?????????? ???????????? ???????? ?????????, ?????????????? ? ????. 1,
??????????????? ? ???, ??? ??? ???????????? ????????? ?????????? ???????? ????? ???????? ?????????? ????, ????????, ??-?? ?????????? ????????? ? ???????????? ????????. ??????
????????? ??????? ?????????????? ?? ????? ???????? ????????? ? ?????? ???????????? ????????? ??????? ?????????.
??? ????????????? ???? ????????????? ????????? ????????? ?????????????? ???????
??????????? ????????? «???????-4» ? ???????? ?????? 56 ? 94 ???. ??????? ???????????
????????? ??????????????????? ??????????? ?????????, ???????????? ??????? ?????????????????? ????????? ?????, ????????? 379 ?2/?, ? ?????????? ????????? ?????, ?????????????
??????? (?????????, ????????? ? ?????????????), ? 0,042 ????? ?-1 (????. 2).
??? ?????????? ??????????? «????????-4» ???? ???? ????????? ????????????? ??????????? ????????? ????????? ?????? ???????? ??? ????????? ???????????? (80, 150, 200 ?
250 °?), ??????? ?????????? ?-S80, C-S150, C-S200, ?-S250 ??????????????. ????? ???????
???? ??????????? ??????????? ??????????? ????????? ???????????, ??????????? ?????????
?????????? ?????????? ????? ??? ????????????? ????????? ?????????? ????. ?????????? ???????????? ???????? ?????????????? ????? ??????? ?????????????????? ????????? ?????
(????. 2) ????????, ??? ????????????? ??? ???????????? ????? 200 °? ???????????? ?? ???????? ? ????????????? ?????????? ??????? ??????????? (SBET). ??? ??????????? 250 °? ??????????? ?????????? ???????? SBET ?? ~30 %, ? ????? ????? ??? ??????????? ??????????
?????? ??????? ?? ????????? ? ??????? ??????????????? ????????? ? ???????? ??????# 92 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
??????? 2. ?????????? ?????????????? ???????? «????????-4» ?? ?????? ??????????????????
????????? N2 ? ???????????? ????????? ????? ?? ???????????, ???????????? ??????? ????????????????? ??????????
???????
SBET, ?2/?
V???????, ??3/?
?????.?????, ?????/?
?????.?????, ?????/?2
C
379
0.213
0.042
1.0·10 -4
C-80
344
0.200
0,14
4.1·10 -4
C-150
360
0.222
0.32
8.8·10 -4
C-200
400
0.240
0.40
10.0·10 -4
C-250
221
0.069
0.62
26.8·10 -4
???, ??? ??????????????? ? ?????????? ???????? ??????????? ?????????, ??????, ? ??????????
??????????? ???????.
??? ??????????? ?????????? ?????????? ????????????? ?????????, ?????????, ????????????? ? ??????????? ???? ????????? ?????????? ???????? NaOH (????. 2). ?????????? ????????? ????? ? ?????????????? ???????? ????? ??????????????? ????????? ? ??????? ?????
????????????? ? ??????????? ??????????? ????????????? ? ? 3?15 ??? ????????? ?????????? ????????? ????? ? ???????? «????????-4». ???????????? ?????????? ????????? ?????
(0,62 ?????/?????????????) ???????? ?-S250. ???????????? ????????? ????? ? ??????? ?? ???????
??????????? ??? ???????? ?-S200 ? ?-S250 (1,0 ? 2,7 ??????/?2 ??????????????) ????????? ??????????? ? ?????????????? ????????? ????? ?? ?????????????? ?????, ????????? ? ?????????? (?? 1,1 ?? 2,0 ??????/?2) [21-23].
?????????????? ???????? ?????????????? ??????? ????????? ????????????? ???? ??????????? ? ??????????????? ??????????????? ??????????? ?????????????? ????????? ?
????????? ??? ??????????? 180 °? ? ????????? ??????. ?????? ??????????? ?????? ?????????
??????? ????. ?????????? ????????????? ????????? ? ????. 3, ? ??????? ??? ????????? ???????? ?????? ????????? ??????????????? ??????????? ????????? ? ??????????? ???????????? ?????? ???????. ???????????? ? ??????????? ??????? ????????????????? ????????
?? ??????? ???????? ??? ?????????????? ??????????. ? ??????????? ???? ??????????????
????????????? ????????? ?????????? ??????? ???????? ??????? ? ??????? ?? ????????????
5-????????????????????? (5-???). ???????????? ?????? ?????????? ??????? ?????????
???????????? ?? ???. 2 ? ???. 3. ????? ????, ?? ?????????????? ??????????? ???? ??????????, ???????, ???????? ? ?????????. ???????? ?????????? 5-??? ? ?????? ?????? ????? ?
??????????? ? ?????????? ??????? ? ????????????? ?? ????. ???????????? ?????????????
??????? ???????? 5-??? ? ??????????? ??????? ????????? ????????????? ? ??????? ?? ??????????? ????????? ?????????????, ? ??????????? ??????? 5-??? ?????? ??????????? ?? ??????????? ? ?????????? ??????, ???????? ?????? ?????? ??????????? ?????? ?????? (???. 3).
???????????? 5-??? ????? ????????????????? ? ??????????????? ???????????? ?????????
???????? ??????????????? ??????????? ???????????, ?????????? ????????????? ??????
????????? ?????????? ? ????????????? ?? ??????????? ??????????? ????????????. ? ??????????? ??????? ?-S200 ???? ????????????? ???????????? ?????? ??????? ? 5-???, ???????
????????? 45,9 ? 21,5 % ????? 2 ? 5 ? ??????? ?????????????? (????. 3). ?? ???? ????????????? ?
# 93 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
??????? 3. ?????? ????????? ??????????????? ??????????? ????????? ? ??????????? ???????
????????? ?????????????. ??????? ????????: ????? ????????? 450 ??, ????? ???????????? 450 ??, ?????
???? 45 ??, ????????????? 1500 ??/???, ??????????? 180 °?
???????**
5
0
0
0
0
0
0
0
0
?-S80
12.1
3
9.3
3
0
5.8
0.5
2.6
8.7
0
0
0
?-S150
33.5
2
17.0
5
1.2
23.5
3.6
4.0
17.0
1.5
0
0
?-S200
45.9
2
21.5
5
1.0
18.9
6.0
9.7
21.5
5.9
0
0
?-S250
35.9
2
19.0
5
1.1
26.7
7.5
9.0
19.0
1.4
0
0
H2SO4
52.0
0.25
-
-
-
11.4
-
-
-
-
5.4
26.6
5-???
???????
???????
t,?
t,?
????????
0
????????
5
??????????
0
?????, %
?
?????, %
???????????
?-??
??????, %***
??????????
?-??
???????????*
5-???**
*?????? ?????????????: ? ? ?????? ???????????????? ???????-4; C-S150 ? ???????-4, ??????????????
??? 150 °?; C-S200 ? ???????-4, ?????????????? ??? 200 °?; C-S250 ? ???????-4, ?????????????? ???
250 °?; H2SO4 ? 0,02 M ?????? ???????.
** ??????? ??????? ?????????? ???????????? ??????? ??????? ? 5-??? ??????????????.
*** ??????? ?????? ????????? ????? 5 ? ???????.
60
1
3
5
????? ???????, %
50
2
4
6
40
30
20
10
0
0
1
2
3
4
5
?????, ?
???. 2. ???????????? ?????? ?????????? ??????? ? ???????? ??????????????? ????????? ? ???????????
?????????????: ? (1), ?-S80 (2), C-S150 (3), C-S200 (4), C-S250 (5), 0,02 M H2SO4 (6). ??????? ????????:
????? ????????? 450 ??, ????? ???????????? 450 ??, ????? ???? 45 ??, ????????????? 1500 ??/???,
??????????? 180 °?
??????????? ??????? ????????? ? 2 ?? 5 ? ??????????? ???????? ??????? ??????? ? ????????? ???, ??? ??????????? ???????????? ??????? ? 5-??? ? ???? ??????? ???????????? (????.
3). ????????? ????????, ??? ???????????? ?????? ??????? ????????? ??????? ? ??????? ?
5-??? ? ?????????? ??? ???????? ?? ??????? ?-S150 ? ?-S200, ??? ????? ???? ????????? ?????? ?????????? ????????? ????? ?? ???????????. ?????? ? ??????????? ???????????? ?-S250
?????? ??????, ??? ? ??????????? ?-S200, ???????? ?? ??????? ????? ??????? ????????????
# 94 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
1
3
5
7
????? 5-???, %
25
20
2
4
6
15
10
5
0
0
1
2
3
4
5
?????, ?
???. 3. ???????????? ?????? ?????????? 5-?????????????????????? ? ???????? ???????????????
????????? ? ??????????? ?????????????: ? (1), ?-S80 (2), C-S150 (3), C-S200 (4), C-S250 (5), 0,02 M H2SO4
(6). (7) ? ???????????? ?????? ?????????? ??????????? ??????? ? ??????????? 0,02 M H2SO4. ???????
????????: ????? ????????? 450 ??, ????? ???????????? 450 ??, ????? ???? 45 ??, ????????????? 1500
??/???, ??????????? 180 °?
????????? ????? ?? ??????????? ???????????? ?-S250 (????. 3). ?????? ??? ?????????? ?????
???????? ?????????? ?????????????? ???????????? ????????????. ????????? ????????????
????? ???????????? ??? ??????????? ??????? ?????????? ???????? ??? ????????? ???????
????????? (??????? ? 5-???).
????????????? ??????????? ???????????? ?????????????? ?????????? ? ???????????? ???????? ?????????????? ?????????? ????????????? ?? ?????? ???????????????? ???????????
????????? «????????-4» ????????? ??????? ????? ? ???, ??? ????? ????????? ???????? ???????? ????????????? ?????????????? «???????-4», ???????????? ?????? ???????? ??? 200 °?
(??????? C-S200), ????????? ???????????? ????????, ???????? ?????????? ????????? ????? ?
?????????? ??????? ??????? ?????????.
??????????
????????? ????????????, ???????????? ?? ?????????? ?? ?????? ????????????? ???????????????? ??????????? ????????? ????? «???????» («???????-4») ??????????, ?????????????? ? ??????????? ?? ????????? ? ?????????????? ???????????? ???????????
(??????? ? 5-???) ??????? ????????? ????????????? ????????? ?????????. ????????????, ?????????? ????? ????????????? «????????-4» ??? ????????? ????????????, ? ???????????????? ?????????? ???????? ??????? ???????? ?????????????????? ?????????
N2 ? ????????-????????? ?????????? ??????????? ??????, ?? ?????????????? ????????
??????????? ? ???????? ????????? ??????????? ?????????????? ????????????????????
?????????.
??????????, ??? ????????? «????????-4» ??? ??????????? ???? 200 °? ????? ? ????????????? ?????????? ???????? ?????????, ??? ????? ?????? ???????????? ???????? ?? ????????. ?????????? ????????? ????? ?? ??????????? ????????????? ? ?????? ???????????
?????????.
# 95 #
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?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
?????????? ?????????????? ?????????? ?????????????? ??????????, ? ?? ????? ??? ?????? ??????? ?? ??????? ???????? ?????????? ? ????????? ?????????. ????????? ?????????? ??????? ???? ??????? ? 5-?????????????????????. 5-??? ? ????????????? ???????????
???????? ???????? ? ?? ???????????? ??????????? ?????????? ? ??????????? ???????. ???????????? ????? 5-??? ???????? 21,5 %.
????? ?????????, ??? ????? ????????? ???????? ???????? ????????????? ?????????????? «???????-4», ???????????? ????????? ?????? ???????? ??? 200 °? (??????? C-S200)
????????? ???????????? ?????????, ???????? ?????????? ????????? ????? ? ????????????
??????? ??????? ?????????.
?????????????
?????????? ????????? ???????????? ???????? ?????????????? ?????????? ??????
??????????????? ???????????? (????? 12-03-93116-?????_?), ??????? ?????????? ?? ???
????????? ??????? ??????? ???? ??-1183.2014.3, ?????????-??????????? ??????? ???????????? «????????». ?.?. ?????? ???????? ????????? ????????????? ?????????? ??????? ?
?????? ?? ???????????? ?????????.
?????? ??????????
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????, ?.?. ?????? ?????????? ?????????????? ????????????? ?? ?????? ???????????????? ????????????
Development of Sulfonated Catalysts Based
on Graphite-Like Carbon Sibunit
for Cellulose Hydrolysis
Nikolay V. Gromova,b,c,
Oxana P. Taran , Dmitriy A. Yatsenkoa,
Artem B. Ayupova, Anne Loppinet-Seranib,c,
Cyril Aymonierb and Vladimir E. Agabekove
a
Boreskov Institute of Catalysis,
Siberian Branch of the Russian Academy of Sciences,
5 Lavrentieva, Novosibirsk, 630090, Russia
b
Institut de Chimie de la Matiиre Condensйe de Bordeaux,
CNRS, 87 av. du Dr Schweitzer, 33608, Pessac, France
?
Universite Bordeaux
1, 351 Cours de la Liberation, 33405, Talence, France
d
Novosibirsk State Technical University,
20 pr. K. Marx, Novosibirsk, 630092, Russia
e
Institute of Chemistry of New Materials NAS of Belarus
36 F. Skorina Str., Minsk, 220141, Belorus
a,d
Solid acidic catalysts for the processing of cellulose in the value-added chemical (glucose and
5-hydroxymethylfurfural) in aqueous media ware prepared on the basis of graphite-like carbon
«Sibunit - 4» using sulfonation by sulfuric acid at different temperatures, followed by treatment in
water at 180 єC. Prepared catalysts were characterized by low-temperature nitrogen adsorption
and acid-base titration. Testing of catalytic activity in the hydrolysis of the mechanically activated
microcrystalline cellulose was carried out at 180 ° C and 1 MPa of argon. The main products of the
process are glucose and 5-hydroxymethylfurfural with yields up to 46 and 22 mol. %. Comparison
of the results of the activity and stability of catalysts showed that the most promising is the catalyst
sulfated at 200 °C.
Keywords: cellulose, carbon, sulfonation, hydrolysis, glucose, 5-hydroximethylfurfural.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 100-111
~~~
??? 676.164 +547.595
C??????? ???????????????,
?????????? ??????????????
?????????? ? ???????? ?? ???????? ????????
?? ???? ???? ??????
?.?. ??????????, ?.?. ??????????,?,
?.?. ?????????,?, ?.?. ?????????,?*
?
???????? ????? ? ?????????? ?????????? ?? ???,
??????, 660036, ??????????, ?????????????, 50, ???. 24
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
Received 21.11.2013, received in revised form 18.12.2013, accepted 12.01.2014
??????? ???????? ???????????????, ?????????? ?????????????? ?????????? ? ???????? ??
???????? ???????? ?? ???? ???? ??????. ???????????, ??? ???????, ?????????? ?????????,
???????? ??????? ??????????? ? ????????? ?????????? ? ? ??????? ???????????? ??????, ???
??????? ?????????? ?? ???????????? ???????????????. ??????????? ??????? ?????????????
???? ??????? ?? ??????????? ?????????? ?????????? ??????????????? ? ?????????
????????? ????????? ???????. ????????, ??? ?? ????? ??????????? ????????? ??? ??
???????? ????? ??????? ???????????????, ???????????? ? ??????????? ????????.
???????? ?????: ?????????????, ??? ???? ??????, ?????????????, ?????????, ???????.
????????
??????, ??????????? ? ???????? ?????????????? ?????????? ??????? ?? ??????????
??????, ??????????? ???????????? ? ??????? ??????? ??? ????????? ?????????, ?????? ?
?????????? ????. ?? ???????????????? ???????????? ? ?????????? ?????? ????????? ????????? ???????????? ?????????????? ?????? ????. ???????????? ????????????? ???? ?????? ?????????????? ????????????? ????? ? ???????????? ??????? ?? ???????. ???????? ?????
??????? ????????? ??? ????????? ? ??????, ???? ????????? ???? ? ????????? ?? ??????????
???????? ?????? ????????????? ?????? ??? ???????????? ?????????? ? ??????????? ??????? ??????????. ???????? ????????????? ???????????? ?????????? ???? ?????? ????????? ??
?????????? ??????????? ? ?????????? ???????????? ???????? ???????. ????????, ?? ???????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru
# 100 #
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?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
???? ?????? ???????? ???????, ??????? ? ??? ??????????? [1?4]. ??? ????? ??????????????
??? ????????? ????????? ??????? ? ???????????????? ?????????? [5]. ????????? ?????????? ???? ?????? ????????? NaOH ????????? ???????? ???????, ??????? ????????? ???????
??????????? ?????????? ? ????????? ??????? ?????? ??????? ? ?? ????????? ?? ????????
?????????? ? ????????????? ?????????????? ?? ???????????? ??????? [5, 6].
? ????????? ????? ??????? ???????? ????????? ????????????? ??????????? ?????????? ??????????????? ? ???????? ????????? ??? ????????????? ???????????? ???????? ?????????? ? ????? ???????? ?????????? ????????????????? ????????. ????? ????????? ????????????????? ???????? ??? ???????? ???????? ????????? ??????? ????????? ??????? [7, 8].
????? ????, ????????????? ????????? ??????? ?? ??????????? ??????????????? ???????????? ?????????? ?? ??????????? ?????????? ? ????????????? [9, 10]. ??????? ???????? ????????? ????????? ?????????, ???????????????? ?????????? ???????. ? ??????????? ?? ?????? ????? ????? ???????? ?????????????? ? ????????? ?????????? [11, 12]. ?????????????
??????????? ????????????? ???????? ?? ???? ???? ?????? ? ???????? ???????? ???????? ???
????????????? ??????? ???????? ??????? ???????? ? ?????? [13].
???? ?????? ?????? ? ???????? ??????? ???????????????, ?????????? ??????????????
?????????? ? ???????? ?? ???????? ?? ???? ???? ??????.
????????????????? ?????
? ???????? ????????? ????? ???????????? ????????-????? ??? (????????? 7,5 ± 0,5 %)
???? ?????? ????????, ?????????? ?? ??????? ????????????? ???????????????????????
?????????. ??? ?????????? ?? ?????????????? ????? «8255 Nossen» ?? ??????? ?????? ?????
0,5 ??. ??? ???? ????????? ?????? (% ?? ????? ????????? ?????? ????????): ?????????????????? ???????????? ? 26,8, ??????????????????? ???????????? ? 22,3, ?????? ? 34,5, ??????????????? ???????? ? 13,5, ??????????? ???????? ? 3,4.
????????? ?????????????? ???????????? ?????????? ???? ?????? ????????? 2%-????
NaOH ??? ??????????? (65±5) °? ?? ????????, ????????? ? ?????? [6]. ????? ????????? ????????????????? ?????????????? ???????????? ?? ???. 1.
????????????? ?????????? (????????????? ???????? ? ??????????? ??????????
97,5 %, «???????????», ??????) ? ???????? (????? ?, ???6-17-421-84) ????????? ?? ??????????????, ???????????? ?? ??????? ????? 0,25 ??.
??????????? ?????????, ?????????? 2,5, 5 ? 13 ??/? ??????????, ???????? ??? ??????????? ?????????????? ?? ?????????????? ?? ???? ???? ??????. ???????????? ?????????? ? ???????? 0,9%-???? NaCl (?? 5,4) ??????????? ?? 15 ?? 200 ??/?. ??????? ????????? ?
??????????? ???????? ??? ????????????? ???????????? ? ?????????????? (120±10) ?????/???
??? ??????????? (20±1) °? ? ??????? 24 ? ??? ??????????? ???????? ? ???????? ??????????
0,1 ? : 50 ??. ???????? ???????? ?? ???????? ? ?????????? ??? ????????? ???????????.
??????? ????????? ?? ?????? ???????????? ??????????????? ??-??? (????????? ?????????????? ?????, ??? «???????????»), ????????? (?????????????? ????? ????? ???-?,
?? «????????») ? ????- 1 (???????-??????????? ??????? ?? ?????? Al2O3, ?????????? 10
???.% ????????????, ???? «?????») ???????? ??????????? ????????, ????????? ??????? ?????????? ???????????? 200 ??/?.
# 101 #
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?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
??? ????
??????
????????
?????????
????????
?????
?????????????
????????
?????
?????
?????????????
??????????
???????????
?????????????
????????
???????????????? ?????????????
???. 1. ????? ????????? ?????????????? ?? ???? ???? ??????
???????? ? ????? ??????? ??????????? ?????????? (20 ??/?) ???????? ??????????????? ????????: ????? ??????? ????? ??????????? ????????????? ?????????? (??????????
?????????? 13 ??/?) ????????? ? ??? ?????? ?????????? ? ??????????? 1:1. ??????? ???????? ??????????? ? ??????? ????? ? ?????????? ???????? ??????, ????? ?????????? ?? ??????? ??? ????????? ???????????.
????????? ?????????? ? ??????????????? ????????? 0,9%-??? ?????? ????????? NaCl
(?? 5,4) ? ????????, ??????????? ??????? ??? ??????????? ???????? ? ????????, ??????
0,1 ? : 25 ??. ???????????? ?????????? ?????????? ????????????????????? ??? ????? ?????
364 ??.
??????????? ????????????? ???????? ?? ?????????????? ????????? ?? ?????? ????????? ??? ?? 4,7. ??????? ???????? ???????? ????????? ??????? ???????????: 0,9%-??? NaCl,
?? 0,2%-??? CaCl2 ? MgCl2. ?????????? ????????????????? ???????? ??????????? ?????????? ????????????????? ? ??????????? ???????, ? ????? ???????????? ???????? ? ????????
???????? ? ???????????? ? ??????? [13]. ????????????? ???????? ?? ????????, ???????????????
???????????? 20%-??? ????????? Na2SO4 ? 3%-??? ????????? MgCl2 ? ??????? 60 ??? ???
????????????? ? ????????? ????? ??? ???????? ???????? ?????. ??????? ????????????? ?????? ??? ????????? ??????????? ? ??????? ?????.
??????????? ??????????? ?????????? ??????????????? ????????? ?? ????????? ????????? ? ?????? ???????????? ??????: ??????????? ?????, ???????????? ??????? ? ???????????? ?????? ?? 500 ??????? ?????? ????? (?. ?. ?.); ??????? ?12, ???????????? ???????
???????????? ????? 500?1500 ?.?.?.; ????????, ?????????????? ??????? ???????? ???????;
????????? ? ?? 584,7 ?.?.?. ? ?????????? ????????? ???????. ??????? ???????????? ??????
? ????????? ????????? ?? ???????? [14], ???????? ?12 ? ???????? [15], ?????????? ? ? ???????????? ? ????????? [16]. ?????????? ?? ????????? ?????????, ?????????? 0,9%-??? NaCl,
??????????? ?? 2,0 ?? 7,5. ??????????? ???????? ???????????? ??????????????? (?????????
??? «????????», ????- 1 ???? «?????», ???-101 ?? «????????»), ????????? ??? ?????????, ?????????? ??????????? ???????.
# 102 #
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?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
?????????? ? ?????? ?????????? ???????????? ????? ??????????? ???????? ?? ???? ??????????.
?????????? ? ??????????
?????????????? ? ???????????????? ??????????
? ???????? ?????????? ??? ???????? ?????????????? ?? ???? ???? ?????? ??????????????? ??????? ???????????? ????????? (?6?6N4O4). ????? ??????????, ??????? ??????? ??????? ?????????? ? ????????, ?????????? ???????????? ???????? ???????? ?????????????
???????? ? ?????????? ?? ?????? ???????????? ??????????????? ????????? ? ????-1, ????????? ? ?????????? [7].
??? ??????? ?? ??????????? ?? ???. 2 ???????? ???????, ?????????? ?????????? ?? ?????????? ???????? ??????????????? ?? ???? ???? ?????? ??????????? ????????? ?????????????? ???? (??? I ?? ????????????? ???). ????????????? ????????? ????????? ???????????
?????????? ? ????????? ??????????? ? ??? ?????????? ??????? ? ????????????? ?????????
???????????? ?????????? 13,2 ??/?.
?? ??????????? ??????????? ????????? ?? ??????????? ???????? ???????????? ??????????????, ????????? ? ???????? ???????? ????????? (????. 1).
????????, ??? ????????????? ????????? ? ???????????????? ?????????? ?????????
???????? ???????????? ??????????? ? ?????????????????? ????????? ?????????????????
14
???????, ??/?
12
10
8
6
4
2
0
0
50
100
150
200
??????????? ???????????? ??????????, ??/?
???. 2. ???????? ??????? ?????????? ????????? ?? ???? ???? ??????
??????? 1. ???????? ?????????????? ?? ???? ? ???????????? ??????????????? ? ????????? ??????? ?
????????? ??????????
?????????????
?????????, ??/?
???????*, ??/?
1?
24 ?
?? ???? ???? ??????
13,2±0,4
2,8±0,1
8,4±0,3
??-???
94,5±2,2
0,3±0,1
0,6±0,1
?????????
98,7±2,3
0,3±0,1
0,5±0,1
????- 1
42,9±1,3
0,5±0,1
1,1±0,2
??????????: ??????? ?? ???????? ?????????? ? ????????????? 200 ??/?.
# 103 #
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?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
????????. ??? ??????? ?? ??????????? ? ????. 1 ??????, ?? ??????????? ????????????? ???????????????? ????????? ????????????? ?? ???? ???? ?????? ??????????? ??????????? ?????????? ?????????????? ??-???, ????????? ? ???????-??????????? ????-1. ??? ?????????
?????????????? ?? ?????? ???? 0,9%-??? ????????? NaCl ? ??????? 1 ? ?????????????? 21,2 %
????????????????? ??????????. ? ?????? ?????????????? ?????????? ? ?????? 0,32 %. ?????????? ????????????????? ????????? ?? 24 ? ???????? ? ?????????? ?????????? ???????????
? ??????? ?????????? ?? 63,6 %. ? ?????? ???????? ????????? ?????????? ????????????????
?????????? ?????????? ????? 0,5?1,1 % (????. 1). ????? ???????, ???????? ?????????? ????????????????? ?? ?????????? ??????????????? ??????????? ???????? ??????????? ??-?? ???
???????? ?????????? ? ?????????. ?????? ?????????? ????????? ????????????? ?????????
????????? ?????? ????????????? ????????? ????????? ?????????? (?? 2?4 % ? ?????? ???????? ?? ?????? ????-1).
??????????? ???????? ????????? ?????????? ?? ??? ?????????? ? ?????????????? ??
???? ???? ?????? ???????????? ???. 3.
????????? ?????????? ?????????? ? ???????? ?? 2,5 ?? 13 ??/? ???????? ?? ?????? ?
?????????? ?????????? ???????????????? ???????????, ?? ? ? ?????????? ??????? ?????????? ??????????. ??? ????????, ??????????? 2,5 ??/? ??????????, ????????????? ??????????
??????????? ????? 10 ?, ? ? ??????? ????????? 88 % ????????????????? ???????????.
??????? ????????, ???, ???????? ?????????? ?????????? ? ???????? ?? 13 ?? 20 ??/?, ????? ???????????? ????????????????? ????????? ????????? ???????? ?????????????? ????????? ?????????? ???????? (???. 3).
???????????, ??? ??????????? ????????????? ?????????? ?? ?????????????? ?? ?????????? ???? ???????? ? ?????????? ??? ??????????? ?????????? ? ????????? ????????????
?????? (??) (????. 2).
?????? ??????????? ?????????? ??????? ??????????? ????, ??? ? ?????? ????????????? ??????????? ?? ??????????????? ??-???, ????????? ? ????-1. ?? ??????? ????????????
?????? ??????? ?? ?????? ????-1 ????? ? 2 ???? ???????? ???????? ?? ?????? ???? ???? ??????. ??? ????????????????? ????????? ?????????? 24 ? ???????? ??????? ?? ??????????-
9
?????????, ??/?
8
7
6
4
5
4
3
2
3
2
1
1
0
0
5
10
15
20
25
????????????????? ?????????, ?
???. 3. ???????????? ?????? ????????? ?????????? ??? ?????????????? ?? ???? ???? ?????? ?
????????? ??????????? ???????????: 1 ? 2,5 ??/?; 2 ? 5 ??/?; 3 ? 13 ??/?; 4 ? 20 ??/?
# 104 #
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?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
??????? 2. ?????????? ????????? ?? ???????????? ?????? (??)
??????? ?? ????????????????
?????????, ??/?
????????
????????????????
???????????????????? ?????
??? ???????
????????? ??????????
??????????
??????????, ??/?
??????? ??
????????
?????????, ??/?
?? ???? ????
??????
13,2
58,5±1,6
45,8±1,4
??-???
94,5
98,7±3,1
40,3±2,6
41,5±2,4
?????????
98,7
123,5±3,6
58,6±2,5
60,8±2,7
????-1
42,9
48,7±1,3
25,2±1,1
28,1±1,3
???????
55,3±1,4
??????????: ????????? ? ??????? 24 ?.
?????? ????????? ?? ???? ??????????? ?? ??, ??? ? ? ?????? ????????? ????????. ????????,
????? ????????? ??????????? ??? ???????? ????????? ?????????? ????? ????????? ?????????
??? ??????? ??, ??? ? ? ???????? ???????? ?? ????.
????????????? ??????????? ? ????. 1 ? 2 ?????? ??????????, ??? ??????? ?? ???? ????
?????? ???????? ????? ???????????????? ????????? ??? ????????? ???????????????? ??????????????? ? ???????????????? ??????????????? ????????? ?? ????????? ? ??????????
????????????? ????????????????. ????????????? ????????????? ???????? ??????? ????????? ?????????? ? ??????? ??????????? ??????????? ??????????? ?????, ????????????
??????? ????????.
??????????????, ???????????????? ?????????
??????? ????????????? ????? ????????, ?????? ????????????? ????????????? ??????? ???????? ???????. ???????? ????????? ???????? ???????? ????????? ? ????????????
???????? ?????????? ?????????, ????????? ??? ????????????? ??????? ??????? ???????. ???
??????????? ???????? ??????????? ? ???????? ???????? ?????????????? ????? ?????????
??????? ? ????????? ????????? ???? ? NH2 , -COOH, ? CONH2 ? ??. [17]. ????????, ??? ????????????? ??????? ???????? ??????? ?? ??????? ??????? ????????? ???????? ??????????????
? ??????? ??????????? ???????????, ????????? ?? ??????? ????? ? ???????????? ????????
[12, 18].
?????? ?? ??????? ?????????? ????????, ????????????????? ?? ?????????????? ?? ????
???? ??????, ?? ??????????? ?????????? ???????????????? ????????? ? ????????? ????????? ??????? ? ????????? ???????????? ?????? ????????? ? ????. 3.
????????????? ???????? ?? ?????????????? ?? ???? ???????? ? ?????????? ??? ??????????? ?????????? ? ????????? ???????????? ?????? ? ??????????. ?????? ?? ??????? ????
????????? ??????? ??????????????, ?????????? 55 ? 100 ??/? ????????, ??????????? ?? ??????????. ??????? ????????, ??? ???????????? ??????????? ??????? ?????????????? ?? ???????? ?????????? ?? ????? 100 ??/?. ???? ???????????, ??? ?????????? ?????????? ????????
? ??????????????? ?? 16?23 % (????????? ???????? ? ????? ????????) ??????????????? ??-??
?????????? ??????????? ?????????? ?? ???????????? ?????? [19]. ???????? ? ????????# 105 #
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?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
??????? 3. ??????????? ?????????? ???????? ?????????????? ?? ???? ???? ??????, ????????????????
????????? (???????????? NaCl ? ????????? ????????? 0,9 %, ?? 5,0, ??????????? 20 °?)
??????? ???????????????
?? ???? ???? ??????
?????????????, ??????????
25 ??/? ????????
?????????????, ??????????
55 ??/? ????????
?????????????, ??????????
100 ??/? ????????
???????? ?????????????
???, ??/?
? ?12 , ??/?
?????, ??/?
????, ??????/?
68,9 ± 3,1
2,9 ± 0,3
27,4 ± 1,4
45,7 ±2,5
75,5 ± 3,5
3,1 ± 0,3
22,1 ± 1,2
51,9 ±2,7
76,7 ± 3,4
2,8 ± 0,3
21,3 ± 1,1
52,2 ± 3,1
58,9 ± 2,4
2,4 ± 0,2
59,1 ± 2,3
38,0 ± 1,5
??????????: ???, ? ?12, ?????, ???? ? ????????? ???????????? ??????, ???????? ?12 , ????????? ? ??????????
??????????????.
???????, ??/?
90
80
70
1
60
2
50
40
30
20
3
10
0
0
2
4
6
8
10
?????, ?
???. 4 ???????????? ?????? ??????? ???????????? ?????? (1), ?????????? (2) ? ????????? (3) ??? 20 °?
?? ????????? ?????????, ?????????? 0,9 % NaCl ? ??????? ?? 5,0
???????? ?????????????? ?? ???? ??????????????? ?????????????? ???????? ???????? ?12.
????????, ?????????? ???????? ?????????, ???????????? ??? ????????? ????????, ???????????? ??? ??????? ????? ???????. ???????????????? ?????????????? ?????????? ?? ?????????? ????????????????? ???????? ????????? ??????????? ?????? ????????? ?? ????????? ? ???????? ???????????????. ??????????? ????????? ??????? ??? ??????? ?????????
?? ???????? ?? ??????????? ? ???????????????? ????? ???????? [20].
???? ??????? ???????? ??????? ???????????? ??????, ????????? ? ?????????? ???????????????? ?????????, ?????????? 100 ??/? ???????? (???. 4).
???????????????? ????????????? ?? ?????? ???? ?????????? ?????? ????????? ??????????? ????? ? ?????????. ?? 30 ??? ??????????? ??????? ????????? 80,2 % ?? ? 77,4 %
?????????? ?? ???????? ?????????? ??????????? ??????? ???? ????????. ??????? ?? ? ??????????, ??????????? ? ??????? 1 ?, ????????????? ?? 93,5 ? 90,2 % ??????????????.
??? ??????? ?? ???. 4, ? ??????? 30 ??? ???????? ??????????? ????????? ?????? ????????? ??????? ? ??????? ?????????? 21,3 % ?? ???????????? ????????. ??? ???????????, ????????, ???????????????? ??????????? ??????? ????????? ?? ??????????? ?????????????????
# 106 #
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?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
80
1
???????, ??/?
70
60
50
40
2
30
20
3
10
0
2
3
4
5
6
7
8
??
???. 5. ??????? ?? ????????? ????????? ?? ??????? ???????????? ?????? (1), ?????????? (2) ? ?????????
(3) ????????? ?? ???? ???? ??????, ???????????????? ????????? (?????????? ???????? ? ????????
100 ??/?, ???????????? NaCl ? ???????? 0,9 %, ??????????? 20 °?, ????? ???????? 1 ?)
????????. ?????????? ????????????????? ??????? ?? 1 ? ???????? ? ?????????? ????????
??????? ????????? ?? 89,4 % ?? ???????????? ????????, ??? ???????? ? ???????? ???????????? ?????? ? ??????????. ???????, ??? ????????????????? ??????? ? ??????? 1 ? ???????????
??????????? ??? ??????????? ??????? ??????????????? ? ????????? ??????? ??? ????????????? ? ????????? ? ??????? ???????????????? [15].
????????, ??? ??????? ???????? ???????? ????????? ? ???????????????? ?????? ??? ??
4,7?5,0 [17, 21]. ????????, ??????????? ???????? ????? ????????????? ???????? ????? ????????? ???????? ????????. ? ?????? ? ???????? ????????? ????????? ??????????? ????????????????? ???????? ????? ??????????? ????????????? ??? ????????????? ?????. ?????
????????????, ??? ??????? ??????????????????? ?????????????? ? ???????????? ????????
????? ?????? ?? ??????? ????????? ????????? ??????? [11].
???????????, ??? ????????? ???????? ?? ????????? ????????? ?????? ?? ??????? ???????????? ?????? (??) ? ????????? ???? ? ??????????? ???????? ??????????? (???. 5).
???????????? ??????? ???? ????????? ??????? ??????????? ??? ?? 5,0, ?.? ?????? ???????????????? ????? ???????? [17, 21]. ??????????? ????? ? ????????????? ????????? ?? ????????? ? ????????? ?????. ??????? ????????? ??????????? ?? ?? 2,0 ???????? ? ????????
??????? ?? ? ?????????? ???????????? ???????????? ?????????? ??????????? ???????? ?
???????? ???????. ????????? ??????????? ?? 5,0 ?? 7,5 ??????????? ?????????? ???????? ??
? ???????????? ?????????? ??????????? ????????, ??? ?????????????? ?? ???????? ? ???????? ?????????? ????????? ???????? [21]. ??????? ??????????? ?????????? ????????????????? ????????? ???????? ? ????????? ???????????? ?????? ????? ??????????? ????????????
?????????????? ????? ???????? (-???? ? ??.) ? ?????????????? ? ????????? ??????????
????????.
???????????????? ????? ????????? (?? 4,8?4,9), ???????????? ? ???????? ?????????
???????, ? ???????? ?? ??????????? ????????????????? ???????? (4,7?5,0) ????????? [17]. ?
?????????? ?????????? ?? ???????? ?? ?????????? ???????? ??????? ????????? ????? ??????# 107 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
??????? 4. ??????????? ?????????? ???????????????? ????????? ?? ???? ???? ?????? ?
???????????? ???????????????
???????
???, ??/?
? ?12 , ??/?
?????, ??/?
????, ??????/?
?? 2,0 ?? 7,5 ?? 2,0 ?? 7,5 ?? 2,0 ?? 7,5 ?? 2,0 ?? 7,5
??????? ?? ???? ???? ?????? (55)*1
57,1
70,6
2,1
2,7
5,3
14,2
46,5
52,2
??????? ?? ???? ???? ?????? (100)*2
58,7
71,5
1,9
2,7
5,5
13,8
48,0
52,9
?????????
49,4
52,6
2,0
2,4
0
32,5
15,4
15,9
???? ? 1
43,5
49,2
8,5
8,1
4,2
12,4
25,6
29,4
???
21,6
22,4
2,1
2,7
1,8
9,5
17,4
18,6
??????????: ???, ? ?12, ?????, ???? ,? ????????? ???????????? ??????, ???????? ?12 , ????????? ? ??????????,
??????????????; *1 ? ?????????? ???????? ? ???????? 55 ??/?; *2 ? ?????????? ???????? ? ???????? 100 ??/?.
?????? ???????? ??????????????????? ???????????? ?????????? ?????????? ????????????
???????? ? ???????????? ?????????. ???????????????? ??????? ????????? ? ?????????? ??
????? ???? ??????????? ???????????????? ??????????? ??? ???????, ????????????? ????????????? ???????????????? [21].
????????? ?? ?????????? ???????? ?????????? ?? ?????? ?? ??? ??????? (???. 5, ?????? 2). ?????????????, ??????? ??????????????????? ?????????????? ?? ????????? ???????
??????? ????? ???????. ????????, ?????????? ?????????? ?????????? ?? ???? ????????? ???
??????? ? ?????????? ???????? ????????? ????????.
????????, ??? ??????? ????????? ??????? ?? ????????? ?????????, ?????????? 0,9 %
NaCl, ??? ?? 2,0 ? 7,5 ????????? ??????? ????????????? ?????????????? ? ????? ??????? ?
????????? ?????????????? [15]. ?????????? ?????? ??????????, ??? ????????????????
????????? ??????? ???????? ????????? ?????????? ??????? ????????? ?? ?????????, ???????????? ????? ??????? ? ????????? (???. 5). ??????????? ? ??????? ????????, ??????? ??
??????? ? ???????????? ??????, ????? ? ????????, ???????????? ????? ?????????. ??????
??? ?? 2,0 ??????? ????? ??????? ????? ?????????? ?????? ? 58,7 ??/?.
???? ????????? ????????? ??????? ?????????, ?????????? ?????????????? ???????? ??
???????? ?? ???? ???? ??????, ? ???????????? ??????????????? (????. 4).
?? ???????? ??????? ???????????? ?????? ? ?????????? ???????????????? ????????
?? ???? ??????????? ????????????? ???????????? ??????? ?????????? ?? ?? ?????. ?? ???????? ??????? ????????? ? ????????? ????? ? ?? 7,5 ???????????????? ???????? ????????
?????? ??????????. ?????? ??? ???????? ??????? ???????? ?? ?????? ????????? ?????????.
??????????? ??????? ?? ???????? ?12 ? ???????????????? ????????? ?????????, ?????????? ? ??? ??????????? ?????????, ? ??? ???????-???????????? ????-1 ??????????? ????
??? ? ??????, ??? ? ? ???????? ?????. ??? ???????????, ????????, ???????? ????? ????????
???????? ????????? ????-1, ????????? ??? ??????? ???????? ?12.
??????????
???????? ??????????? ????????? ???????????????? ????????? ?????????? ??????????
????? ????????????? ?????????? ? ???????? ?? ???????? ?? ???? ???? ??????. ???????????,
# 108 #
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??? ? ??????? ?? ???????????? ??????????????? ???????? ? ???????????????? ??????????,
?????????? ?????????????? ?????????? ?? ????, ???????? ??????? ??????????? ? ????????? ?????????? ? ? ??????? ???????????? ??????. ??? ???????? ??????????????? ??????????
???????? ????????? ?????????? (?? ????? 24 ?) ? ????????? ??????????? ??????????? ???????, ???????????? ??????????? ?????.
???????????, ??? ????????????? ???????? ?? ?????????????? ?? ???? ???? ?????? ???????? ? ????????????? ?????????? (? ??????? ? 1,3 ????) ??? ??????????? ?????????? ? ????????? ???????????? ?????? ? ??????????. ?????????? ???? ???????????????? ?????????
????????? ??? ???????? ???????? ?????? ??????? ???????? ?????????? ? ?????????, ???????????? ????? ?????????. ????????, ??? ?? ????? ????????? ?????????? ???????? ????????
? ????? ???????? ????????????? ?????????.
?????? ??????????
1. ???????? ?.?. ????????????? ???????? ???????: ?????????, ??????, ????????,
?????????? // ????? ?????????. 1994. ? 3. ?. 3-28.
2. ???????? ?.?., ?????????? ?.?., ?????? ?.?., ????????? ?.?. ????????? ????????
? ???????? ?? ???? ??????, ?????????????? ? ???????? «????????? ?????????????» // ?????
????????????? ?????. 1998. ? 1. ?. 5-9.
3. ?????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?., ?????????? ?.?.
??????? ????????? ???? ?????? ?????????? ????? ?? ????? ? ?????? ??????????, ??????????
??????? ? ????????? ???????? // ????? ????????????? ?????. 2005. ? 2. ?. 15-20.
4. ???????? ?.?., ???????? ?.?., ????????? ?.?. ???????? ???????? ????????? ???????????
??????? ?? ??????? ????????? ???? // ????? ????????????? ?????. 2008. ? 1. ?. 41-44.
5. ????????? ?.?., ?????????? ?.?., ???????? ?.?., ????? ?.?., ???????? ?.?., ?????????
?.?. ????????? ????????? ???????, ?????????? ? ??????????????? ?? ???? ????????? ???? //
????? ? ????????? ??????????? ????????. 2005. ? 13. ? 3. ?. 401-409.
6. ????????? ?.?., ????????? ?.?., ???????? ?.?., ???????? ?.?. ????????
???????????????, ?????????? ?? ??????????????????? ???? ?????? // ????? ? ?????????
??????????? ????????. 2012. ?. 20. ? 6. ?. 673-678.
7. ????????? ?.?., ????????? ?.?. A???????? ???????????? (??????????, ?????????????)
? ???????? ? ?? ????????????????? ??????????????? // ??????-???????????????? ??????.
2000. ?. 34. ? 6. ?. 45-49.
8. ??? ?.?., ??????????? ?.?., ???????????? ?.?. ????????????? ?? ?????? ????????
???????????? ????? ? ??? ???????????????? ??????????? ?????????????? ????????????? //
??????-???????????????? ??????. 2007. ?. 41. ? 1. ?. 21.
9. ??????? ?.?. ?????????? ???????? ? ???????? ? ?????????? // ????? ? ?????????
??????????? ????????. 2011. ?. 20. ? 1. ?. 113-122.
10. ???????? ?.?. ?????????????: ????????? ??????? ? ??????????? ?? ??????? // ???????
??????? ???????? ? ????????. 2007. ? 4. ?. 7-17.
11. Sarnatskaya V.V., Lindup W.E., Walther P et. Albumine, bilirubine and activated carbon:
new edges of an old triangle. // Art.Cells, Blood Substit. And Immobiliz. Biotechologe. 2002. ?2.
?. 113-127.
# 109 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
12. ????????? ?.?., ??????? ?.?., ???????? ?.?., ???? ?.?. ???????? ?? ??????
????????? ????????? ???????. I. ??????????? ?????????????? ????????? // ???????
??????????????? ??. 2003. ???. 34. ?. 111-115.
13. ????????? ?.?., ????? ?.?., ????????? ?.?., ???????? ?.?. ???????? ???????
??????? ???????? ??????? ? ???????? ?? ???????? ???????? ?? ???? ?????? // ??????? ?
??????????????. 2011. ? 2. ?. 72-76.
14. ?????????? ?.?. ?????? ????????????? ??????????? ??????????????? ? ??
????????????? ???? //??????-???????????????? ??????. 2003. ?. 37. ? 5. ?. 28-32.
15. ???????? ?.?., ????? ?.?., ????????? ?.?. ????????????? ???????? ?????????????
?????????? ??????????? ????????? // ??????-???????????????? ??????. 2008. ?. 42. ? 7.
?. 30-33.
16. ???? ?., ??????? ?., ???? ?., ????? ?. ?????? ???????? / ??? ???. ?.?. ???????????.
?.: ???, 1981. ?. 2. 726 ?.
17. ??????? ?.?. ???????? ???????????? ??????. ?.: ????????, 1974. 248 ?.
18. Bettelheim Fredericr A., Priel Zvi. Adsorption of biopolymers on solid surface // journal of
colloid and interface science. 1979.V 70. P. 395-398.
19. ????????? ?.?., ????? ?.?., ??????? ?.?. ???????? ??????????????? ?
??????????????? ?????????? ?? ?????? ?????????????? ?? ???? ???? ?????? // ?????
????????????? ?????. 2010. ? 2. ?. 31-36.
20. Baszkin A., Boissonnade M.M. ?ompetitive adsoption of albumin against collagen at
solution ? air and solution ? polyethylene interfaces // Journal of biomedical materials research. 1993.
V. 27. P. 145-152.
21. ?????? ?., ?????? ?., ????? ??. ? ??. ????????? ?? ????????? ?? ???????????
??????? ??? / ??? ???. ?. ???????, ?. ?????????. ?.: ???, 1986. 488 ?.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ?????????, ?.?. ?????????? C??????? ???????????????, ?????????? ?????????????? ???????????
Properties of Enterosorbents Obtained
by Immobilization of Furacilin and Gelatin
on the Porous Carrier from Inner Birch Bark
?ugenia V. Veprikovaa, Cvetlana ?. Kuznetsovaa,b,
Nikolay V. Chesnokova,b and Boris N. Kuznetsova,b
?
Institute of Chemistry and Chemical Technology SB RAS,
Siberian Branch,
50/24 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
Properties of enterosorbents obtained by immobilization of furacilin and gelatin on the porous carrier
from inner birch bark were studied. It was established, that the sorbent containing furacilin in contrast
to commercial enterosorbents combines a high ability for desorption of the furacilin and for sorption
of the methylene blue. Influence of furacilin and gelatin immobilization obtained enterosrbents on
the sorption of different mark substances was investigated. It was found, that they have the sorption
properties similar to more expensive enterosorbents using in medical practice.
Keyword: enterosorbent, inner birch bark, immobilization, furacilin, gelatin.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 112-121
~~~
??? 665.6.7
??????????? ????????????
?????? ????????? ??????????
??????? ???????? ???????? ??? «???? ???»
?.?. ????????, ?.?. ?????????*,
?.?. ??????????????, ?.?. ????????
?
??? «???? ???»,
??????, 662110, ???????????? ????,
?????????????? ?????, ????????
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
Received 10.09.2013, received in revised form 14.09.2013, accepted 15.01.2014
???????????? ??????????? ???????????? ??????????????? ? ?????????? ?????????????
???????, ??????-?????????? ??????????? ?????? ?????????, ???????????? ??? ??????????
??????? ??? «???? ???» ??? ????????? ???????????? ? ???????? ??????????, ??? ??????
??????????? ?? ?????????? ? ???????????? ???????? ?????????. ?????? ???????? ???????
?????????????? ??????????? ??????????????? ??????? ???????????? ???????, ? ?????
?????? ?????????? ????? ? ????????????? ????. ???????? ?????????????? ?????????
??????? ? ??????? ????? ??????? ?????? ????????? ?????????? ?? ???????????????
?????????? ????????. ??????????? ??????????????? ???????????? ?? ??????????
????????????? ?????????? ?????? ? ???????????? ??????????????? ??????? ????????????
???????.
???????? ?????: ??????????, ?????? ???????? ??????????, ?????????????? ??????,
?????????? ????.
????????
??? ?????????? ???????????? ???????? ????????? ? ??? «???? ???» ???????????? ????????????? ????????? ????????? ???????????? ?????????? (????? ? ???). ????????? ???????? ???????? ?? ?????? ??????? ???????? ???????????????? ?? ???????????, ?? ?
???????? ?????????????????? ??????????????? ????????, ? ????????? ???????? ?????
? ???? [1].
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: kositcyna_ss@mail.ru
# 112 #
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3000
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????
241,7
????????????? ?????? ????????? ?????????? ???????? ???????????? ????????? ???
???????????? ????????? ????? ??? ??????????? ??????????????. ??????? ????????????
???????????? ?????????? ? ???? ? ????????? ???????? ?????????, ????????? ?????????
?????????, ??????????????? ?????????? ??????????? ???????? ?????????? ? ????????
?????????? ???????? ??? ??????? ???????? ?????????. ??? ??? ?????????? ?? ???? ??????????? ????????????? ?????????? ? ???????? ????????, ??? ????????????? ???????? ??
???????????? ???????? ? ??????????? ???????????????? ? ????????????????? ????????????????.
? ????????? ????? ????? ?????????? ??????? ???????? ?????? ? ?????? ??????? ??????
????? ????? ??? ???????? ?????????? ????????????? ????? ? ??? ??????????? ??? ???????????? ?? ??? ??? ???? ??????????, ??? ???????, ?????? ?? ??????????? ?????????????????
???????????? [2].
??? ???? ?????? ? ????????????? ??????????????? ? ?????????? ????????????? ???????? ?????? ????????? ?????????? ????????? ??????? ??????????? ????????? ???????? ????????? ? ?????????? ? ?? ?????? ??????????? ???????? ??????????, ??? ????? ??????????
??????? ????? ?????? ??? ???????????? ????????? ????? ?? ???????? ???????? ????????.
???? ??????
????? ?????? ?????? ???????? ??????????? ????? ??????????? ??????? ??????? ??????
????????? ??????????, ??? ?????????????? ??????, ???????? ???? ????? ???? ? ?? ??????????, ??????? ?????????? ?????????? ??????????? ??????????? ???????????? ?????????? ??
?????? ?????????????? ????????????.
?????????, ????????
? ???????????? ??? ????????????
??? ?????????? ????????????? ??????????? ? ??????????? ??????-?????????????????
????????? ??????????, ?????????? ??????????????? ??????? ? ???????, ??????????? ????????? ????? ???????????? ? ?????? ????????? ??? ????????????. ??????? ?????????? ? ????????? ????, ????????? ???????????? ??????????? ?? 1100 °? ? ???????? ???????? ? ?????
???????. ?????????? ????? ???????? ?????????? ????? 500 ??3.
????? ????????? ???????????? ?? ???. 1.
# 113 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ??????????? ???????????? ?????? ????????? ?????????? ??????? ?????????
???. 1. ????? ??????-????????????????? ????????? ??????????: 1 ? ???????????? ??????? ??????????;
2 ? ????????? ???????????; 3 ? ?????????; 4 ? ??????????????????? ????; 5 ? ?????? ?????? ????????????
? ?????? ????????? ??????????; 6 ? ??????? ?????? ????????? ??????????; 7 ? ??????? ???????????;
8 ? ???????? ??????; 9 ? ????????; 10 ? ????????????????? ???????? ?????? ????
??????? 1. ??????-?????????? ?????????? ??????? ????? ??????-????????????????? ?????????
??????????
???????????? ??????????
?????????
?????????
?????????? ????, %
????? ?????????
1,63
???? ? 51947
(ASTM D 4057)
303
???? 4333
??????????? ??????? ? ???????? ?????
(?? ?????? ?????????), °?
???????? ??????????????, ??2/? ??? 80 °?
687
???? 33 (ASTMD 189)
???????? ????????, ??? 80 °?
27
???? 11503
???????????? ?? ?????????? ????????? ? ????????? ?????????? ?? 480 ?? 520 °? ???
??????????? (101,3 ???) ? ?????????? (210, 310 ???) ?????????. ????? ?????????? ?????????
?????????? ?????? ? ????????? ??????????? ???????? ? ??? «???? ???». ?????? ????????
?????????? ?????? ??????, ?????????? ??? ????????? ????????? ??????, ??????????? ?????????? ???????? ???????? ????????? ? ????. 1.
?????????? ???????????????? ?????????? ??????????? ???????? ????? ??? ?????? ?????????? ?????? ??????? ??????? ??????????????, ??????? ????? ???? ????????? ? ????????????????, ? ??????:
? ?????????? ??????? (?.?. ? 180 °?),
? ??????? ??????? ??????? (180 ? 350 °?),
? ??????? ???????? ??????? (350 °? ? ?.?.).
??????????? ??????????????? ? ?????????? ??????????????? ??????? ?????????? ??????? ?????? ????????? ?????????? ??????????? ??????? ??????????? ??????? ?????????????
?? ???? ? 52714. ????????? ?????????????? ?????? ??????? ??????? ??????? ???????????
?????????? ?????????? ? ?????????????? ?????? ?????????????? ???????????? ?????????
(FIA) ?? ASTM D 1319.
# 114 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ??????????? ???????????? ?????? ????????? ?????????? ??????? ?????????
?????? ? ???????? ?????????? ????? ???? ?? ???????? ?????? ????????? ?????????? ???? ???????? ??????? ??????????????????? ?????????????????????? ?????????????
(???? ? 51947), ??????????? ? ??????????????????? ??????????? ???????????? ??????????
??????? ? ?????????????? ???????????????? ????????? ? ???????????????? (Ag2S) ?????????? ????????.
?????????? ????????????
??? ?????????? ????????????? ?? ?????????? ??????? ???????? ???????? ????????,
??? ???????? ?? ???????? ????? ? ???????? ?? ?????? ????????? ?????? ????????? ?????????? 1 ?. ????????? ????????? ????????? ?????????? ?????????? ????? 4 ? ????? ??????
????????????.
???????????, ??? ? ???????? ?????????? ????????? ?????????? ????? ?????????? ?????????, ???????? ? ?????????? ?????????? ????????? ????????? ???????. ??????-??????????
???????? ?????????? ???? ??????????????? ???????? ????? 2 ? ????? ?????? ????????????,
??? ??????? ? ?????????? ??????????? ??????????????? ????? ? ???? [3].
??? ????????? ??????????? ??????????? ???????????? ??????? ?????? ????????? ?????????? ??? ????? ?????????????, ?????????? ??? ?????????? ????????, ??????????? ?????????? ???? ?????? ??????? ???????? ??????? ??? ????????? ?????????? ?????? ??????????
???????. ??? ??????????? ???, ??? ? ???????? ?????????? ???????????? ???????????? ? ??????? ????????? ???????????????, ???????????? ??????????????? ???????????????? ????????????? ? ????????-????????????? ???????, ???????????? ????? ??????? ??? ??????????
???????? ????????? ? ??????? ???????, ? ????? ? ???????? ????.
??? ????????, ??? ????? ?????????, ??? ??????????? ??????????, ?????????? ??????? ??????????? ?????????? ? ????????, ?????????? ? ?????? ????. ?????????????, ? ????????????
??????????? ???????? ?????????? ?????????? ?????????? ??????? ??????????? ?????????????, ???????????????? ????????????? ???????????? ?????????, ????????????? ??????????????? ???????????????? ????????????? ? ????????? ????.
?????? ??????????? ?????? ??????? ???? ?????? ????????? ?????????? ??????????, ???
? ??????????? ??????????? ?????????? ??????????? ????????? ? ????????? ???????????
?????? ??????? ????????? ??????? (???. 2).
?????????? ???? ? ??????????? ?????????? ???????, ?????? ?????, ?? ?? ?????????? ?
?????. ??? ?????????? ???????? ???????????????? ??????? ????? ????????? ??????????
????????????? ? ????? ? ?????? ?????????, ? ????????? ????????? ?? ???? ??????? ? ?????? [4].
?????????? ??????????? ???? ?? ???????? ?????? ????????? ?????????? ????????? ?
????. 2.
??????? ??????? ?????, ??? ??? ?????????? ??????? ??? «???? ???» ???? ?????
30 % ????????? ?????????? ???????????? ??????????? ?????????? ? ???????????? ????????????.
?????????? ???????? ???????????? ????? ???? ??????????? ?? ??????? ???????? ???????, ?????? ???????? ??????????????? ??????? ??????????? ?????????, ?????????????,
?????????? ???????, ? ????? ??????????????? ????????????? ?????????????. ??????????
# 115 #
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???????????? ?????? ???????, ??
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95
??????????? ?????? ???????
??? ?????????, ?????????? ???
???????? ?????????? 101,3 ???
85
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???????? ?????????? 210,0 ???
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??? ?????????, ?????????? ???
???????? ?????????? 310 ???
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65
??????????? ???????? ??????????, ??
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??????? 2. ???????? ???? ???? ? ????? ? ????????? ?????????? ???????
????????????
??????? ???????? ???????? ???? ????? ????, %
?????:
?????? ??? «???? ???»
1,63
???????? ??????????:
???????? ????
1,8
?????? ???????? ??????????:
- ?????????? ??????? (?.?. ? 180 °?)
- ??????? ??????? ??????? (180 ? 350 °?)
- ??????? ???????? ??????? (350 ? ?.?.)
???? ??????????
1,04
0,2
0,9
1,4
5,7
???????? ?????????? ???? ??????????? ? ?????????? ???????. ?????? ??? ????????????????
?????????? ?????????? ???? ?? 0,05 ?? 0,15 % ???. ??? ???????? ???????? ? ?? 0,01 % ????. ???
????????? ?????? ??????????? ?????????? ?????????? ?????????? ? ??????????? ????????
??????????.
??? ??? ? ?????????? ?????????????? ???? ?????????? ? ?????? ??????? ? ?????????
????????? ?????????, ???? ??????????? ?????? ??????????????? ?????????? ??????????? ?
????????????? ???????? ??????????? ???????? ??????????. ???????? ????????? ??????????? ? ??????????? ?????????????? ? ????????????? ???? ??????????????????? ???????????
???????????? ?????????? ???????. ?????????? ??????????? ????????????? ???? ? ??????????? ??????? ???????????? ?? ???. 3.
?? ??????? ?????????? ?????? ???????, ??? ?????????? ????? ???? ?????????? ? ??????????? ??????????? ????????? ???????. ??? ???? ???????????? ??????????? ????????
# 116 #
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1
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- 180 ?)
(180- 350 ?)
??????? ????????
??????? (350 ? - ?.?. )
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50
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?????????? ??? ???????? 101,3 ???
???? ???????????, ???????????? ?? ??????? ??????????? ??????????, ?????????? ?? ?????????? ??????? (?.?. ? 180 °?).
???????? ?????? ??????????????????? ??????? ??????????????? ???????????????
??????? ??????????? ????????, ??? ? ???????? ?????????? ??? ?????? ???????????? ? ?????????? ??????? ?????????? ???????????? ??????????? ???????? ??????????? ??? ?????????????. ? ?????????? ??????????? ??????????? ???????? ??????????? (???. 4). ???
??????? ????? ????????? ???????????????? ??????? ???????? ????????????? ? ?? ????????????? ??? ????????? ??????? ??????????. ????????????? ???????????? ? ??????
# 117 #
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???????????? ??????, ???????? ? ?????? ?????????? ???????, ??????????????? ???????
??????????? ?????????????, ? ??? ??????????????? ?????????? ?? ?????????? ? ?????? ??????????? ???????? ??????????.
? ??????????? ???????? ?????????? ??????????? ????? ??????? ? ?????????? ? ?????????? ??????? ????????? ?????????? ????? ?????????? ? ?????? ???????????? ?????????.
?? ??????? ??????????? ???????????? ?????, ??? ? ?????? ??????????? ???????? ?????????? ?????????? ???????? ?? ???????? ????????????? ????????? ??? ?????????? ???????????? ????????????? ??????????. ??? ??????????? ???, ??? ????????????? ???????????? ? ?????? ???????????? ??????, ???????? ? ?????? ?????????? ???????, ??????????????? ???????
??????????? ?????????????. ? ?? ?? ????? ???????????? ????????????, ??????? ?????????
????????????? ????????????, ??? ??????? ???????????? ???????????? ????????????? ?????????. ?????? ??????????????? ???? ? ??????, ??????? ????????, ??????? ? ??????????
???????????? ? ?????, ?????????? ? ????????, ? ????? ??????????? ?? ????? ?????? ????????, ???????, ? ???? ???????, ???????? ? ??????? ??????? ??? ?????????? (??????????? ?
?????????????).
?????? ??????????? ??????????? ?????????? ??????? ???????? ?????????? ??????????
?????????? ?????? ?????????? ????????????? ? ?????? ??????????? ??????????. ?????????
??????????? ??????? ????? ???????? ? ???????????? ??????? ???????? ????????????? ? ????????????????. ??? ???????????? ???? 500 °? ???????????? ???????????? ????? ???????????? ???????? ??????????, ??????? ??????????????? ?????????? ????????????.
?????? ?????????????? ????? ????? ???? ????????? ??????????????? ????????? ???????? ????????????? ????? ?? ???????????? ????????? ? ?????? ??????????? ??????????, ???
???? ?????????? ??????????? ? ????????????? ???????? ???????? ????? ? ??????????.
?? ????????? ?????? ?????????????????? ???????????? ?????????? ??????? ??????????
??????? ?????? ????????? ?????????? ??????? ????????????? ?????????????? ????????????? ?? ???????????? ??????? ? ??????????? ?? ????? ?????????? ??????. ?????????? ????????????, ??????????? ??? 480 ? 510 °? ? ??????????? ????????, ???????????? ?? ???. 5 ? 6
??????????????.
?? ??????? ??????????? ???????????? ???. 5 ? 6 ???????, ??? ????? ???????? ??????????? ??????? ? ??????. ???????? ? ??????????? ???????????? ? ???????? ????????? ??????,
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??????????? ?????????? 480 °? ? ??????????? ????????
# 118 #
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???
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??????????? ?????????? 510 °? ? ??????????? ????????
????????????? ?????????? ? ????????? ??????? ? ????????????, ? ?????????? ???????????? ? ????????? ?7 ? ?9.
? ?????? ??????????? ?????????? ?????????? ???????? ????????? ?????????? ??? ???????? ? ??????? ?? ?????, ?????????? ????????????????? ?????????? ??????????? ????????????? ? ??????? ?????????? ?9. ??????? ????????, ??? ? ??????????? ??????????? ?????????? ?????????? ??????????????? ??????? ???????? ??????????.
???????????? ?????????? ??????????????? ??????? ?? ?????? ?????????????? ???????????? ????????? ????????, ??? ? ????????? ??????? ???????? ???????????? ??????????
????????????? ? ???????? ? ??????????? ??????????? ???????? ?????????? ?????????????
????????? ??? ?????????? ?????? ????????????? ?????????????.
?????? ??????????? ??????????? ??? ??? ??????? ??????? ??????????, ??????????? ???
??????????? ????????, ??? ? ??? ?????????, ?????????? ??? ?????????? ????????. ??? ??????? ??????????? ???, ??? ????????????? ???????????? ? ???????? ??????? ?????????? ???????? ?????????. ??? ??? ?????????? ??????? ??????????? ? ??????????: ???????? ??????????? ???? ? ?????? ??? ? ?????????? ???????????? ????????????? ? ????? ??????? ????????;
??????? ????-, ??- ? ???+ ? ????????????? ????????????? ?????????? ??? ??????? ????????
???????????.
??????
????? ???????, ???????????? ?? ???????????? ???????? ?????????? ?? ??????????????????????? ????????? ????????, ??? ??? ?????????? ????????????? ?????? ??????
????????? ?????????? ????????????? ????????? ??????? ??? ??????????? ???????? ? ???????????? ??????????? ????????. ??? ???? ?????????? ??????????? ?????????? ???????? ?
?????????? «??????????» ??????? ???????????.
??? ????????? ?????????? ??????? ? ???????? ?????????? ?????????????? ????????
????????????? ???????????? ??????? ??????????? ? ???????? ??????, ??? ???????????? ???????? ???? ???????? ? ??????????? ?????????? ??????????, ???????? ? ????????????? ?????????????.
????????? ???????? ? ???????? ?????????? ???????? ? ?????????? ???? ????????????,
??????, ?? ??????????? ??????? ????? ????? ???????????.
# 119 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ??????????? ???????????? ?????? ????????? ?????????? ??????? ?????????
?????????? ??????????? ??????? ??????????????? ?????????? ?? ?????????? ????????,
?????? ??????????? ??????? ????????? ??????? ????????????? ? ??????????????? ????????? ??????? ???????? ?????????? ? ??? «???? ???» ?? ?????? ?????????????? ? ????????????? ?????????, ??? ???????????? ??????????? ???????????????? ????????? ???????????, ???????????? ?? ?????????? ??????? ??????????? ?????.
?????? ??????????
1. ??????? ?.?., ????????? ?.?., ????????????? ?.?. ????????? ? ??????????? ???????
??? ????????????? ????????? ???????????? ?????????? // ??? ??????????????, ???????
???????? ????????. 2012. ? 7. ?. 53-55.
2. ???????????? ?.?. ???????? ?.?., ??????? ?.?. ???????? ???? ??? ???????????
??????????????. ?????????? ? ???????? // Journal of Siberian Federal University. Chemistry.
2010. Vol. 3(4). ?. 369-386. http://elib.sfu-kras.ru/handle/2311/2319.
3. ?????? ?.?. ????????????, ??????????????? ? ?????????? ????????? ?????. ?.:
?????, 1973. 296 ?.
4. ??????????? ?.?., ????????? ?.?., ???????? ?.?. ?????? ????????? ???????????
???????? ??????? ???????????? ?????????? ? ?????????? ?? ???? ????? ??????? // ?????. ???.
???????. 2011. ? 1. ?. 62-65.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ???????, ?.?. ????????? ??????????? ???????????? ?????? ????????? ?????????? ??????? ?????????
Complex Research of Liquid Products
of Delayed Coking of Heavy Petroleum Residues
of ?Achinsk Refinery?
Sergey E. Proshkina, Svetlana S. Kositcynab,
Ilya S. Grayvoronskyb and Fedor A. Buryukinb
a
OJSC Achinsk Refinery,
Bolsheuluysky District,
Krasnoyarsk Territory, 662110 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Carried out a comprehensive study of individual and group component composition, physical and
chemical parameters of liquid products formed during coking tar of «Achinsk Refinery» at various
temperatures and pressures coking in order to assess the possibility of involving them in the range
of marketable products. Special attention is paid to the quantitative indicators of the hydrocarbon
composition of distillate fraction, as well as evaluating the content of general and mercaptan sulfur.
Revealed regularities of changes in the composition and properties of narrow fractions of liquid products
of coking on the technological parameters of the process. Developed preliminary recommendations
for the achievement of the maximum rate of output and optimal hydrocarbon composition of distillate
fractions.
Keywords: coking, fluid coking products, hydrocarbon composition, the content of sulfur.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 122-133
~~~
??? 676.017.2
??????? ???????????? ? ?????????? ?????????
???????????????????? ?????????
?? ?? ???????? ? ??????????? ???????????
? ????????? ? ??????? ?????????
????????????? SBA-15
?.?. ?????????,?*, ?.?. ?????????,
?.?. ???????, ?.?. ???????????,
?.?. ????????, ?.?. ??????????, ?.?. ?????????,?
?
???????? ????? ? ?????????? ?????????? ?? ???,
??????, 660036, ??????????, ????????????? 50, ???. 24
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
Received 04.10.2013, received in revised form 22.11.2013, accepted 15.01.2014
??????? ??????? ????????? ???????? ????????? ???????????????????? ????????? (???)
?? ?? ???????? ? ??????????? ??????????? ? ??????? ????????? ??? ??????????? 150 °? ?
??????????? ????????-????????????????? ???????????? SBA-15. ???????? ??????? ????????
????????? ????????? (70?82 % ???.) ? ?????? ??????? (27?37,5 % ???.) ?????????? ???
????????? ??? ????? ?? ??????? ? ??????? ????????, ? ????? ????? ???????????? ?????????
? ???-2 ???, ???????????? ????????? ?????? ? ?????????. ??? ??????? ????????? ???????
??????? ????????????? ??? ? ?????? ?? ???????????????.
???????? ?????: ???????????????????? ?????????, ?????????, ????????????, ??????????,
?????????????? ????????, SBA-15, ???????.
????????
????????? ???????? ???????? ??????????? ???????????????? ????????, ????????? ?????????? ??????? ???????? ????? ?????? ?????????? ??????????, ??? ???????, ????????,
5-????????????????????? ? ??????????? ???????, ??????????? ????????????? ? ??. [1, 2].
???????? ????????? ????????? ??????????? ?????????????? ? ?????????????? ????????????? ?? ?????? ??????????? ??????. ? ???????????? ????????? ????????? ??????????-
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru, Yatsenkova@icct.ru
# 122 #
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?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
?? ????? ????????? ??????????????? ?????? ??????? [3]. ?????????? ?????????? ??????????????? ???????????? ??????? ? ???????????? ? ???????????? ??????????? H2SO4, ? ?????
? ?????????? ?? ??????????? [4].
? ????????? ????? ?????????? ??????????? ??????????? ?????????? ? ???????? ????????? ????????? ?????? ???????????-???????? ? ???????????? ??????? ??????????? ??????,
??????? ????????? ?????????????, ????? ??? ?????? ??????? [5], ???????????????? ???????
[6], ???????????? ????????, ???????????????? ???????????? ????????? [7?9]. ?? ??????
??????? ???? ????????, ??? ?????? ??????????? ????????? ????????????? ?? ??????? ????????? ?????? ???????? ????????? ????????? ??????? ?? ???????????? ? ???????????? ??? ???????????? ????????????? [10?17].
?????? ??? ???????????-?????????????? ????????? ????????? ?????? ??????????
??????????? ??????? ???????? ???????????? ? ??????? ?????????. ? ???? ????? ??????
??????? ???????????? ?????????? ???????? ???????? ????????? ? ??????????? ??? ????????????? ?????????. ??????? ?????? ????????? ????????? ?????????, ????????? ??? ?????????????? ???????????, ????????? ?? ?????? ?????? ???????????? ??????????? ?????????????, ????????? ????????? ????????? ? ??????????? ?????????, ?? ? ?? ???????????
????????? ?? ???????????. ? ?????????? ??????? ??????? ?????? ???????????????? ??????? ???????????-??????????????? ????????? ???????????? ????????? [18, 19]. ????????
????????? ????????? ??? ????????? ?? ??????????? ??????????? ? ????????? ?????????
?? ???? ???????? ??????? ?? ????????????? ? ??????????????? ????????? ??????? ??????
?????????? [20-23].
????????? ????????????? ???????? ????????? ????????? ????? ??????????? ????? ??
???????????? ? ?????????? ?????????. ??? ???? ?????????? ??????????? ??????????? ????????? ? ????????? ? ????????????? ????????????? ?? ????????? ???????? ???????? ? ???????.
? ????????? ?????? ???????????? ??????? ????????????, ?????????? ? ??????????????? ???????? ????????? ???????????????????? ????????? ?? ?? ????????? ? ???????????
??????????? ? ????????? ? ??????????? ????????-????????????????? ????????????? ???????????? SBA-15.
????????????????? ?????
?????????????? ???????? ??????????
? ?????? ???????????? ???????????????????? ????????? (???) ????? Vivapur®101 ??
??????? ???????? ????????????? 350, ???????? ??????????????? 0,75.
? ???????? ???????????? ????????? ????????? ????????? ???????????? ???????? SBA15, ???????????????? ?????????? ? ??? ????????? ????? ?SO3H ??????? ????????????? [24].
???????????? SiO2 (SBA-15) ?????????????? ?????? ? ??????? 3 ? ??? ??????????? 120 є?.
?????????? 4 ? ????????????????? Pluronic P123 ??? ????????? ??????????? ? 125 ? HCl 1,9 ?
? ??????????? ??? ????????????? ? ??????? 45 ??? ?? ?????????? 3-?????????????????????????????? (MPTMS). ????? ?????????? ?? 40 °? ????????? ????? 37 ????? (7,7 ?) ????????????????? (TEOS) ? 10 % ???. MPTMS ???????????? TEOS. ??????????? ????? ????????????
? ??????? 20 ? ??? 40 °?. ????? ? ??? ?? ?????? ??????????? ??????????????? ????????? ?
??????? 48 ? ??? 80 °? ? ??????????? ????????. ????? ??????? ??????????? ? ??????????
# 123 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
??????? 1. ?????????? ?????????????? ????????????????? SBA-15
???????? ? ???????????????? ????????
SBET, ?2/?
V???, c?3/?
<d>???, ??
???????? SBA-15
550
0,82
5,9
????????-???????????????? SBA-15, ??????????
??????? ?????????????
370
0,20
2,0
?? ???????. ????????? ? ?????? ???????????? ????? ????????????????? ????????? ???????
?????????????????? ?????????, ???????? ???????????? ????? ????? ?????????????? ??????
???? ??????????. ??? ???????? ??? ???????????? ?????????????? ?????.
???????? ??? ?? ???????? ???????????? ?????????? ? ??????? ? ??????? 24 ? ??? ??????????? ???????????????? 1:100. ?????????? ??????? ??????????????? ? ?????? ?? ???????. ????????? SH-????? ?? SO3H ????????? ?????????? 1 ? ??????? SBA15, ????????????????? MPTMS, 50 ?? 30 % ????????? ???????? ??? ????????????? ? ??????? 48 ? ??? ?????????
???????????.
?????????? ???????? ????????????????? ??????? ???? ??????????? ??????? ?????????????????? ????????? N2 ?? ????????? ASAP-2420 (Micrometritics, ???) ??? T=98 ? ? ????????? ????????????? ???????? (?/??) 0,06?0,99 ? ????? 0,015. ???????? ??????? ???????????
???????????? ?? ?????? BET ? ????????? p/p? 0,06?0,25, ?????????? ????? ??? ? ?? ??????
«Single point BET» ? ????????????? ??? ?? ???????? ???????? ?? ????????? ???????? BJH.
? ?????????? ???????? ?????????????? ????? ??????????? ???????????? ??????????
??????? ???????? ??????????? ? ??????? ??? ?? ????????? ? ???????? SBA-15 (????. 1), ?
????????????? ????? SBA-15 ????? ???????????????? ????????.
????? ?????????? ?????????????? ???????? ?? ???????????????? ???????? SBA-15
?????????? ?? ??????????? ??????????? SDT Q600 (TA Instruments, ???). ??? ???????? ????????? ????? 5 ??, ???????? ?????? ? 40-900 °?, ???????? ??????? ? 20 °?/???.
????????????? ?????????????? ????????????? (???) ????????? ? ??????????????
???????????? «Axios Advanced» (PANalytical, ??????????). ?? ?????? ???, ? ????????????????????????? SBA-15 ?????????? ???????? ???? ?????????? ????? 1,6 ?????/?.
????????? ?????????
???????????? ????????? ???????????? ? ?????????? ??????? ????????????? ?????????: ?????? ? ??????? ????????, ????????? ??????? ?????????? ?????? ? ???????? ??? ???????, ?????? ???, ???????????? ??????? ?????????? ??????+????????.
?????? ??? ???????????? ? ??????? ???????? ??-1 ? ??????? 24 ?. ?????????? ????????? ????????? ??????? ?????????? ?????? ? ???????? ????????? ??? ??????????? ????? 2 °?, ??????????? 30 ? ??????? 16 ?. ??????????????? ????? ??????? ???????????????
?????????? ????????? ??? ??????? ?????????? ??????+???????? ? ??????? 16 ? ? ??????????? ????????? ????????? ? ??????????? ???????? ???-2 ??? ????????? 60g ? ???????
30 ??? ? ????? ???? ??? ??????????? (??) 12 ? ? ?????????? ????. ??? ?????????? ????????? ????????? ???????????? ?????-???????? ???????????? ??????? ??????? (? % ???.): 6 %
NaOH ? 4 %(NH2)2CO ? 4,2 % LiOH ? 12 % (NH2)2CO ?? ???????? ? ???????? [25, 26].
# 124 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
?????? ?????????????? ?????????
?????????????? ???????? ??? ???????? ? ??????????? ????????????? PANalytical
X?Pert Pro ? ?????????? Cu-K? (?=0,154 ??). ?????? ????????????? ???????????? ? ????????? ????? 2? ?? 5 ?? 70 ° ? ????? 0,01 °. ?????? ??????????????? ????????? ???????????? ???
????????? ????? ???????? ????? ??????????????? ????????? ? ????????? ??????? ????
????? ? ???????????? ? ?????????, ????????? ? [27].
?????????? ? ???????? ? ???????? ?????? ?????????????? ????????? ???????? ? ?????????????? ?????????? ???????????? ?????????? «??-1000 HITACHI».
??????? ????????????? (??) ????????? ?????????? ? ???????????????????? ?????????
? ???????????? ? ???? 25438-82 ?? ??????????? ???????????? ???? ???-3 ?? ????????, ?????????? ? ?????? [28].
????????? ???????? ?????????
???????? ?????????????? ??? ???????????? ??? ??????????? 150 °? ?? ??????????? ???????? ????????? ? ?????????? ?????????????? ????????? ??????? 35 ??, ??????????
? ????????????? ????????? ?????????. ???????? ???????? ????????? ?????????? 11 ??/???.
??????? ????????? ? ?????????? 0,45 ? ? ??????????? ???????? ? ???????? ? ???????? ???????????????? ?????. ?? ????????? ????????? ??????? ??????? ????????? ? ??????????????? ????????????????? ????????? ? ??????????? ?? ??????? ??????? ?? ???????? ???????
??? ????????, ????????? ????? ? ?????????? ? ????????? ????? ??? ??????????? 103 °C.
????????? ????????? ?????????? ??????? ??????? ? ????????? ±2?3 %.
?????? ???????????? ?????????
?????????????? ?????? ? ?????????? ??????????? ? ???????????? ??????????? ?????????????????? ??????? ? ??????????? ???????? ???????????? «VARIAN-450 GC» ? ????????????????????? ??????????. ???????????? ??????????? ??????? VF- 624ms ?????? 30 ?,
?????????? ????????? 0,32 ??. ??????? ???????????????????: ???-???????? ? ?????; ??????????? ????????? 250 °?; ????????? ??????????? ?????????? ??????? 50 °? (5 ???), ??????
??????????? ?? 180 °? ?? ????????? 10 °?/???, ???????? ??? 180 °? 37 ???. ???????????
????????? 280 °?. ????????????????? ??????????????????? ?????????? ????????????? ?????????? 55 ???. ??? ??????????? ?????? ?????????????? ????? 55 ??? ??????? ???????????
?????????? ????????? ?? 250 °? (10 °?/???) ? ??????????? ??????? ??? ?????? ???????????
30 ???. ????? ????? ??????? ??? ???? ?????????? 92 ???.
????? ??????????? ???????????? ????????????? ? ???????????? ????????????????? ???????????. ? ???????????? ????? ???????? 15 ??3 ??????? ????? ????????????????? ???????????, ??????????? ????? 10 ?? ??????? ? 4 ?? ??????? (??????? ??????? ???????? ?????:
1,0000 ? ??????? ? 25 ?? ???????????????? ????). ?????????? ??????? ????????? ?????? ???
??????????? 40-42 °?. ??? ???????? ?????? ???? ? ????????? ????? ?????? ????????? ??
1 ?? ???????????????? ????? (4:1), ??????? ????? ??????? ???????????. ? ?????? ???????
?????????? 1 ?? ????????????????? ?????? ????????. ???? ????????????? ????? ????? ????????????, ????? ????????? ?? ??????? ???? ??? ??????????? 75-85 °? ? ??????? 2-3 ???. ???
???????????? ??????????? ?????????? ????? ???????????? ??????? ????????????? ???????
# 125 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
????? ?????????? ??????????? ? ???????? ??????????? ? ??????? 12-20 ?. ????? ? ???????? ????????? 0,3 ?? ???????????????????? ? 0,15 ?? ??????????????????. ????? ?????????
???????, ????????? ??????????? 30 ? ? ??? ????????? ??????????? ??????????? ???????????
????? ? ??????? 10 ???. ??? ?????????? ?????????????????? ??????? ?????? ??-?? ?????????
? ?????? ?????????? ???????. ??????? ????????? ?? ??????????? ????? ??? ?????? ????????????? ?????? ??? ??????????? 40 °?. ????? ? ????? ??????? 1 ?? ?-???????, ??????????????? ?????????? ??????? ????? ?????????????? ?????????? ??????? ? ???????? ????????
? ?????????? ??????????????????? [29].
?????????? ????????????? ???????? ???? ???? ???????????? ? ????? ??????????? ?????????? ?????????????. ????????????? ????? ?????????, ????????? ????? ??????????????
??? ?????? ??????? ??????????????????? ?????????? ?????? ??????????? ???????????
???? ?????????????. ???????????? ????????? ????? ???????? ?????????????????? ?????
???????????? ? ??????? ???? ??????????? ????????? (Si/S??). ?? ???? ???????????? ? ??????? ??????????????? ??????? ???????? ????? ??????? ???????????? ? ????? ???????????
(?????????????? ??????? ??? ????????? ????????? ????????????? ??????? ?????).
? ???????? ?????????? ??? ??????? ???????????? ????????? ??????????: ??????? ??????????????? ????????? (???? 975-88), D-??????? 142080.1208 (Panreac), D-??????? 373195,1208
(Panreac), D-?????? (Panreac).
?????????? ? ??????????
??????? ????????? ??? ?? ?? ????????
? ???? ??????????? ???????????? ???????????, ??? ???????? ???????????? ???????????
????????? ????????? ??????????? ??? ?? ???????????? ?????????. ??? ??????? ?? ??????????????????? ??????, ???????????? ?????? ????????? ? ??????? ???????? «??-1» ? ???????
24 ? ???????? ? ????????? ??????????? ??????????????? ????????? ????????? (???. 1). ?
?????????? ????? ?????????? ?????? ????????????, ???? ??????? ? ???????????? ????????
???. 1. ?????????????? ????????? Vivapur®101: ? ? ?? ??????? ? ??????? ????????; ? ? ????? ??????? ?
??????? 24 ?; ? ? ????? ???????????? ? ???-2 ???, ???????????? ?????? ????????? LiOH+????????
# 126 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
????????????? ???? ? ??????? 10-30° ? 35-40° 2?, ??????????????? ????????? ?????????????
????????.
????????? ????????? ?????? ????????? LiOH+???????? ?? ?????? [26] ? ???????????
????? ???????? ? ????????-?????????? ???-2 ? ??????? 30 ??? ??????? ? ?????????? ????????????? ? ?????????? ?????? ????? ? ????????? 101, 10 1, 002 (???. 1, ????? ?). ??? ????????, ?????? ????????????? ????????????? ????? ??????? ?? ???????? ???????? ??????????????? (???????? ???????????? ?????????): ??? ?????? ?????? ???? ????????, ??? ??????
?????? ???? ?? ?????????????? [27]. ???????????? ?? ????????????? ??????? ??????????????? ???????? ? ?????????????? ??? ????????? ? ????. 2.
????? ??????????????? ???????????????????? ????????? ? ??????? ???????? ? ???????
24 ? ????????? ????????? ??????? ?? ????????????? (??) ? 350 ?? 185, ? ?????? ???????????????, ?? ?????? ???, ????????? ?? 0,35.
??????? ????????? ??????????? ??????????? (???) ???????????, ??? ????????? ???
????? ??????? ? ??????? ???????? ?????????? ????? ??????????????? ? ??????????, ? ??????? ?????? ?????? ?????????? ? 60?70 ?? 10?15 ??? (???. 2).
??????? 2. ?????????????? ?????????????? ???
???????
??????? ????????? ??? Vivapur®101
???????
??????
????????????? ???????????????
350
0,75
1
???????? ??? Vivapur®101
2
????????? ? ??????? ???????? 24 ?
185
0,35
3
????????? ?????? ????????? NaOH+(NH2)2CO 16 ?
172
0,70
4
????????? ?????? ????????? LiOH+(NH2)2CO 16 ?
156
0,69
5
??????? 3, ????????? ? ???-2 30 ??? ? ???? ??? ??=12
119
0,76
6
??????? 4, ????????? ? ???-2 30 ??? ? ???? ??? ??=12
62
0,78
7
??????? 3 (????? ?????? ? ???-2 30 ???)
135
0,62
8
??????? 4 (????? ?????? ? ???-2 30 ???)
101
0,60
?
?
???. 2. ???-??????????? ????????? Vivapur®101: ? ? ?? ??????? ? ??????? ????????; ? ? ????? ???????
? ??????? 24 ?
# 127 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
????????? ??? ???????????????? ???????? ?????????????? ???????????? ??????????????? ????????? ? ????????? ??????? ??????? ?? ?????????????. ?? ?????? ?
????. 2 ???????, ??? ??? ???????? ?? ????????? ???????? ???????? ?????? ???????? ??
?????? ?????????? ?????. ????? ????????? ??? ?????????? 4,2 %LiOH+12 %(NH 2)2CO ?
6 %NaOH+4 %(NH 2)2CO ??? ??????????? ????? 2 °? ? ??????? 16 ? ??????? ?? ????????????? ????????? ?? 156 ? 172 ??????????????, ? ? ?????????? ??????????? ???????????? ?
???-2 ? ??????????? ???? ?? ??? ????????? ?? 62 ? 119 ??????????????. ????????? ????????????? ????????? ?? ?????? ?????????? ????? ???????? ?????????? ??????? ???????
??????????????? ??????????????? ??????? ????????? I. ???????????????? ????? ????????? ????? ????????? ????????? II, ??? ??????????? ?? ?????????????? ????????? ?????
??? 2?, ?????? 22°.
????????-?????????????? ????????
?????????????? ???
?????? ??????? ???????????-??????????????? ????????? ????????? ???????????? ?? ??????? ???????????????? ???. ? ???????????? ? ????????????? ??????? [6, 11, 17, 30] ????
??????? ??????????? ????????? 150 °?. ???????????, ??? ??? ????????? ????????? ?????? : ??????? (??????????? ???????? ?????????) ? 16 ?? 48 ?? ?????????? ????????????? ?????????? ????????? ????????? ? ????? ??????? ?????????? 2-3 % ???. (???. 3?). ??? ?????????? ???????????? ??? ?????? ??????????? 24.
?? ?????????? ???????? [11, 30], ??? ? ???????? ????????? ????????? ? ???????? ?????????? ?????????????? ????? ???????????? ?????? ????? ????????? ????? ????????? ??? ????
????????? ?? [16, 31]. ?????????? ????? ???????????? ? 0,15 ?? 0,45 ?, ??? ????????? ?????????? ????????? 0,45 ? ? ?????? ????????? ???????? ????????? ????????? ? 19,7 ?? 39,6 % ???.
? ?????????? ??????? ? ??????????? ? 2,3 ?? 5 % ???. (???. 3 ?). ? ?????????? ?????????????
???????????? ??????? ???????????? 0,45 ?.
?
?
???. 3. ??????? ??????????? (?) ? ????? ???????????? (?) ?? ????????? ???????????????? ??? ? ?????
??????? ? ??????? ????????? ? ??????????? ????????-????????????????? SBA-15 (????? ?????????
0,45 ?, ??????????? ??????? 150 °?, ????????????????? 3 ?)
# 128 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
??????? ????????, ??? ? ?????????? ???????????? ???????? ????????? ? ???? ??? ??????????? 150 °? ? ????????????????? 3-24 ? ??????????? ?? ?????????? (???. 3?), ??? ??????
??????????? ? ????????????? ??????? [31].
??? ????????? ???????????????? ??? ? ??????? 24 ? ? ??????????? ?????????????????
SBA-15 ??????? ????????? ????????? 66 % ???., ?????? ????? ??????? ?????????? ?????? 8,1 %
???. (???. 4?). ? ???? ???????? ?????????????? ???????? ?????????? ? ??????? ???????? ???
???? 100%-??? ?????????, ?????? ?????????? ???????? 42 % ???. ??????? (???. 4?). ?????
???????, ??? ???????????? ????????? ??? ?? ??????? ???????? ????????????? ??????????
??????????????? ????????? ??? ? ????? ?????????? ?? ??????????????? ?????????.
?? ??????, ?????????????? ?? ???. 5, ???????, ??? ???????? ??????? ??????????? ???????????? ? ???????? ???????????-??????????????? ????????? ???????? ???, ???????????? ?
??????? ???????? ? ??????? 24 ?, ? ????? ???, ?????????????? ?????? LiOH + ???????? ???
NaOH + ???????? ? ??????????? ????? ???????? ? ???-2 (?????? 2, 7 ? 8). ? ?????????? ????
???????????? ????????? ????????? ????????? ????? ????????? ?????????? 70?82 % ???., ?
?????????? ??????? ? ???????????? ????????? ?? 27 ?? 37,5 % ???.
??? ????????? ???????? ???, ? ????? ?????????, ?????????????? ? ???? ???????? 3 ?
4, ???????????? ????????? ?????????? 41,0?51,7 % ???., ? ?????????? ??????? ? ????????????
5,2?15,3 % ???., ?????????? ?????? ??????????? ??????????? ?????? ??????????? ??????????????? ????????? ?????????. ????????? ????????? ??????? ?????????? ??????+???????? ?
??????????? ?? ?????????? ? ???-2 ? ????? ???? (?????? 5 ? 6) ???????????? ???????? ? ??????? ??????????????? ?????????, ???????????? ?? ???????? ????? ?????????, ??? ???????
????? ??????? ??? ?????????. ????????? ??? ???????? 2, 7 ? 8, ??????????? ?????????
?? ? ??????? ??????????????? ?????????, ??????????? ?? ??????????? ???????????, ???
??????????? ? ????????? ????????? ????????? ? ?????? ???????.
???????? ????????????? ???????????? ?? ?????????????? ????????? ???????????? ??
???. 6. ?????????? ????????????? ???????? ???? ???? ???????????? ? ????? ???????????
?????????? ?????????????.
?
?
???. 4. ??????? ????????????????? ????????? ???????????????? ??? (?) ? ?????????? ??? (?) ?
??????????? ????????-????????????????? ???????????? SBA-15 ?? ????????? ????????? ? ?????
??????? (????? ????????? 0,45 ?, ???????????? 0,45 ?, ??????????? ??????? 150 °?, ??????????? 24)
# 129 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
???. 5. ??????? ??????? ????????? ??? ?? ?? ????????? ? ????? ??????? ??? ??????????? 150 °?
? ??????????? ????????-????????????????? SBA-15 (????? ????????? 0,45 ?, ???????????? 0,45 ?,
????????????????? 6 ?, ??????????? 24): 1 ? ???????? ???, 2 ? ????? ???????????? (24 ?), 3 ? ?????????
????????? LiOH + ????????, 4 ? ????????? NaOH + ????????, 5 ? ????????? LiOH + ???????? +
???????????? ? ????? ????, 6 ? ????????? NaOH + ???????? + ???????????? ? ????? ????, 7 ? ?????????
LiOH + ???????? + ????? ????????????, 8 ? ????????? NaOH + ???????? + ????? ????????????
? ? ????????? ??????? 5
? ? ????????? ??????? 7
???. 6. ????????????? ???????????? ?????????????? ??? (??????????? ????????? 150 °?, ?????
????????? 0,45 ?, ???????????? SBA-15 0,45 ?, ????????????????? 6 ?, ??????????? 24)
????? ???????, ???????????? ????????? ??? ???????? 2, 7 ? 8 ??????????? ?? ??????????? ??????????? ? ???????????-?????????????? ????????? ?????????? ?????????????????
??????????????? ????????? ? ???????? ??????? ????????????? ?????????. ?????????????
??????? ???????????? ????????? ??????????? ? ????????? ????????? ??? ? ?????? ???????.
??????????
??????? ??????? ????????? ???????? ????????? ???????????????????? ????????? ?? ??
??????????? ??????????? ? ??????? ????????? ??? 150 °? ? ??????????? ???????? ????????????????????????? ???????????? SBA-15.
# 130 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
???????????, ??? ????????????? ????? ???????? ????????? ???, ??? ???????????? ?????? ? ??????? ???????? ? ????????? ??? ?????? ????????? ??????+???????? ? ??????????? ????? ???????? ? ????????-?????????? ???-2, ??????????? ??????????? ?????????
????????? (?? 70?82 % ???.) ? ????? ??????? (?? 27?37,5 % ???.) ??? ??????????? 150 °? ?
????????????????? ????????? 6 ?.
??? ??????? ????????? ????????? ??????? ????????????? ????????????????? ??????????????? ????????? ??? ? ???????? ??????? ????????????? ?????????.
?????? ??????????
1. Zhou C-H., Xia X., Lin C-X. at al. Catalytic conversion of lignocellulosic biomass to fine
chemicals and fuels. Critical Review Chem. Soc. Rev. 2011. 40. P. 5588-5617.
2. Geboers J. A., Vande Vyver S., Ooms R. at al. Chemocatalytic conversion of cellulose:
opportunities, advances and pitfalls Catal. Sci. Technol. 2011. 1. ?. 714-726.
3. ???????, ?.?. ?????????? ??????????? ???????????. ?.: ?????? ??????????????,
1989. 496 ?.
4.Wyman C.E. ed. 1996. Handbook on. Bioethanol: Production and Utilization. Applied Energy
Technology Series. Washington, DC: Taylor & Francis. 424 p.
5. Fukuoka A., Dhepe P.L. Catalytic Conversion of Cellulose into Sugar Alcohols Angew Chem
Int Ed. 2006. Vol. 45 (31). P. 5161-5163.
6. Onda A., Ochi T., Yanagisawa K. Selective hydrolysis of cellulose into glucose over solid acid
catalysts Green Chem. 2008. 10(10). 1033?1037.
7. Nakajima, K., Okamura, M., Kondo et al. Amorphous Carbon Bearing Sulfonic Acid Groups in
Mesoporous Silica as a Selective Catalyst Chem. Mater. 2009. 21. P. 186-193.
8. Bootsma, J. A., Shanks B. H. Cellobiose Hydrolysis Using Organic- Inorganic Hybrid
Mesoporous Silica Catalysts. Appl. Catal. A: Gen., 2007, 327. P. 44-51.
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sulfonated mesoporous silicas Catalysis Letters. 2005. Vol. 102. P. 163-169.
10. Degirmenci V., Uner D., Cinlar B. et al. Sulfated Zirconia Modified SBA-15 Catalysts for
Cellobiose Hydrolysis Catalysis Letters. 2011. Vol. 141. P. 33-42.
11. Takagaki A., Nishimura M., Nishimura S. et al. Hydrolysis of Sugars Using
Magnetic Silica Nanoparticles with Sulfonic Acid Groups Chem. Lett. 2011. Vol. 40. P. 11951197.
12. Zhao, D.; Huo, Q.; Feng, J.; Chmelka, B.F.; Stucky, G.D. Nonionic triblock and star diblock
copolymer and oligomeric surfactant synthesis of highly ordered, hydrothermally stable, mesoporous
silica structures J. Am. Chem. Soc. 1998. 120. P. 6024?6036.
13. Zhao D.Y., FengJ.L., HuoQ.S. et.al. Triblock Copolymer Syntheses of Mesoporous Silica with
Periodic 50 to 300 Angstrom Pores Science. 1998. Vol. 279. P. 548-552.
14. Beck J.S., Vartuli J.C., Roth W.J. et al. A New Family of Mesoporous Molecular Sieves
Prepared with Liquid Crystal Templates J Am Chem Soc. 1992. Vol. 114. P. 10834-10843.
15. Du Y.C., Sun Y.Y., Di Y. at al. J Porous Mater. 2006. 13:163.
16. Suganuma S., Nakajima K., Kitano M. at al. Hydrolysis of Cellulose by Amorphous Carbon
Bearing SO3H, COOH and OH Groups J. Am. Chem. Soc. 2008. 130. P.12787-12793.
# 131 #
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?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
17. Pang J., Wang A., Zheng M. at al. Hydrolysis of cellulose into glucose over carbon sulfonated
at elevated temperatures Chem. Commun. 2010. 46. P. 6935-6937.
18. Rinaldi R., Palkovits R., Schuth F. Depolymerization of cellulose using solid catalysts in ionic
liquids Angew. Chem. Int. Ed. 2008. 47. P.8047-8050.
19. Rinaldi, R., Meine, N., V. Stein, J. Which Controls the Depolymerization of Cellulose in Ionic
Liquids: The Solid Acid Catalyst or Cellulose? Chem Sus Chem. 2010. 3. P. 266-276.
20. Fan L.T., Gharpuray M.M., Lee Y.H. Cellulose Hydrolysis, Springer-Verlag, 1987. 198 p.
21. Hilgert, J., Meine, N., Rinaldi, R., Schьth, F. Mechanocatalytic depolymerization of cellulose
combined with hydrogenolysis as a highly efficient pathway to sugar alcohols Energy & Environmental
Science. 2013. 6. P. 92-96.
22. Hua-yu Hu, Yan-meng Chen, Yan-juan Zhang. A comparative analysis of crystal structure
changes in mechanically activated natural cellulose and cellulose laurate produced by mechanical
activation-strengthened solid phase synthesis J. Chem. Pharm. Res. 2013. 5(12). P.129-134.
23. Carrasquillo-Flores, R., Kдldstrцm, M., Schьth, F. Mechanocatalytic depolymerization of dry
(ligno)cellulose as an entry process for high-yield production of furfurals ACS Catalysis, 2013. 3.
P. 993?997.
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109:513.
25. Ying Wang, Yulin Deng The Kinetics of Cellulose Dissolution in Sodium Hydroxide Solution
at Low Temperatures Biotechnology and Bioengineering. 2009. Vol. 102. ? 5. April 1. ?. 1398-1405
26. Jie Cai, Lina Zhang Rapid Dissolution of Cellulose in LiOH/Urea and NaOH/Urea Aqueous
Solutions Macromol. Biosci. 2005. 5. 539?548.
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measurement techniques and their impact on interpreting cellulose performance Biothechnology for
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28. Bassem B. Hallac, Arthur J. Ragauskas. Analyzing cellulose degree of polymerization and its
relevancy to cellulosic ethanol Biofuels, Bioprod. Bioref. 2011. 5. ?. 215?225.
29. Ruiz-Matute A.I., Hernandez-Hernandez O., Rodriguez-Sanchez S., Sanz M.L., MartinezCastro I. Derivatization of carbohydrates for GC and GC?MS analyses J. Chromatogr. B. 2011.
V. 879. P. 1226-1240.
30. S Van de Vyver., Peng L., Geboers J. et al. Sulfonated silica/carbon nanocomposites as novel
catalysts for hydrolysis of cellulose to glucose Green Chem. 2010. 12. P. 1560-1563.
31. Wang H., Zhang C., He H. ?t al. Glucose production from hydrolysis of cellulose over a novel
silica catalyst under hydrothermal conditions J Environmental Sci, 2012. 24(3). ?. 473-478.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????? ??????? ???????????? ? ?????????? ????????? ?????????????????????
Influence of Mechanical and Chemical Activation
of Microcrystalline Cellulose on its Structure
and Reaction Ability
in Hydrolysis Over Solid Acid Catalyst SBA-15
Boris N. Kuznetsova,b,
Olga V. Yatsenkovaa, Anna I. Chudinaa,
Andrei M. Skripnikova, Svetlana A. Kozlovaa,
Natalya V. Garyntsevaa and Nikolai V. Chesnokova,b
a
Institute of Chemistry and Chemical Technology SB RAS,
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041, Russia
Influence of different methods of microcrystalline cellulose (MCC) activation on its structure and
reaction ability in hydrolysis reaction at 150 °C over acid-modified catalyst SBA-15 was studied. The
most high cellulose conversion (70?82 % wt.) and glucose yield (27.0?37.5 % wt.) were achieved for
MCC treated in ball-mill and for MCC activated in AGO-2 after treatment by water solution of alkali
with urea. These activation methods reduce the degree of cellulose polymerization and its crystallinity
index.
Keywords: microcrystalline cellulose, activation, mechanical, chemical, catalytic hydrolysis, SBA-15,
glucose.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 134-138
~~~
??? 536.66:541.8
??????????????? ?????????????
????????????????????
? ?????????????????????? ?????? ? ????
?.?. ??????a*, ?.?. ?????????a,
?.?. ???????????, ?.?. ???????a
?
????????? ??????????????? ??????????????? ???????????,
??????, 660049, ??????????, ??. ????, 82
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
Received 15.03.2012, received in revised form 28.11.2012, accepted 15.12.2013
??????? ??????????????? ????????????? ???????????????????? ? ??????????????????????
?????? ? ????. ?? ????????????? ??????????? ????????????? ??????????
????????????????? ????????? ???????? ??????????? ??? ????? ??????.
???????? ?????: ?????????????, ???????????????????? ? ??????????????????????
???????.
????????
????????????? ???????? ????? ?? ????????? ??????-?????????? ????????????? ??????????? ??????????. ?????? ?????????????, ?? ????????????? ??????????? ????????? ?????? ?
?????????? ???????? ???????? ?? ????????, ????????? ??? ??????? ?? ????????, ????? ????????????? ??????????? ? ?.?. ????? ???? ?????? ?? ????????????? ?????? ????? ?? ????????
??????????, ??????? ????? ? ?????? ?????????? ????????????? ????????????? ? ?????????.
???????? ???????? ??????-?????????? ??????? ????????? ? ??? ?????????????????? ???????????, ??????? ????????? ?????????????, ???????????? ??????? ??????????? ??????
?????????? ? ????????? ???????? ???????????? ????????????. ? ???? ????? ????? [1, 2, 3, 4]
???? ??????? ??????????????? ????????????? ????????? ? ???? ??? ?????????????????? ??????????? (????????-, ??????-, ???????????????-) ? ???? ? ? ????????? ?????-????????????
?????????????. ? ?????????? ?? ??????????? ???????????? ?????? ?? ????????????? ????????????? ??????????? ????????????? ???? ? ??????????? ??? ?? ???????????, ??? ? ???????
????????????. ??????? ????? ?????????? ???????????? ???????? ???????????? ???????????-
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: anton-chervov@mail.ru
# 134 #
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?.?. ??????, ?.?. ?????????? ??????????????? ????????????? ?????????????????????
???? ? ????????????? ?????????????????? ??????????? ????????? ? ????, ??????? ????????
????????? ? ????????????????? ???????.
????????????????? ?????
???????????????????? (???) ? ?????????????????????? (????) ??????? ???? ???????? ? ??????? ?? ????????? ????????? [5]. ?????? ???????? ??? ? ???? ???????? ??
?????????????????? ????. ??? ??????????? ????????????? ???????????? ????? ??????????????? ????????? ????????? [6]. ?????????????? ??????? ??? ????????? ????????? ??????????
??????? ?????? ???????, ???????????? ? ??????????? ? ??????? ????? ? ???????????????? ?
??????? ???????? ?????????? (± 0,2 °?). ???????? ?????????? ???????? ??????????? ??????????????? ? ??????? ?????????? ????? (?? 5-6 ?????). ?????? ? ?????????? ???????????? ??? ??
??????? ?????? ??????????, ??? ? ?? ??????? ????? ??????? ??????????, ??? ???? ????????
?????????? ? ???????? ?????? ??????????? ??????????. ?????? ???? ?????????, ??? ???????, ? ???? ??????????.
????????????? ??? ? ???? ? ???? ?????????? ?????????????????????? ???????. ???
????????? ?????????? ????????? ????????? ???? ????????? ?? ???????????????? ??-26 ?
???????? ????????????????? ???? 1 ??. ??????????, ??????????, ????????????? ??????????????? ????????? ? ????????? ???????????? ??? ?????????? ???????? ?????????????????.
??????????? ???????????? ????????? ???????????? ?? ????????, ????????? ? ?????? [7].
?????????? ???????????
??????????? ????????? ?????? (??? ? 210 °?, ???? ? 300 °?) ????????????? ???????????? ?????? [5]. ??? ?????????????? ????????????? ???? ????? ??????????? ??????? ?????????? (???. 1). ??? ?????? ???? ? ??????? ??????? ???????, ??????????????? ?????????
?????????? ??? ??? ? 440 ??, ? ??? ???? ? 470 ?? ???? ????????? ????????????? ???????
??? ??????????? ?????????????.
??????? ????????, ??? ???????? ????? ?????? ???????? ??????????????????????, ??????? ?????, ? ??????? ?????????? ?????????????, ???????????? ?? ???????? ?????. ? ????? ?
??????? ???????? ????????????????????? ???? ??? ???????????? ???? 25 °? ?????????????
??????? ?????????? ???? ?????????? ?????? ?? ???? ???????????. ??????? ?????? ?? ????????????? ????????? ? ????. 1.
?????????? ????????????? ??? ???????? ?? ????????? ? ??? ????????? ????????, ???????, ??????? ? ?????????? ????? (???) ??? ???? (????) ????????????? ????? ? ????????
?? ? ??????????? ?????????? ?????? ? ?????????? ????. ????????????? ????????? ??????
? ???? ????????? ?? ????????? ????????? ????? ?????????????? ? ?-???????????????
???????????? ?????????. ??? ????? ?????????, ? ????? ???????, ??????????? ??????????
????????????? ?????? ?? ????????? ? ????????????? ??????????? ? ??????????? ??????, ?,
? ?????? ???????, ??????? ??????? ??????? ????????????? ??????????? ?? ????????? ?
?-??????????????? ???????????? ?????????.
??? ???? ???????????? ????????????? ??? ??????, ??? ????. ? ??????????? ??????????? ????????????? ????? ?????? ?????????????, ??? ??????????????? ?? ???????????????
????????? ?? ???????????.
# 135 #
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?.?. ??????, ?.?. ?????????? ??????????????? ????????????? ?????????????????????
0,3
0,25
0,2
0,15
????
???
0,1
0,05
0
350
370
390
410
430
450
470
490
510
530
-0,05
???. 1. ?? ??????? ?????????? ??? ? ???? ? ????
??????? 1. ?????? ?? ????????????? ??? ? ???? ? ???? ??? ????????? ????????????
???
????
?????????????,
-lgS±0,02
3,07
2,97
2,92
2,89
2,83
2,71
2,64
t, C°
15
20
25
30
35
40
45
t, C°
10
12,5
15
17,5
20
25
?????????????,
-lgS±0,01
3,74
3,70
3,66
3,62
3,58
3,52
??? ??????????? ????????? ????????? ??? ??????????? ???????????? ????????? ???????
????-?????:
d lg S
§1·
dЁ ё
©Т№
'+
2,303R
??????????? ??????????? ????????? ????????????? (S ? ?????????????, ????/?) ?? 1/T
???????? ????????? (???. 2). ?? ???????? ???? ??????? ???? ???????? ???????????? ??????# 136 #
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-2,5
0,0031
-2,7
0,0032
0,0033
0,0034
0,0036
y = -1239,4x + 1,2287
R2 = 0,9611
-2,9
lgS
0,0035
-3,1
????
-3,3
???
-3,5
-3,7
y = -1281,4x + 0,7878
R2 = 0,9904
-3,9
1/T,K
???. 2. ??????????? ????????? ????????????? ??? ? ???? ?? ???????? ?????????? ???????????
??????? 2. ????????????????? ?????????????? (???/????) ????????? ??????????? ????????? ? ???
?????? ? ????
?????????????????
??????????????
?Go
????????
???
????
23,6±0,4
16,7±0,2
20,1±0,2
24,8±0,3
23,6±1,1
24,5±0,2
1,2±0,7
6,9±0,7
4,5±0,2
?(?G )
6,9
3,5
?(?H)
1,2
0,3
?(T?S )
-5,7
-3,3
?H
T?S
o
o
o
???? ???????? ????????? ???????? ????????? ???????? ??????????? (??). ????? ?? ???????
????????????????? ???????????? ???????? ???????? ????????? ???????? ??????????? ????????? ??????? ?????? ???????? ???????????:
?G? = ? RT ln S?
? ????? ????????? ???????? ??????????? ????????:
To?S? = ?H ? ?Go
?????????? ??????? ????????????????? ??????? ???????? ??????????? ??? ? ???? ?
???? ????????? ? ????. 2. ?????????? ????????????? ??? ???????? ?? ????????? ? ??? ????????????? ??????????? ??????????? ????????? ????????????? ???????, ? ???? ?????, ??? ??????????? ?????? ??? ???? ????????? ????????????????? ????????. ??? ?????? «?????????????? ??????» ? ??????? ???????? ???? ???? ???????? ?????? ?? ?????????(?) ???????????(?) ?
???????????? ?????? ?????????? ??? ???????? ????? ???????? ? ?????????? ? ????????????
? ????. 2. ?????????????? ??????????? ???????????????? ?????????????? ????-?????? ???????? ? ????????????? ????????? ??????????? ???????????? ? ???????. ???, ??-????????,
??????? ? ??????????? ????????????? ????? ? ????? ?????????? ?????? ???? ? ??? ?????
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?.?. ??????, ?.?. ?????????? ??????????????? ????????????? ?????????????????????
????????????? ?????????????, ??????????????????? ??????????, ? ???????? ??????? ??????????.
?????? ??????????
1. ????????? ?.?., ?????????? ?.?., ??????? ?.?. ? ??. ????????????? ??????????? ????????? ? ????????? ???????????????????? ? ???? / /??????????????? ?????. 1997. ?. 23. ? 5.
?. 366-367.
2. ??????? ?.?., ????????? ?.?., ??????? ?.?. ????????????? ??????????? ?????????
? ??? ?????????????????? ??????????? ? ???? // ??????? ????????????? ????????????????
????????????. ???????????? ?????. 2006. ? 2. ?. 94-96.
3. ????????? ?.?., ??????? ?.?. ????????????? ??????- ? ????????????????? ? ????????? ?????-????????? ????????????? // ?. ????? ?????. 2003. ?. 73. ???. 1. ?. 74-78.
4. ??????? ?.?., ????????? ?.?., ??????? ?.?. ????????????? ??????????? ????????????? ???????????- ? 1,1'-???-(???????????)????????? ? ????????? ?????-??????????? ????????? // ?. ?????????? ?????. 2007. ?. 81. ? 7. ?. 1204-1208.
5. ?????????? ?.?., ???????? ?.?., ????????? ?.?. ?????????????????? ??????????. ????????. ? ?.: ?????, 1983. 554 ?.
6. ????????????????? ?????? ????? ????????? / ? ??. ?.?. ??????????, ?.?. ????????,
?.?. ?????????? ? ??. ?.: ?????. 1997. 351 ?.
7. ????????? ?.?., ????????? ?.?., ??????? ?.?. ????????????? ??????????? ????????????????????????? ?? ?????? ????????? ????????? ???????????? // ??????????????? ?????. 1997. ?. 23. ? 4. ?. 316-320.
Polythermal Solubility of Ferrocenylcarboxylic
and Ferrocenyldicarboxylic Acids in Water
Anton A. Chervova, Pavel V. Fabinskiia,
Nina V. Gavgolenkob and Vladislav A. Fedorova
a
Siberian State Technological University,
82 Mira, Krasnoyarsk, 660049, Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041, Russia
Studied the polythermal solubility ferrocenylcarboxylic and ferrocenyldicarboxylic acids in water.
The temperature dependence of the solubility calculated thermodynamic parameters of the dissolution
process for both acids.
Keywords: solubility, ferrocenylcarboxylic and ferrocenyldicarboxylic acids.
# 138 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 139-150
~~~
??? 543.421/424 + 543.632
???????? ????????? ?????? ??? ???????
?????????? ??? ??????????????? ????
? ????????? ??????? ????????
?.?. ???????????*, ?.?. ??????????
?
???????? ??????????????? ??????????? ???????????,
??????, 163000, ???????????, ??. ????????, 37
?
???????? (???????????) ??????????? ???????????
????? ?.?. ??????????,
??????, 163002, ???????????, ??. ??????????, 4
Received 26.11.2013, received in revised form 17.12.2013, accepted 10.01.2014
????????? ???????????? ??????????-?????????????? ???????????? ???????? ?????????
?????? ????????? ????, ????? ? ??????? ???????? ??????????? ???????, ??-??????????????????, ?????????????????. ???? ?????? ??????????? ?????????? ???
??????????????? ??????? ? ????????? ??????? ????????.
?????????? ???????? ??????? ?????? ?????????? ? ???? ????????? < ???????????????
< ????????? ???????. ????????? ??????????? ????????? ?????? ????? ?????? ???????
???????????????? ????????????? ? ????????????? ???????????? ? ??????? ???????
???????????? (W = +3,34?+10,48). ???????????? ??????? ???????????? ?????????? ???
????????? (a = 42,3) ? ??????????????? ?????? (a = 43,2) ??????? ? ???????????? (a = 43,2)
???????????? ?????.
????????? ?????, ???? ?????????? ?????? ??????? ???????????? ????????? ?????? ? ?????
??????? ? ?????????, ???????? ?????? ???????????? ???????? ?? ????????? ? ???????
????????. ?????? ? ????, ????????, ???????? ? ????? ??????? ????????? ??????? ? ???????
??????????? ????????????, ???????? ???????????? ? ???????? ?????????????? ??????,
??? ????????? ?? ??????????? ?????????? ??????? ???????????? ????????? ??????? ?
????????? ??????? ????????. ??????? ??? ????????? ????????? ????? ?????????????
??? ????????????? ? ???????? ???????? ??????? ? ????? ????????? ??????????????? ???????
????????? ????.
???????? ?????: ????????? ???????, ??????????????? ????, ?????, ??????, ????, ???????
???????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: takorelskaya@yandex.ru
# 139 #
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?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
????????
???? ?? ????????? ???? ????????????? ? ?????? ?????????? ????????, ????????? ?
?????????? ???????????? ????????? ????. ? ???? ????? ???????????? ????????????????
? ??????????? ????????? ???????? ????? ?? ???????????? ????? ??????????? ???????????? ???? ? ???????????? ????? ????????? ??????????? ??? ? ??????????, ??? ? ? ???????
????? [4].
? ???????? ??????????? ??????????? ?????? ???????? ?????????? ????????? ?????
??????????????? ??????? ??????? ??????????? ???????? ?? ?????????. ??????????? ???????
???????? ? ????????? ?????? ?????????? ??????????? ?????????? ?? ?????????????, ???????? ? ????????? ????, ?? ??????????? ?????????, ????????????? ?????? ????? ??????????,
? ??? ????? ????????. ?????? ??????????? ???????? ?? ??????? ?? ?????? ?????????? ? ?????,
? ???????????? ?????? ?? ????????? ? ????????????? ?? ???????????? ? ???????????????
??? ???????? [1, 2, 6, 10, 14, 15]. ?????? ? ??? ???????? ????? ?? ????????? ???????? ????????????? ???????? ??? ???? ?????????? ?? ???? ?? ??????????? ? ????????? ???? ? ????????.
??????, ???????? ?? ?????????????? ???????? ? ?????????? ?? ?????? ???? ???????????
??????? ???? ? ????????? ???????????? ????????? ????????????? [3, 5, 7?9], ??????????? ??????????? ??????????? ????????????, ???????????? ?? ???????? ? ????????????? ??????????????? ??????? ????????? ????? ???? ? ????????????? ? ??? ????????? ???????? (???).
??????? ???????????? ???????? ??? ??????????????? ?????? ???????????? ?????????? ? ????????? ? ??????????? ?????.
??????? ? ?????? ????????????
? ???????? ???????? ???????????? ???? ???? ??????? ??????? ????????? ????? ????
??????????? ????????? ?. ???????????? (????????? ? ?, ??????????? ? ?, ??????????? ? ?),
???????????? ???????? ????? ? ??, ? ????? ????????? ????? ? ? ? ???????????? ??????? ? ?.
?? ???? ???????? ????????? ???????? ???? ???????? ????????? ????????? (??), ?????????
(??) ? ??????????????? (???) ?????? ?? ????????????? ???????? [11, 13] ? ?????????? ??
???????? ?????????? ? ????????????? ???????? ??????????????? ? ???????????????? ????????. ??????????? ????????? ? 3?4 ????????????. ?????? ???? ?????????? ?????????????
??????? ?????????. ?? ?????? ?????????? ?????? ???? ???????? ?? ??????????? ?????????? ? ?????? ? ?????.
?????????? ?????? (??????????? ??N) ?????????? ??, ??? ? ?? ??? ???????? ?
?????????????? ???????????? ?????? ????????????? ??????????? ??????? ????????????? «???????» ????????? (????????????) ???????????? ???????????? ??. ?.?. ?????????? ??? ?????????? ????????? ???????????? ??????????? ? ????? ??, ?? ?? 29.04.2011 ?.
?16.552.7023. ?????? ???? ????????? ?? ?????????? ??????????? ??N. ?????????? ??????
???? ???????????????? ???????-?????????????? ??????? ? ?????????? ? ???????????
??????????????? ???????.
??? ???????????? ??????????-??????????????? ??????? ??? ??? ??????????? ????? ???????????????. ???????????? ? ??-??????? ????????? ? ?????? ????????? ???, ???????
?????????????? ?????????? ? ???????? ? KBr ? ????????????? ?? ??-?????-????????????.
?????????????????? ?????????? ???????? ??? ????????? ??? ? ????????? ????? ???# 140 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
???. 1. ????? ????????? ????????? ?????? ? ????????? ?? ?????
?????? ?? ???. 1. ????? ? ?????: ?? ? ????????? ???????; ?Na ? ????? ??????; ?Zn ? ?????
????? (????); ?? ? ?????????????; ?Na ? ??????? ??????; ?Zn ? ??????? ????? (????); ??? ?
??????????????? ???????; ??Na ? ????????????? ??????; ??Zn ? ????????????? ?????
(????).
?????????? ???????????? ? ?? ??????????
??????????? ????????????? ????????? ???????? ???????? ??????? ?????????? ?? ?
??? ?? ????????? ? ??; ?????????? ?????????? ?, ? ??????? ?????????? ?? ??????????? ?????????? ?? ? ??? ? 2 ???? (???. 2).
????? ?? ????????? ????????????? ????????? ?????? (???) ?????????? ????????????? ???????? ?? ?????????? ??????. ?? ????????? ???????? ?????????? ? ????????? ???????? ????????? ??????, ????????? ?? ?????????, ? ????? ??????? ?????????? ????????? ?
????????, ???????????? ??? ???????????. ?????????? ?????? ????????????? ????????????????????? ???????. ? ?????? ????? ???? ??????? ????? ?????????? ??????? ?????????
?:?, ?:? ? N:?.
??? ?? ?????????? ???????? ???????? ??????????? ?:? (1,39?2,73) ???????, ??? ??? ??
(1,52?5,85) ? ??? (1,52?3,14), ??? ????????? ?? ?? ????? ????????????? ???????? ? ???????
????????????. ??????? ?? ???????? ? ? ? ???????? ??????????????? ?????????? ???????
????, ??? ??? ?? ???????? ?:? ????? 2,0, ????? ??? ?? ????????? ???????? ????? ????? ?????????? ???????????? ????????, ???????? ??????????? ????????????? ?????????? ?????????????? ????????. ??? ?? ? ?????????? ? ????? ??????? ????????? ?:? (6,30), ??? ???????
? ???????????? ?????????????? ????? ??? ????????????? ? ??????? ??????? ????????????
???? ????????. ??????? ?? ????? ?????? ???????? ??????????? N:? (0,08?0,13), ??? ??????????? ??????????? ???????? ????????? ???????????? ? ?? ????????????. ??? ??? ?
# 141 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
???. 2. ?????????? ????????? ?????? ? ??????????? ????????
?????????? ?????????? ???????? ???? ??????? ?????????: ?:?, ?:? ? N:? (3,14; 10,05 ? 0,16
??????????????), ??? ??????????????? ? ???????????? ?????????????? ????????????? ?????
??? ?????????????. ????? ?????????? ????????????? ???????? ????? ??????? ??? ?????
? ????????? ????. ????????? ?:? ??, ?????????? ?? ???????? ????? ? ???????, ???????????
????????? ?? ????????? ? ???????? ??? ??, ?????????? ????? 1,5, ? ????????? ?? ???????????? ??????????????? ??? ?????????? ????????? ?????? ??????????. ??? ???? ???????? ?:?
?? ?? ????????? ? ?:? ?? ???????? ?, ? ? ??, ????????, ??????????: ? (5,85) > ? (5,23)> ??
(3,77) > ? (1,64) ? ? (1,52) ? ? (1,53). ? ??????? ?? ?? ?? ??????????????? ????? ?????? ??????????? ???????? ? ??????? ? ?????????, ??? ??????????????? ? ???????????? ?????? ?????????????? ????? ? ????????? ?? ? ???????????? ????? ???????? (??????? ?????????? ?????
? = ?; ????; ??? ? ??). ?? ??????????? ?:? ?? ????????????? ???????? ????????????? ?
????????? ???: ?? (10,83) > ? (6,33) > ? (5,85) ? ? (5,85) ? ? (5,23) > ? (2,81). ???????????? ?????????? N:? (0,55) ?????????? ??????? ?? ????????????, ??? ??????? ? ????????? ????? ???
???????????? ???? ??????? ????, ? ??????? ?? ??????? ? ??????????, ?? ?????? ???????, ??
???????? ????? ????? ??? ???????? ??? ? ?????????? ???? ??????? ???????????.
??? ????????? ????????????? ???????? ??, ??? ? ?? ????? ????? ????????? ?????????? ??????? ???????????? ????????? ?????? W = 2QO ? QH/QC, ??? QO, QH, QC ? ????? ??????
?????????, ???????? ? ???????? ? ???????? [12, 13]. ??? ???????? ?????? ????????????? ?
????????????? ???????????? ???????????? ?????????? ???????????? ? ?:
? = ?????/( ????? + ?????) ??? ? = ?????/????·100 %,
??? ????? ? ?????????? ???????? ????????????? ??????????; ????? ? ?????????? ????????
?????????? ?????????? ? ????????? ?????????. ?????? ?? ??????????? ????????? ?????
???????????? ?????????? ???????? ?? ???????????????? ??????? ???-????????? ????
????????? ??????? ????????????. ?????????? ?????????? ????????? ? ????. 1. ??? ????
???????????, ??? ?:? ????????????? ????? ????? 0,33 ? ? ? ??????????? ????? ???????????
??????? ????? 0,67.
????? = ((?:?)?.?. + 2(?:?)·? ? (?:?)????/ ((?:?)???? + (?:?)????).
????? ????, ???? ????????? ?????????? ??????? ?????? ??????????.
# 142 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
??????? 1. ?????????? ??????? ??????? ???????????? ? ????????????
??? ???????
?? ?
?? ?
?? ??
?? ?
?? ?
?? ?
??? ?
??? ?
??? ??
??? ?
??? ?
?? ?
?? ?
?? ??
?? ?
?? ?
?? ?
??????????
???????
?26?72?100N4
?35?74?219N4
?59?108?142N4
?38?56?143N4
?48?67?209N4
?30?52?117N4
?73?102?82N4
?24?76?244N4
?25?73?128N4
?34?57?91N4
?44?83?114N4
?35?53?98N4
?36?52?220N4
?23?88?252N4
?28?46?164N4
?8?42?336N4
?5?28?244N4
W
?/? ????
+4,81
+10,48
+3,34
+6,03
+7,25
+6,11
+0,84
+16,96
+7,52
+3,67
+3,29
+4,10
+11,14
+17,88
+10,05
+87,23
+88,76
7,79
10,55
5,62
6,53
7,19
7,04
2,89
16,61
9,95
5,25
5,34
5,29
10,01
18,28
9,48
13,19
12,24
????
?????
0,92
0,94
0,89
0,90
0,91
0,91
0,80
0,96
0,94
0,88
0,88
0,88
0,94
0,96
0,93
0,95
0,88
???????
????????????, ?
41,40
42,30
40,05
40,51
40,95
40,95
36,03
43,20
42,30
39,63
39,60
39,60
42,31
43,20
41,85
42,75
39,60
? ???????? ????????? ???? ??????????? ???????? ??????????? ??????? ???????????? ??
??? ? ?? ? ?? (?? 1,5 ???? ? ? ?? 24?27 ??? ? ? ? ?). ? ?? ????????? ????? ??????????? ???
?? ????????? ? ??. ?????????? ????????????? ??????????????? ? ????????? ??? ???????
?? ????????? ? ?? ? ??, ???????? W ??????? ????????? ?? ????? ??????. ??????????? ?????????? ?????? ???????? ?????????? ??? ?????????, ?????????? ?? ?????, ??? ?????? ?????
??????? ? ????????????? ????????? ??? ????????????.
??? ????????? ??? ???????? ??????? ??????? ??????? ????????????. ?????? ?????????? ??????? ? ????: ? > ? > ? > ? > ? > ?? ??? ??; ??? ???: ? > ?? > ? ? ? > ?, ? ??? ??:
?? > ? > ? > ? > ? > ?. ??? ?????????? ??? ? ?? ?????????? ??????? ?????????????? ?????
????? ???????? ???????????? ? ???????? ???????????? (r = 0,85 ? r = 0,82 ??????????????). ?
?????????? ?? ?????? ?????????????? ????? ?? ???????????.
????? ?? ???????? ?????? ???????????????? ???????, ????????????? ??? ??????????
???????? ???????? ??? ? ????? ????????? ??????????????? ?? ??????????? ? ?????????????, ???????? ?????????? ???????? ?. ??? ?????????. ?????? ???????????? ?? ???????????
????????????? ?????? ? ??????????? (H/C)?????/? ? ?????? ??????? ??????? ??? ???????????? ?????? ????????? ????????? ? ??????????? ? ????????? ??????????? ??????? ??????????.
?? ???. 3 ???????????? ????????? ?. ??? ????????? ???, ?????????? ?? ????????? ????????? ????????.
?? ????????? ?????? ????????? ???????????, ??? ??????? ??????????? ?? ???????? ?????????? ??? ??????????? (H/C)???, ??? ? ?/?, ?.?. ?????????????? ??????????? ???? ????????????? ???????? ? ??????????? ??????? ????????????. ????????? ??, ?????????? ?? ????
????????????? ????????, ????? ?????? ???????? ?????? ???????????, ?.?. ? ?? ?????????
?????????? ???? ????????????? ?????????? ? ??????????? ?????????? ??????????????????
?????????????? ?????.
# 143 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
???. 3. ????????? ?. ??? ?????????
??? ???????????? ??????????-?????????????? ???????????? ???????? ??? ???????????? ????? ??-?????????????. ??-??????? ???? ???????? ??? ??????, ? ??? ???????????
??????????? ?????? ??????????, ????????????????? ? ????????????????????? ???????
???? ??????: ?????????? ??????? ??????????? ?????? ? ??????? 3500?2500 ??-1 ? ???????
????? 3200 ??-1, ??????????? ?????????? ??????????? ????????????? ??????????. ?????? ????????? ???????? ????? -??3 ??????????? ??? 2860 ??-1; ?????? ??????????? ?????
(-??2-) ???????????????? ? ??????? ????????? ????????? ??? 2920, 1410, 900?700 ??-1. ? ??????? 1700?1600 ??-1 ??????????? ??????????? ??????, ??? ??????? ? ????????? ?????????
? = ? ? ???????????? ?????? ? ????????? ?????????? ???????? (? = ? ????????.). ?????
????, ???????? ?????? ?????????? ???? ? ????? ??????????????? ??????? ??????? ????????? ?? ??????? ?????????? ? ???????. ? ??????? ?????????? ???????? ??????????????? ??????
1100?1000 ??-1. ?????? ???????? ?????? 1450, 1140?1120 ??-1, ????????? ? ?????????????
??????? ? ??????? ???????.
???????????, ??? ?????????? ???????? ??????? ?????? ?????????? ? ???? ?? >???>??
??? ???? ????????????? ????????, ????? ? (???. 4). ??????? ??? ???????? ?? ???? ??????????? ?????? ? ????????? ???????? ????????????? ? ????????????? ???????????, ??? ????
????????????? ????????? ?????????? ?????????????????? ? ?????????? ?????????. ??????????? ??????????????? ???????????? ?????????? ?????????? ??????????? ?????????
?????????????? ????? ????????? ??????? ??? ?????????? ?? ?? ???????, ??? ????????? ??
??????? ???????????? ???????? ????????????????? ? ???? ??????.
?????? ??????? ?? ????????? ? ???? ???????? ? = ?>?>?>?>??. ??? ????????? ????
????? ?????????? ???????? ????????? ?? ????????? ? ? ? ?. ?????????? ?????????? ??? ?,
??????? ??????? ????????????? ?? ???? ????????????? ?????? ??-????? ? ?????????? ??????????. ????????????? ?? ? ??? ?????????? ? ????? ???????????????????: ?>?>?>?>?>??
? ?>?>?>?>?>?? ??????????????.
?? ?????? ??????????? ?????????? ????????????? ????? ??? ????????????? ????????
????? ??????????? ? ????????? ???: ?>?>?>?>?>??. ??? ???????????? ?????????? ????????????? ????? ? ???????? ??? ???????????? ?????????? ??????? ??????? ????????? ?????,
? ??? ???????????? ?? ?????????? ??????????. ??????? ??????????? ????????? ??-?????
? ?????????? ??????????? ?????????? ??: ?>?>?>?>?>?? ? ?>?>?>?>?>?? ????????????# 144 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
?
?
???. 4. ?????????????? ????? ?????????? ??? (?), ?????????? ?? ????????? ????????? ????????, ?
????????????? ????????? ?????????? ?????????????? ????? ? ??? (?)
??????? 2. ???????????? ???????????? ?????????????????? ????? ????????? ??????
???????????
???????????
?????????
???????????
????
??????
??
??3400/? = ?1610
?2N2350/? = C1610
???2100/? = ?1610
????1720/? = ?1610
N = O1450/? = ?1610
????1120/? = ?1610
???1070/? = ?1610
???? 2920/? = ?1610
??3400/???? 2920
?2N2350/???? 2920
???2100/???? 2920
????1720/???? 2920
N = O1450/???? 2920
1,10
0,62
0,29
0,34
0,41
0,99
0,84
0,84
1,31
0,74
0,35
0,40
0,49
1,09
0,06
0,15
0,78
0,96
1,08
1,81
1,23
0,89
0,05
0,12
0,49
0,77
1,63
0,14
0,45
0,99
1,92
0,97
1,09
0,13
12,23
1,07
3,41
7,41
14,47
2,32
0,16
0,05
0,79
0,55
2,45
2,79
1,05
2,19
0,15
0,05
0,73
0,52
2,33
0,15
0,06
0,78
0,53
2,46
2,90
1,06
2,09
0,16
0,05
0,73
0,53
1,24
1,27
0,94
1,43
0,98
6,47
6,07
1,24
1,00
1,03
0,76
1,43
0,79
??. ? ???????????? ?? ???????????? ???????????? ????? ?????? ????????????? ? ????????????? ??????. ?????? ?????????????? ??????? ? ??????????????? ????????? ??????????
?????, ????????? ??? ???????? ????? ???? ????. ??????? ?? ? ??? ? ? ? ???????????????
????????? ??????? ??????? ?????????? ?????????????????? ?????????????? ????? ? ?????????? ??????????? (???. 4), ??? ??????? ?? ??????? ????????????? ???? ???????? (???????
????????????? ?????????).
????????????? ?????????? ?????????? ? ????????? ?? ??????????? ? ?? ? ? (???. 4?).
??? ??????? ? ???, ??? ? ?????? ?????? ? ???????? ??????????? ???????????? ???? ??????
???????????? ? ????????. ??? ????????? ????? ???? ??? ??????????? ??????, ?? ???? ????
?????????? ?????????? ??????? ?????. ??? ????????? ?? ???????????? ????????????? ????????? ? ???? ??????.
????????? ??????????? ??? ????? ?????? ??????? ???????????????? ????????????? ?
????????????? ???????????? (????. 2?4). ?????????? ?????????? ?? ?, ??? ? ? ?, ?? ?. ??
?????? ?????????????????? ?????? ??? ???????? ????? ??????????????????.
?? ???????? ????????????? ? ??????? ???????????? ?? ?????????? ?? ??????????? ???????? ????? ??????????? ? ???: ?>?>?>?>??>? (???. 4?), ? ?? ??????????? ??????????
# 145 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
??????? 3. ???????????? ???????????? ?????????????????? ????? ??????????????? ??????
???????????
???????????
?????????
???????????
????
??????
??
??3400/? = ?1610
?-?2600/? = C1610
?2N2350/? = C1610
C???1720/? = ?1610
????1160/? = ?1610
???1060/? = ?1610
???? 2920/? = ?1610
??3400/???? 2920
?-?2600/???? 2920
?2N2350/???? 2920
????1720/???? 2920
????1160/???? 2920
???1060/ ???? 2920
1,43
1,70
0,68
1,05
1,19
1,14
1,34
1,02
0,78
0,64
0,78
0,88
0,85
2,64
0,29
0,16
0,76
2,23
3,56
1,07
2,45
0,27
0,19
0,66
2,08
3,31
2,25
0,06
1,30
2,36
5,09
3,70
1,52
3,00
0,09
0,85
3,61
7,41
5,67
2,27
2,07
0,10
1,14
1,23
1,65
0,36
0,81
0,74
0,26
0,41
0,44
0,59
0,91
0,68
0,59
0,57
1,02
3,62
0,75
1,21
0,91
0,44
0,76
1,36
0,83
1,24
1,47
1,30
1,43
6,47
6,07
1,25
1,00
1,19
0,09
1,16
5,23
4,92
??????? 4. ???????????? ???????????? ?????????????????? ????? ????????? ??????
??? ?????
???????????
?????????
???????????
????
??????
??
??3400/? = ?1610
?2N2350/? = C1610
??C2100/? = ?1610
C???1720/? = ?1610
N = O1440/? = ?1610
????1120/? = ?1610
???? 2920/? = ?1610
??3400/???? 2920
?2N2350/???? 2920
??C2100/???? 2920
????1720/???? 2920
1,19
0,99
0,75
1,11
0,63
1,10
1,10
1,08
0,90
0,69
1,01
0,61
0,20
0,24
0,82
1,39
2,60
0,29
2,08
0,67
0,80
2,80
0,71
0,45
0,47
0,72
1,40
1,48
0,60
1,18
0,75
0,78
1,39
0,38
0,56
0,36
1,01
1,01
3,00
0,73
0,52
0,39
0,99
1,40
0,63
0,69
0,17
1,42
1,41
2,34
0,475
1,31
0,47
0,98
2,91
7,20
0,83
0,36
1,40
1,42
1,72
0,40
1,80
0,25
0,37
3,50
?????????????? ?????: ?>?> ?>?>?>??, ??? ??? ??????? ? ??????? ???????????????? ???????? ?? ??????????, ??????? ???????? ??????? ?????? ?????? ????. ????? ???????? ??
? ???????? ?????????? ???????? ???????????????????: ?>??>?>?>?>? (????. 4).
????? ?????????????? ???????????? ??? ????????????? ?? ??????????????????? ???????????. ?????????? ????????????? ??? ???????? ????? ?????????? ??????????????? ?
???????????????????? ????????? ??????. ? ???????? ??????? ????? ? ???? ?????????????
????? ?????????? ??????????? ? ??????? 3400 ??-1, ??????????? ??? ????????? -?? ????? ?
?????????? ?????? (???. 4).
???????????? ????????? ????????????? ????? ?????????? ??????????? ? ???????? ?????????????????? ????????? -??2- ????? (2920 ??-1), ????????????? ?????, ?-? ????????? ?????.
??? ??????? ? ???, ??? ??? ?????? ?????? ???? ????? ? ??????? ????????????????????. ?????????? ?????? ???????????????? ????????? ????????? ? ??????? 1550 ??-1 ? ????? ?????? ??????
???????????? ????????? ????? 1400 ??-1, ??? ????????? ?? ??????? ???????????-????; ????????
?????? ?????????? ? ??????? 1620 ??-1, ??????????????? ??????????? ????????????? ?????? ? ??# 146 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
???. 5. ??-??????? ??, ?????????? ?? ???????????? (1), ?????? ????? (2) ? ?????? ???? (3)
?????? ??????? ??. ????? ???????, ???????????? ???? ? ?????????? ????? ??????? ????????
?????? ????????????? ? ????????????? ??????:
? ????????? ?? ??????????? ???????? ???????????????????? ?????????????? ?? ????
??????? ? ??????? ?????:
??? ??????????? ????????? ? ?????????? ?????? ?????????? ? ??????? 1450 ? 1300 ??-1.
?????????? ????????? ?????????????? ????? ?????? ?????????? ? ??????? 2350 ??-1.
??? ???????????? ??-???????? ???, ?? ? ?? ???????? ? ?????? ????? ??????????? ??
?? ???????? ????? ??????????, ??? ? ??? ???????.
??????????
??????? ?????????? ??????????, ????? ??????? ????????? ??????: ? ??????????? ????????????? ??????????, ?????????? ?? ????????? ????????? ????????, ???????? ???????
?????????? ?? ? ??? ?? ????????? ? ??????????? ??, ?????????? ?????????? ???? ???,
# 147 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
?????????? ?? ????????????, ? ??????? ?????????? ?? ??????????? ?????????? ?? ? ??? ?
2 ????.
????????? ?????? ??? ?????????? ?? ???????????? ?????? (???????? ???????), ??????? ?? ?????????????, ??????????????????? ? ????????????.
?????????? ???????? ??????? ?????? ?????????? ? ???? ?? >???> ?? ??? ???? ????????????? ????????, ????? ?. ??????? ??????????? ?? ?????????????? ??????????? ????
????????????? ???????? ? ??????????? ??????? ???????????? (?? >?? > ???). ? ?????????
?? ?????????? ???? ????????????? ?????????? ? ??????????? ?????????? ?????????????????? ?????????????? ?????, ??? ????? ?????????? ?? ????????? ? ??, ????? ????????
????????????? ???????? ? ??????? ??????? ????????????. ??? ???? ???????? ??????????
????????????? ???????? ????? ???????? ?? ? ? ? ?? ????????? ? ??????????? ?????????
????????.
??????? ????????????? ?? ? ??? ?????????? ? ????? ???????????????????:
?>?>?>?>?>?? ? ?>?>?>?>?>?? ??????????????.
??????? ??????? ???????????? ????????? ?????? ??????? ? ???????? ????????????
????????????-?????????????????? ??????, ???????????? ??? ???????????? ? ?????????????
???????. ????????????? ?????????? ??????? ???????????? ?????????? ??. ?? ???????
?????????? ? ?????? ????????????? ?? ??????????? ???????? ????? ??????????? ? ???:
?>?>?>?>??>?, ?? ??????? ??????????????????: ?>??>?>?>?>?. ??????????? ?????????? ??????? ???????????? ?????????? ??? ?????????, ?????????? ?? ?????, ??? ?????? ?????
??????? ? ????????????? ????????? ??? ????????????.
??????????? ??????????????? ???????????? ?????????? ?????????? ??????????? ????????? ?????????????? ????? ????????? ??????? ??? ?????????? ?? ?? ???????, ??? ????????? ?? ??????? ???????????? ???????? ????????????????? ? ???? ??????.
? ??????? ??-????????????? ???????????, ??? ? ?????? ??? ?????? ??? ????????? ?????? (-????), ??? ? ???????? (-NH2, = NH), ??? ??????? ?? ???????????? ?????? ??????; ?????????, ???????????; ????????? -?-? ??????, ?????????? ? ????????????? ?????????, ?
??? ????? ????????????? ?????- (-NO2) ? ???????- (-N = O) ??????; ? = ? ? ??? ?????.
??? ???????? ????????? ? ????????? ?? ???? ????????????? ? ????????????? ?????,
??????????. ????????? ????? ???????????? ?????????? ????????? ?????? (??????????????? ??) ???????????? ???????? ?????????????? ?? ?????????? ??????? ? ????????? ? ??
?????????? ? ????????? ??? ???????? ?????. ? ?? ?? ????? ????????????? ???????????
??????? ??? (??????????????? ?? ? ???) ????????????? ????????? ????????????? ??????? ???????? ? ?????? ? ????????? ???????????, ????????? ? ???????? ???????? ??? ??????????????, ???????? ?? ? ?????????, ????? ???????, ?????? ?? ??????????????.
? ?????????? ?????????? ????????, ??? ????????? ????? ???????? ??????????? ????????????? ???????? ?????? ???????????? ???????? ?? ????????? ? ??????? ????????, ???
??? ????????? ?????????? ? ??????????? ????????? ? ????????? ????, ?????????? ?????????? ??????????????????? ??????????????? ???????? ??, ?????????? ?????????????
?????????? ? ? ???????????? ??????????? ?? ????? ???? ??? ????????????? ? ??????
????????. ??? ???? ???????????? ??????????, ??? ?????? ? ???? ???????? ? ????? ???????
?? ? ???, ???????? ??????? ????? ??????? ?????????? ???????????? ?????? ? ????????
# 148 #
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?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
?????????????? ?????? ? ??????? ???????? ????????????, ??? ????????? ?? ???????????? ?
?????? ?????????? ??????????? ??????? ? ??????????? ?????????? ??? ????????? ???????
? ????????? ??????? ????????. ??????? ?????? ????????? ????????? ????? ?????????????
??? ????????????? ? ???????? ???????? ??????? ? ????? ????????? ??????????????? ???????
????????? ????.
???????????? ?????????? ??????? ????-? ? 12-05-31512.
?????? ??????????
1. Basta N. Heavy Metal and Trance Element Chemistry in Residual-Treated Soil: Implications
in Metal Bioavailability and Sustainable Land Application // Abstracts of Sustainable Land Application
Conference. Lake Buena Vista, Florida. 4?8 January. 2004. P. 3?10.
2. Cao J., Lam K.C., Dawson R.W., et al. // Chemosphere, 2004. V. 54. P. 507?514.
3. ???????????? ?.?. ???????????? ???????? ????? ? ???????? ??? ?????????????.
?.: ?????, 1980. 287 ?.
4. ???????????? ????????? ?????????????? ?????????? ??????-?????? ??????? ????
?????? (?? ??????? ?????????? ???????) / ???. ?.?. ??????, ?.?. ???????. ????????????:
????? ???, 2005. 188 ?.
5. ?????? ?.?. ?????????????????? ?????????????? ????????? ?????? ?????? ????????? // ??????? ?????????? ???. ??-??. 2008. ? 3. ?. 153-160.
6. ????????? ?.?., ????????? ?.?., ???? ?.?. ????? ???? ???. ???????????? ???????????? ???????? ????????? ???????????? ??????????? ? ?????????????????? ???? ? ?????????????? ??????????? ?????????? // ??????????. ?., 2009. ? 3. ?. 41-43.
7. ????????????? ?.?., ??????? ?.?., ??????? ?.?., ???????? ?.?., ??????? ?.?.
??????? ????????????? ?????????? ?????? ?? ???????????????? ??????????? ???? ? ??????? «?????-????????» // ???????? ? ?????????????? ??????. ?.: ??????, 2012. ? 6.
?. 50 52.
8. ??????? ?.?., ??????? ?.?., ????????????? ?.?., ??????? ?.?. ??????? ????????????? ?????????? ?????? ?? ??????? ?????????????? ?????? ? ?????? ?? ???????????? ???? //
???????? ?????? ??????? ?????????. ?????: ????? ? ?????????? ??????????. ???????: ????? ?????, 2013. ? 56, ? 11. ?. 68-73.
9. ??????? ?.?., ??????? ?.?., ???????? ?.?., ????????????? ?.?., ??????? ?.?. ?????????? ???????? ??????? ? ???????? ?????????????? ?????? ? ?????? ?? ???????????? ????
????? // ??????? ?????. ? ?., 2010. ?.5, ? 5. ?. 102-105.
10. ??????? ?.?., ??????? ?.?., ??????? ?.?. ? ??. // ?????????. 2005. ? 8.
?. 58?64.
11. ????? ?. ?, ??????? ?. ?. ????????? ?? ????? ??????: ????. ???????. ? ?: ???-??
????. ??-??, 1981. 272 ?.
12. ????? ?.?. ????????? ??????? ???? ? ????? ?????? ???????????. ?.: ?????, 1993.
325 ?.
13. ????? ?.?. ????????? ????????: ????????, ????????, ??????????? / ??? ???. ?.?. ????????. ???.: ???-?? ?.-??????. ??-??, 2004. 248 ?.
# 149 #
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?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
14. ????????? ?.?., ????????? ?.?., ?????? ?.?., ?????????? ?.?. ?????????? ??????
??????????? ???????? ????????? ????????????? ????????? ? ??????????????? ?????: ??????? ?????????? ???????? ???????????????????? ????. ?., 2012. ? 6. ?. 53-55.
15. ??????? ?.?., ????????? ?.?., ??????? ?.?., ??????? ?.?. ??????? ????????? ????????? ?? ?????????????? ?????? ?? ???????????? ????? // ??????? ?????. ?., 2013. ?.8,
? 1. ?. 106-111.
The Structure of Humic Acids
as a Function of the Performance
of Ecoprotective Role for Heavy Metals
Tatiana A. Korelskayaa and Tatiana I. Rumyantsevab
a
Northern State Medical University,
51 Troitsky, Arkhangelsk, 163000 Russia
b
Northern ( Arctic) Federal University
named after M.V. Lomonosov,
4 Lomonosov, Arkhangelsk, 163002 Russia
Research of structural and functional features of humic acids in the urban soils, peat and lignin is
conducted by methods of the element analysis, IK-Fourier-spectroscopy, spectrophotometry.
The assessment of possibility of performance of tread functions by them concerning heavy metals is
given.
Increasing the size of acid molecules occurs in a number of fulvic < Himatomelanic < humic acid. The
majority of preparations of humic acids have the same degree of formation of aromatic and aliphatic
component and a high degree of oxidation (W = +3,34 ... +10,48). The maximum degree of benzenoid
characteristic of humic (a = 42,3) and Himatomelanic acid (a = 43,2) lignin and fulvic acids (a = 43,2)
of natural soil.
Urban soil, which have a sufficiently low degree of oxidation of humic acids and very high ? fulvic,
have low tread function in relation to heavy metals. However, lignin and peat contain a humic acid
composition with a high benzenoid, oxidation and developed peripheral portion, which indicates
the possibility of the barrier function for heavy metals. Therefore, these natural materials can be
recommended for use in the making lawns to improve tread function of urban soils.
Keywords: humic acid, tread function, soil, lignin, peat, heavy metals.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 151-158
~~~
??? 661.72.886
????? ???????????? ?????? ?????????
?.?. ????????*, ?.?. ????????
????????? ???????????? ?????????????????
??????????????? ???????????
??????, 420015, ?????????? ?????????,
??????, ??. ?. ??????, 68
Received 21.10.2013, received in revised form 05.11.2013, accepted 24.12.2014
??????? ?????????????? ??????? ????????? ? ?????????????? ???????? ???????. ?
?????????? ??????-?????????? ???????????? ???? ??????????? ???????? ????????? ????
?????????? ???????.
???????? ?????: ?????? ?????????, ????????????, ????????? ????????? ?????, ??????????
???????????.
????????
?????? ????????? (??) ??????? ? ????? ??????????? ?????????, ??????? ??????
???????-????????????? ????????. ?? ???????? ??????? ????????? ???????, ??????, ????? ?
????????????? ?????????? ???????? ??????????. ???????????????? ???????? ?????????????
??, ??????? ???????? ?????, ??????????????? ??????????? ??????????????? ??????????????, ? ??????? ??????? ?????????? ????? ????????????? ???????? ?????????? ??????? ???????????? ?????????? ??????????, ?????????? ?? ?????? ?????????????? ? ?? ???????????
[1, 2].
? ????????? ???? ????????? ???????? ????????????? ?? ????????? ??????-??????????
? ???????????????? ??????? ???????? ????????? ????????????? ??? ????? ????????? ???????? ?????????? ???????????.
??????????? ????????? ???????????? ???? ?? ????? ??????? ?????????????????? ?????????? ? ?????? ???????????? ???????????. ??? ???????, ?????????? ?? ???????????
????? ????????? ? ??????, ? ??????? ???????? ??????? ???????????? ?????????? ??? ?????????? ????????????, ? ?????????? ???? ?? ???????????? ? ??????? ????? ??????????? ????????. ????? ???????, ??????????? ????????? ???????? ?????? ????????????? ???????, ??????????? ? ??????? ????????? ???????? ? ???????? ??????????? ?????????? ? ??????????
???????? ?????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: romsvetlana80@mail.ru
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? ????????????????.
? ?????? ?????? ????????? ???????????? ?????????????? ????????????? ???????? ??????? ? ?? ? ???????? ????????????? ????? C6H7O2(OH)0,46(ONO2)2,54.
???? ?????? ???????????? ? ???????? ??????????? ?????????? ??????????? ?? ?????????????? ??? ?????????? ????????????? ? ??????? ??????-?????????? ? ???????????????? ???????? ?????????? ??????????.
???????? ????????????
????????? ?????????. ? ???????? 1 ? ?? ? 25 ?? ???????? ? ?????????? ????? ???????
250 ??, ?????????? ????????, ???????? ????????????? ? ?????????????? ??????? ? ???????????, ????????? ??????? ????????????? ? ???????? ?? ??????? 1 ???? ????????????? ???????? ??????? ?? ?????? ????????? ?????? ????????? ????????.
??????? ????????? ??? ????????? ???????????? ? ????????? ??????? ???????? (????. 1).
??? ????????? ???????? ???????????????????? ?????????????????? ???????? ??????????
?????????? ??????? ?????????? ? ???????????????? ???? ??? ?? ???????????, ??? ???????
????????? ???????, ???????? ??????? ?????? ??????????????? ?? ??????? ????? ? 2, ????????? ??????? ????? ? ?????? ?? ?????????? ?????.
????????? ????????? ? ??????????. ?? ?????????, ??????????? ????? ?????????? ?? ????
????????, ??????? ??? ???????? ??? ?????????? ???????? 20 ?? ??. ??. ???????????? ? ????.
????????? ????????? ?? ??????????? ????????? ???????? ??? ??????????? 100 °?. ?? ????????? ???????? ?? ?????????? ????? ????????? ?????-?????????? ??????????? ???????, ??????? ????????? ?????????? ??????? ?? ?????????? ??????????? ???????, ????? ?????????? ? ?????????? ??? ???????? ??????? ?? ?????????? ????? (????. 2).
?????????? ? ?? ??????????
? ??????? ?????????? ???????????? ???????? ? ?????????????? ?? ? ???????????????
?????????? ?????? ?????????????? ? ?????????????? ????? ? ??????????? ????????????? ?
?????? ?????? (SnCl4, AlCl3, SbCl5, TiCl4, ZnCl2, BF3?O(C2H5)3) [3?6]. ?? ????????????? ? ???????? ????????????? ????????????? ????????? ??????? ? ??????? ?????????????? ?????? ??
?? ???? ? ???????????, ??????? ? ?????? ?????? ?????????? ????? ?????????? ???????????
?? ?????????????? ???????? ??????? ??? ?????????? ????????????? ? ????? ????????, ??????? ???????? ? ???????? ?????????????? ???????? [?5?5NCOC2H3]Cl. ?????????? ?????????
???????????? ????????? ???????? ??????? ??????????? ???????? ????? ?? ? ?????????????
?????????, ??? ????????? ????????? ??????? ? ????????, ?? ????????? ??????? ??????????
? ??????????? ??????? ????????. ????? ???????, ??????? ? ???????? ?????????????? ???????? ?????????????? ???????????.
??????? ????????? ??? ??????????? 20, 30, 40, 60 °C ? ??????? ???????? ?? 2 ?? 6 ?. ?
?????????? ???????? ??????? ???????? ?????-??????????? ?????, ??? ??????. ?? ?????????,
??????????? ????? ?????????? ?? ???? ????????, ???????? ??????????????? ????????? ??
??????? ?????.
# 152 #
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27,46
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6
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14
16
6
13
37,16
38,01
4
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12
30
41,66
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9
10
11
46,87
49,13
51,32
56,85
61,12
67,39
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0,16
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1,09
1,25
1,45
2,65
2,78
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2,96
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0,48
0,49
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1,12
1,24
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48,84
47,77
46,91
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44,04
42,24
40,41
26,89
26,74
26,62
24,46
26,23
5,83
5,83
5,82
5,79
5,88
5,85
5,82
5,79
5,44
5,39
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C6H7O2(OH)0,39(ONO2)0,93(??2?3)1,68 44,98
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C6H7O2(OH)0,53(ONO2)1,12(??2?3)1,35
C6H7O2(OH)0,37(ONO2)1,04(??2?3)1,59 44,01
C6H7O2(OH)0,43(ONO2)0,80(??2?3)1,77
2,71
2,71
2,77
2,83
2,55
2,66
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C6H7O2(OH)0,07(ONO2)0,48(??2?3)2,45 53,15
C6H7O2(OH)0,06(ONO2)0,45(??2?3)2,49 53,97
C6H7O2(OH)0,07(ONO2)0,50(??2?3)2,43 52,58
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C6H7O2(OH)0,05(ONO2)0,47(??2?3)2,48 52,49
C6H7O2(OH)0,05(ONO2)0,49(??2?3)2,46 52,69
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C6H7O2(OH)0,04(ONO2)0,49(??2?3)2,47 53,01
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12,66 C6H7O2(OH)0,45(ONO2)2,47(??2?3)0,08 26,86
C6H7O2(OH)0,42(ONO2)0,74(??2?3)1,84 47,67
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C5H6(OH)2,03(ONO2)0,54COOH0,43
C5H6(OH)1,75(ONO2)0,71COOH0,54
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??? ????????????? ???????????? ????????? ?????????? ????????? ????????? ??????:
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1061 (?????); 1073 (??????????????? ??????); 1284, 1650 (?ONO2); 1385 ?1355 (???3); 1420 ?
1450 (?CH2?ONO2); 1707 ? 1727 (??=?); 1715 ?1757 (?????); 2930, 2980 ? ????? ?? ? ??????????? ???????????; 3500-3800 (??H).
??????? ??? 1? ??????????????? ? ????????? ?????????????? ????? ?? ????????
???????. ???? ???????? ?? ????? ???????, ??????????????? ???????? ????????????????
?????? (?. ?.): 4,1 (1,5?), 4.8 (6?), 5,15 (2,4?), 5,75 (3?), ?? ? ??????? ??? 1? ????????? ??????? ?????? ????????, ??????????????? ???????? ????????? ????????????? ????? ?????????, ???????????? ??????? 0,8012 ? 0,8525 ?. ?. (???3).
??? ??????????? ??????? ???????????? ????? ????????? ??????? ?????? ????????? ?
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T C lN O 2
m <n
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C H 2O N O 2
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???. 1. ????? ??????????? ?????????????? ?? ? ????????? ????????????? ? ????? ????????: 1 ? ????????
????????? ?????; 2 ? ?????? ?-??????????? ????? ? ?????????????? ???????? ????????? ?? ??????
?????????? ???? ? ????????? ?1 ? ?4 ? ??????????????? ???? ????????????? ???????? ? ????????????
??????????????? ?????????; 3 ? ????????? ?????????????? ????? ?? ???????? ???????; 4 ? ?????????
????????????????? ????? ? ???????????? ????????????? ???????
????? ??????-?????????? ??????? ???????????? ? ??????????? ??????? ??????? ??????????, ??? ??????????????? ???????? ???????, ?????????? ?? ?????????, ???????????? ?????
???????? ??????????????? ?????????? ???? ????????????? ??.
?? ????????? ?????? ???????????? ???????????? ????????????? ???? ?????????? ????????? ????? ???????????????? ??????????? ??????????? ??????????? ??, ??????????????
?? ???. 1.
?? ????????? ?????? ??????????? ????????????? ?????????? ???????????????? ??????????? ??????????? ?????????: ????????? ???????? ????????? ?????; ????????? ?????????????? ????? ?? ???????? ???????, ????????? ???????????????? ?????? ?? ? ??????????????? ?????????? ???? ? ?????????? ?????????? ??????? ???????????? ?????.
# 156 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????. ????? ???????????? ?????? ?????????
? ?????? ???? ??????? ??????? ??????? ? ??????????? ?????????????? ?? ???????? ????????? ???????. ??? ???????? ?????????? ????????????, ? ??????????? ?????????????????
??????? ??????? ????????? ?????????????? ????? ?? ???????? ??????? ??????????. ???
?????? ???????????? ?????????????? ??????????? ?? ??????????, ? ??? ???????????? ????
40 °? ?????????? ????????? ?????????? ?????????? ???? ????????????? ??. ?? ????????????? ?????????? ?????????????? ?????????, ??????????? ? ????????????????? ?????, ????? ?????, ??? ? ??????????? ????????????????? ? ??????????? ???????? ????? ??????????
????????? ??????? ?????????. ????? ???????, ? ????????? ?????????? 38?41 °? ??????? ??????????? ?????????????? ????????? ????????? ???????? ??????????.
??????
?????????????? ? ?????? ?????????? ??????-?????????? ???????? ?????????? ????????? ??????????????? ? ??????????? ?????????? ??????????? ?? ?????????????? ????????
??????? ? ?????????? ????? ????????. ?????????? ?????????? ????? ?????????????? ???????????? ????? ????????????? ??? ?????????? ? ??????? ??????, ????? ? ??? ????????????
?????? ??????? ???????-?????????????? ??????????.
?????? ??????????
1. ???????? ?. ?. ?????? ?? ? 2215720. 2003.
2. ??????? ?. ?. ???????????????? ?????? ??????????? ???????? ????????? ? ?????????? ??????? ?????????? ?????????? // ????????? ???????? ????????????? ????????????????? ???????????. ??????: ???-?? ?????. ???. ??????. ??-??, 2002. ?. 150-152.
3. ??????? ?. ?. // ?????????????????? ??????????. 1972. ? 14. C. 1278-1282.
4. ???????? ?. ?., ??????????? ?. ?., ???????? ?. ?. // ???. ?????. ????? ? ???. ??????????. ???????, 2012. ?. 55. ? 3. ?. 68-73.
5. ???????? ?. ?., ???????? ?. ?., ???????? ?. ?., ???????? ?. ?. // ?????? ????? ?????. 2013. ? 83. ? 1. ?. 65-69.
6. ????????? ?. ?. // ?????? ?????????? ?????. 1983. ?. 25. ? 11. ?. 2560-2564.
7. ???????? ?. ?., ???????? ?. ?., ???????? ?. ?. // ???. ?????. ????? ? ???. ??????????.
???????, 2003. ?. 46. ? 8. ?. 134-138.
8. ????????? ?. ?. // ?????????????????? ??????????. 1983. ?. 25. ? 9. ?. 1844-1849.
9. ????????? ?. ?., ???????? ?. ?. ?????? ?? ? 523109. 1976.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????. ????? ???????????? ?????? ?????????
Chemistry of Nitrate Cellulose Ethers
Svetlana M. Romanova and Liliia A. Fatykhova
Kazan National Research Technological University,
68 K. Marks Str., Kazan,
Republic of Tatarstan, 420015, Russia
The interaction of cellulose nitrate with chloride acetic acid is studied. As a result of physico-chemical
studies the most probable paths of the reactions were established.
Keywords: cellulose nitrate, chloride, nitrate groups substitution, chemical modification.
???????????? ??????; ??Zn ? ????????????? ?????
(????).
?????????? ???????????? ? ?? ??????????
??????????? ????????????? ????????? ???????? ???????? ??????? ?????????? ?? ?
??? ?? ????????? ? ??; ?????????? ?????????? ?, ? ??????? ?????????? ?? ??????????? ?????????? ?? ? ??? ? 2 ???? (???. 2).
????? ?? ????????? ????????????? ????????? ?????? (???) ?????????? ????????????? ???????? ?? ?????????? ??????. ?? ????????? ???????? ?????????? ? ????????? ???????? ????????? ??????, ????????? ?? ?????????, ? ????? ??????? ?????????? ????????? ?
????????, ???????????? ??? ???????????. ?????????? ?????? ????????????? ????????????????????? ???????. ? ?????? ????? ???? ??????? ????? ?????????? ??????? ?????????
?:?, ?:? ? N:?.
??? ?? ?????????? ???????? ???????? ??????????? ?:? (1,39?2,73) ???????, ??? ??? ??
(1,52?5,85) ? ??? (1,52?3,14), ??? ????????? ?? ?? ????? ????????????? ???????? ? ???????
????????????. ??????? ?? ???????? ? ? ? ???????? ??????????????? ?????????? ???????
????, ??? ??? ?? ???????? ?:? ????? 2,0, ????? ??? ?? ????????? ???????? ????? ????? ?????????? ???????????? ????????, ???????? ??????????? ????????????? ?????????? ?????????????? ????????. ??? ?? ? ?????????? ? ????? ??????? ????????? ?:? (6,30), ??? ???????
? ???????????? ?????????????? ????? ??? ????????????? ? ??????? ??????? ????????????
???? ????????. ??????? ?? ????? ?????? ???????? ??????????? N:? (0,08?0,13), ??? ??????????? ??????????? ???????? ????????? ???????????? ? ?? ????????????. ??? ??? ?
# 141 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
???. 2. ?????????? ????????? ?????? ? ??????????? ????????
?????????? ?????????? ???????? ???? ??????? ?????????: ?:?, ?:? ? N:? (3,14; 10,05 ? 0,16
??????????????), ??? ??????????????? ? ???????????? ?????????????? ????????????? ?????
??? ?????????????. ????? ?????????? ????????????? ???????? ????? ??????? ??? ?????
? ????????? ????. ????????? ?:? ??, ?????????? ?? ???????? ????? ? ???????, ???????????
????????? ?? ????????? ? ???????? ??? ??, ?????????? ????? 1,5, ? ????????? ?? ???????????? ??????????????? ??? ?????????? ????????? ?????? ??????????. ??? ???? ???????? ?:?
?? ?? ????????? ? ?:? ?? ???????? ?, ? ? ??, ????????, ??????????: ? (5,85) > ? (5,23)> ??
(3,77) > ? (1,64) ? ? (1,52) ? ? (1,53). ? ??????? ?? ?? ?? ??????????????? ????? ?????? ??????????? ???????? ? ??????? ? ?????????, ??? ??????????????? ? ???????????? ?????? ?????????????? ????? ? ????????? ?? ? ???????????? ????? ???????? (??????? ?????????? ?????
? = ?; ????; ??? ? ??). ?? ??????????? ?:? ?? ????????????? ???????? ????????????? ?
????????? ???: ?? (10,83) > ? (6,33) > ? (5,85) ? ? (5,85) ? ? (5,23) > ? (2,81). ???????????? ?????????? N:? (0,55) ?????????? ??????? ?? ????????????, ??? ??????? ? ????????? ????? ???
???????????? ???? ??????? ????, ? ??????? ?? ??????? ? ??????????, ?? ?????? ???????, ??
???????? ????? ????? ??? ???????? ??? ? ?????????? ???? ??????? ???????????.
??? ????????? ????????????? ???????? ??, ??? ? ?? ????? ????? ????????? ?????????? ??????? ???????????? ????????? ?????? W = 2QO ? QH/QC, ??? QO, QH, QC ? ????? ??????
?????????, ???????? ? ???????? ? ???????? [12, 13]. ??? ???????? ?????? ????????????? ?
????????????? ???????????? ???????????? ?????????? ???????????? ? ?:
? = ?????/( ????? + ?????) ??? ? = ?????/????·100 %,
??? ????? ? ?????????? ???????? ????????????? ??????????; ????? ? ?????????? ????????
?????????? ?????????? ? ????????? ?????????. ?????? ?? ??????????? ????????? ?????
???????????? ?????????? ???????? ?? ???????????????? ??????? ???-????????? ????
????????? ??????? ????????????. ?????????? ?????????? ????????? ? ????. 1. ??? ????
???????????, ??? ?:? ????????????? ????? ????? 0,33 ? ? ? ??????????? ????? ???????????
??????? ????? 0,67.
????? = ((?:?)?.?. + 2(?:?)·? ? (?:?)????/ ((?:?)???? + (?:?)????).
????? ????, ???? ????????? ?????????? ??????? ?????? ??????????.
# 142 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
??????? 1. ?????????? ??????? ??????? ???????????? ? ????????????
??? ???????
?? ?
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?26?72?100N4
?35?74?219N4
?59?108?142N4
?38?56?143N4
?48?67?209N4
?30?52?117N4
?73?102?82N4
?24?76?244N4
?25?73?128N4
?34?57?91N4
?44?83?114N4
?35?53?98N4
?36?52?220N4
?23?88?252N4
?28?46?164N4
?8?42?336N4
?5?28?244N4
W
?/? ????
+4,81
+10,48
+3,34
+6,03
+7,25
+6,11
+0,84
+16,96
+7,52
+3,67
+3,29
+4,10
+11,14
+17,88
+10,05
+87,23
+88,76
7,79
10,55
5,62
6,53
7,19
7,04
2,89
16,61
9,95
5,25
5,34
5,29
10,01
18,28
9,48
13,19
12,24
????
?????
0,92
0,94
0,89
0,90
0,91
0,91
0,80
0,96
0,94
0,88
0,88
0,88
0,94
0,96
0,93
0,95
0,88
???????
????????????, ?
41,40
42,30
40,05
40,51
40,95
40,95
36,03
43,20
42,30
39,63
39,60
39,60
42,31
43,20
41,85
42,75
39,60
? ???????? ????????? ???? ??????????? ???????? ??????????? ??????? ???????????? ??
??? ? ?? ? ?? (?? 1,5 ???? ? ? ?? 24?27 ??? ? ? ? ?). ? ?? ????????? ????? ??????????? ???
?? ????????? ? ??. ?????????? ????????????? ??????????????? ? ????????? ??? ???????
?? ????????? ? ?? ? ??, ???????? W ??????? ????????? ?? ????? ??????. ??????????? ?????????? ?????? ???????? ?????????? ??? ?????????, ?????????? ?? ?????, ??? ?????? ?????
??????? ? ????????????? ????????? ??? ????????????.
??? ????????? ??? ???????? ??????? ??????? ??????? ????????????. ?????? ?????????? ??????? ? ????: ? > ? > ? > ? > ? > ?? ??? ??; ??? ???: ? > ?? > ? ? ? > ?, ? ??? ??:
?? > ? > ? > ? > ? > ?. ??? ?????????? ??? ? ?? ?????????? ??????? ?????????????? ?????
????? ???????? ???????????? ? ???????? ???????????? (r = 0,85 ? r = 0,82 ??????????????). ?
?????????? ?? ?????? ?????????????? ????? ?? ???????????.
????? ?? ???????? ?????? ???????????????? ???????, ????????????? ??? ??????????
???????? ???????? ??? ? ????? ????????? ??????????????? ?? ??????????? ? ?????????????, ???????? ?????????? ???????? ?. ??? ?????????. ?????? ???????????? ?? ???????????
????????????? ?????? ? ??????????? (H/C)?????/? ? ?????? ??????? ??????? ??? ???????????? ?????? ????????? ????????? ? ??????????? ? ????????? ??????????? ??????? ??????????.
?? ???. 3 ???????????? ????????? ?. ??? ????????? ???, ?????????? ?? ????????? ????????? ????????.
?? ????????? ?????? ????????? ???????????, ??? ??????? ??????????? ?? ???????? ?????????? ??? ??????????? (H/C)???, ??? ? ?/?, ?.?. ?????????????? ??????????? ???? ????????????? ???????? ? ??????????? ??????? ????????????. ????????? ??, ?????????? ?? ????
????????????? ????????, ????? ?????? ???????? ?????? ???????????, ?.?. ? ?? ?????????
?????????? ???? ????????????? ?????????? ? ??????????? ?????????? ??????????????????
?????????????? ?????.
# 143 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
???. 3. ????????? ?. ??? ?????????
??? ???????????? ??????????-?????????????? ???????????? ???????? ??? ???????????? ????? ??-?????????????. ??-??????? ???? ???????? ??? ??????, ? ??? ???????????
??????????? ?????? ??????????, ????????????????? ? ????????????????????? ???????
???? ??????: ?????????? ??????? ??????????? ?????? ? ??????? 3500?2500 ??-1 ? ???????
????? 3200 ??-1, ??????????? ?????????? ??????????? ????????????? ??????????. ?????? ????????? ???????? ????? -??3 ??????????? ??? 2860 ??-1; ?????? ??????????? ?????
(-??2-) ???????????????? ? ??????? ????????? ????????? ??? 2920, 1410, 900?700 ??-1. ? ??????? 1700?1600 ??-1 ??????????? ??????????? ??????, ??? ??????? ? ????????? ?????????
? = ? ? ???????????? ?????? ? ????????? ?????????? ???????? (? = ? ????????.). ?????
????, ???????? ?????? ?????????? ???? ? ????? ??????????????? ??????? ??????? ????????? ?? ??????? ?????????? ? ???????. ? ??????? ?????????? ???????? ??????????????? ??????
1100?1000 ??-1. ?????? ???????? ?????? 1450, 1140?1120 ??-1, ????????? ? ?????????????
??????? ? ??????? ???????.
???????????, ??? ?????????? ???????? ??????? ?????? ?????????? ? ???? ?? >???>??
??? ???? ????????????? ????????, ????? ? (???. 4). ??????? ??? ???????? ?? ???? ??????????? ?????? ? ????????? ???????? ????????????? ? ????????????? ???????????, ??? ????
????????????? ????????? ?????????? ?????????????????? ? ?????????? ?????????. ??????????? ??????????????? ???????????? ?????????? ?????????? ??????????? ?????????
?????????????? ????? ????????? ??????? ??? ?????????? ?? ?? ???????, ??? ????????? ??
??????? ???????????? ???????? ????????????????? ? ???? ??????.
?????? ??????? ?? ????????? ? ???? ???????? ? = ?>?>?>?>??. ??? ????????? ????
????? ?????????? ???????? ????????? ?? ????????? ? ? ? ?. ?????????? ?????????? ??? ?,
??????? ??????? ????????????? ?? ???? ????????????? ?????? ??-????? ? ?????????? ??????????. ????????????? ?? ? ??? ?????????? ? ????? ???????????????????: ?>?>?>?>?>??
? ?>?>?>?>?>?? ??????????????.
?? ?????? ??????????? ?????????? ????????????? ????? ??? ????????????? ????????
????? ??????????? ? ????????? ???: ?>?>?>?>?>??. ??? ???????????? ?????????? ????????????? ????? ? ???????? ??? ???????????? ?????????? ??????? ??????? ????????? ?????,
? ??? ???????????? ?? ?????????? ??????????. ??????? ??????????? ????????? ??-?????
? ?????????? ??????????? ?????????? ??: ?>?>?>?>?>?? ? ?>?>?>?>?>?? ????????????# 144 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
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?
?
???. 4. ?????????????? ????? ?????????? ??? (?), ?????????? ?? ????????? ????????? ????????, ?
????????????? ????????? ?????????? ?????????????? ????? ? ??? (?)
??????? 2. ???????????? ???????????? ?????????????????? ????? ????????? ??????
???????????
???????????
?????????
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????
??????
??
??3400/? = ?1610
?2N2350/? = C1610
???2100/? = ?1610
????1720/? = ?1610
N = O1450/? = ?1610
????1120/? = ?1610
???1070/? = ?1610
???? 2920/? = ?1610
??3400/???? 2920
?2N2350/???? 2920
???2100/???? 2920
????1720/???? 2920
N = O1450/???? 2920
1,10
0,62
0,29
0,34
0,41
0,99
0,84
0,84
1,31
0,74
0,35
0,40
0,49
1,09
0,06
0,15
0,78
0,96
1,08
1,81
1,23
0,89
0,05
0,12
0,49
0,77
1,63
0,14
0,45
0,99
1,92
0,97
1,09
0,13
12,23
1,07
3,41
7,41
14,47
2,32
0,16
0,05
0,79
0,55
2,45
2,79
1,05
2,19
0,15
0,05
0,73
0,52
2,33
0,15
0,06
0,78
0,53
2,46
2,90
1,06
2,09
0,16
0,05
0,73
0,53
1,24
1,27
0,94
1,43
0,98
6,47
6,07
1,24
1,00
1,03
0,76
1,43
0,79
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?????, ????????? ??? ???????? ????? ???? ????. ??????? ?? ? ??? ? ? ? ???????????????
????????? ??????? ??????? ?????????? ?????????????????? ?????????????? ????? ? ?????????? ??????????? (???. 4), ??? ??????? ?? ??????? ????????????? ???? ???????? (???????
????????????? ?????????).
????????????? ?????????? ?????????? ? ????????? ?? ??????????? ? ?? ? ? (???. 4?).
??? ??????? ? ???, ??? ? ?????? ?????? ? ???????? ??????????? ???????????? ???? ??????
???????????? ? ????????. ??? ????????? ????? ???? ??? ??????????? ??????, ?? ???? ????
?????????? ?????????? ??????? ?????. ??? ????????? ?? ???????????? ????????????? ????????? ? ???? ??????.
????????? ??????????? ??? ????? ?????? ??????? ???????????????? ????????????? ?
????????????? ???????????? (????. 2?4). ?????????? ?????????? ?? ?, ??? ? ? ?, ?? ?. ??
?????? ?????????????????? ?????? ??? ???????? ????? ??????????????????.
?? ???????? ????????????? ? ??????? ???????????? ?? ?????????? ?? ??????????? ???????? ????? ??????????? ? ???: ?>?>?>?>??>? (???. 4?), ? ?? ??????????? ??????????
# 145 #
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??????? 3. ???????????? ???????????? ?????????????????? ????? ??????????????? ??????
???????????
???????????
?????????
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????
??????
??
??3400/? = ?1610
?-?2600/? = C1610
?2N2350/? = C1610
C???1720/? = ?1610
????1160/? = ?1610
???1060/? = ?1610
???? 2920/? = ?1610
??3400/???? 2920
?-?2600/???? 2920
?2N2350/???? 2920
????1720/???? 2920
????1160/???? 2920
???1060/ ???? 2920
1,43
1,70
0,68
1,05
1,19
1,14
1,34
1,02
0,78
0,64
0,78
0,88
0,85
2,64
0,29
0,16
0,76
2,23
3,56
1,07
2,45
0,27
0,19
0,66
2,08
3,31
2,25
0,06
1,30
2,36
5,09
3,70
1,52
3,00
0,09
0,85
3,61
7,41
5,67
2,27
2,07
0,10
1,14
1,23
1,65
0,36
0,81
0,74
0,26
0,41
0,44
0,59
0,91
0,68
0,59
0,57
1,02
3,62
0,75
1,21
0,91
0,44
0,76
1,36
0,83
1,24
1,47
1,30
1,43
6,47
6,07
1,25
1,00
1,19
0,09
1,16
5,23
4,92
??????? 4. ???????????? ???????????? ?????????????????? ????? ????????? ??????
??? ?????
???????????
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??
??3400/? = ?1610
?2N2350/? = C1610
??C2100/? = ?1610
C???1720/? = ?1610
N = O1440/? = ?1610
????1120/? = ?1610
???? 2920/? = ?1610
??3400/???? 2920
?2N2350/???? 2920
??C2100/???? 2920
????1720/???? 2920
1,19
0,99
0,75
1,11
0,63
1,10
1,10
1,08
0,90
0,69
1,01
0,61
0,20
0,24
0,82
1,39
2,60
0,29
2,08
0,67
0,80
2,80
0,71
0,45
0,47
0,72
1,40
1,48
0,60
1,18
0,75
0,78
1,39
0,38
0,56
0,36
1,01
1,01
3,00
0,73
0,52
0,39
0,99
1,40
0,63
0,69
0,17
1,42
1,41
2,34
0,475
1,31
0,47
0,98
2,91
7,20
0,83
0,36
1,40
1,42
1,72
0,40
1,80
0,25
0,37
3,50
?????????????? ?????: ?>?> ?>?>?>??, ??? ??? ??????? ? ??????? ???????????????? ???????? ?? ??????????, ??????? ???????? ??????? ?????? ?????? ????. ????? ???????? ??
? ???????? ?????????? ???????? ???????????????????: ?>??>?>?>?>? (????. 4).
????? ?????????????? ???????????? ??? ????????????? ?? ??????????????????? ???????????. ?????????? ????????????? ??? ???????? ????? ?????????? ??????????????? ?
???????????????????? ????????? ??????. ? ???????? ??????? ????? ? ???? ?????????????
????? ?????????? ??????????? ? ??????? 3400 ??-1, ??????????? ??? ????????? -?? ????? ?
?????????? ?????? (???. 4).
???????????? ????????? ????????????? ????? ?????????? ??????????? ? ???????? ?????????????????? ????????? -??2- ????? (2920 ??-1), ????????????? ?????, ?-? ????????? ?????.
??? ??????? ? ???, ??? ??? ?????? ?????? ???? ????? ? ??????? ????????????????????. ?????????? ?????? ???????????????? ????????? ????????? ? ??????? 1550 ??-1 ? ????? ?????? ??????
???????????? ????????? ????? 1400 ??-1, ??? ????????? ?? ??????? ???????????-????; ????????
?????? ?????????? ? ??????? 1620 ??-1, ??????????????? ??????????? ????????????? ?????? ? ??# 146 #
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???. 5. ??-??????? ??, ?????????? ?? ???????????? (1), ?????? ????? (2) ? ?????? ???? (3)
?????? ??????? ??. ????? ???????, ???????????? ???? ? ?????????? ????? ??????? ????????
?????? ????????????? ? ????????????? ??????:
? ????????? ?? ??????????? ???????? ???????????????????? ?????????????? ?? ????
??????? ? ??????? ?????:
??? ??????????? ????????? ? ?????????? ?????? ?????????? ? ??????? 1450 ? 1300 ??-1.
?????????? ????????? ?????????????? ????? ?????? ?????????? ? ??????? 2350 ??-1.
??? ???????????? ??-???????? ???, ?? ? ?? ???????? ? ?????? ????? ??????????? ??
?? ???????? ????? ??????????, ??? ? ??? ???????.
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??????? ?????????? ??????????, ????? ??????? ????????? ??????: ? ??????????? ????????????? ??????????, ?????????? ?? ????????? ????????? ????????, ???????? ???????
?????????? ?? ? ??? ?? ????????? ? ??????????? ??, ?????????? ?????????? ???? ???,
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?????????? ?? ????????????, ? ??????? ?????????? ?? ??????????? ?????????? ?? ? ??? ?
2 ????.
????????? ?????? ??? ?????????? ?? ???????????? ?????? (???????? ???????), ??????? ?? ?????????????, ??????????????????? ? ????????????.
?????????? ???????? ??????? ?????? ?????????? ? ???? ?? >???> ?? ??? ???? ????????????? ????????, ????? ?. ??????? ??????????? ?? ?????????????? ??????????? ????
????????????? ???????? ? ??????????? ??????? ???????????? (?? >?? > ???). ? ?????????
?? ?????????? ???? ????????????? ?????????? ? ??????????? ?????????? ?????????????????? ?????????????? ?????, ??? ????? ?????????? ?? ????????? ? ??, ????? ????????
????????????? ???????? ? ??????? ??????? ????????????. ??? ???? ???????? ??????????
????????????? ???????? ????? ???????? ?? ? ? ? ?? ????????? ? ??????????? ?????????
????????.
??????? ????????????? ?? ? ??? ?????????? ? ????? ???????????????????:
?>?>?>?>?>?? ? ?>?>?>?>?>?? ??????????????.
??????? ??????? ???????????? ????????? ?????? ??????? ? ???????? ????????????
????????????-?????????????????? ??????, ???????????? ??? ???????????? ? ?????????????
???????. ????????????? ?????????? ??????? ???????????? ?????????? ??. ?? ???????
?????????? ? ?????? ????????????? ?? ??????????? ???????? ????? ??????????? ? ???:
?>?>?>?>??>?, ?? ??????? ??????????????????: ?>??>?>?>?>?. ??????????? ?????????? ??????? ???????????? ?????????? ??? ?????????, ?????????? ?? ?????, ??? ?????? ?????
??????? ? ????????????? ????????? ??? ????????????.
??????????? ??????????????? ???????????? ?????????? ?????????? ??????????? ????????? ?????????????? ????? ????????? ??????? ??? ?????????? ?? ?? ???????, ??? ????????? ?? ??????? ???????????? ???????? ????????????????? ? ???? ??????.
? ??????? ??-????????????? ???????????, ??? ? ?????? ??? ?????? ??? ????????? ?????? (-????), ??? ? ???????? (-NH2, = NH), ??? ??????? ?? ???????????? ?????? ??????; ?????????, ???????????; ????????? -?-? ??????, ?????????? ? ????????????? ?????????, ?
??? ????? ????????????? ?????- (-NO2) ? ???????- (-N = O) ??????; ? = ? ? ??? ?????.
??? ???????? ????????? ? ????????? ?? ???? ????????????? ? ????????????? ?????,
??????????. ????????? ????? ???????????? ?????????? ????????? ?????? (??????????????? ??) ???????????? ???????? ?????????????? ?? ?????????? ??????? ? ????????? ? ??
?????????? ? ????????? ??? ???????? ?????. ? ?? ?? ????? ????????????? ???????????
??????? ??? (??????????????? ?? ? ???) ????????????? ????????? ????????????? ??????? ???????? ? ?????? ? ????????? ???????????, ????????? ? ???????? ???????? ??? ??????????????, ???????? ?? ? ?????????, ????? ???????, ?????? ?? ??????????????.
? ?????????? ?????????? ????????, ??? ????????? ????? ???????? ??????????? ????????????? ???????? ?????? ???????????? ???????? ?? ????????? ? ??????? ????????, ???
??? ????????? ?????????? ? ??????????? ????????? ? ????????? ????, ?????????? ?????????? ??????????????????? ??????????????? ???????? ??, ?????????? ?????????????
?????????? ? ? ???????????? ??????????? ?? ????? ???? ??? ????????????? ? ??????
????????. ??? ???? ???????????? ??????????, ??? ?????? ? ???? ???????? ? ????? ???????
?? ? ???, ???????? ??????? ????? ??????? ?????????? ???????????? ?????? ? ????????
# 148 #
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?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
?????????????? ?????? ? ??????? ???????? ????????????, ??? ????????? ?? ???????????? ?
?????? ?????????? ??????????? ??????? ? ??????????? ?????????? ??? ????????? ???????
? ????????? ??????? ????????. ??????? ?????? ????????? ????????? ????? ?????????????
??? ????????????? ? ???????? ???????? ??????? ? ????? ????????? ??????????????? ???????
????????? ????.
???????????? ?????????? ??????? ????-? ? 12-05-31512.
?????? ??????????
1. Basta N. Heavy Metal and Trance Element Chemistry in Residual-Treated Soil: Implications
in Metal Bioavailability and Sustainable Land Application // Abstracts of Sustainable Land Application
Conference. Lake Buena Vista, Florida. 4?8 January. 2004. P. 3?10.
2. Cao J., Lam K.C., Dawson R.W., et al. // Chemosphere, 2004. V. 54. P. 507?514.
3. ???????????? ?.?. ???????????? ???????? ????? ? ???????? ??? ?????????????.
?.: ?????, 1980. 287 ?.
4. ???????????? ????????? ?????????????? ?????????? ??????-?????? ??????? ????
?????? (?? ??????? ?????????? ???????) / ???. ?.?. ??????, ?.?. ???????. ????????????:
????? ???, 2005. 188 ?.
5. ?????? ?.?. ?????????????????? ?????????????? ????????? ?????? ?????? ????????? // ??????? ?????????? ???. ??-??. 2008. ? 3. ?. 153-160.
6. ????????? ?.?., ????????? ?.?., ???? ?.?. ????? ???? ???. ???????????? ???????????? ???????? ????????? ???????????? ??????????? ? ?????????????????? ???? ? ?????????????? ??????????? ?????????? // ??????????. ?., 2009. ? 3. ?. 41-43.
7. ????????????? ?.?., ??????? ?.?., ??????? ?.?., ???????? ?.?., ??????? ?.?.
??????? ????????????? ?????????? ?????? ?? ???????????????? ??????????? ???? ? ??????? «?????-????????» // ???????? ? ?????????????? ??????. ?.: ??????, 2012. ? 6.
?. 50 52.
8. ??????? ?.?., ??????? ?.?., ????????????? ?.?., ??????? ?.?. ??????? ????????????? ?????????? ?????? ?? ??????? ?????????????? ?????? ? ?????? ?? ???????????? ???? //
???????? ?????? ??????? ?????????. ?????: ????? ? ?????????? ??????????. ???????: ????? ?????, 2013. ? 56, ? 11. ?. 68-73.
9. ??????? ?.?., ??????? ?.?., ???????? ?.?., ????????????? ?.?., ??????? ?.?. ?????????? ???????? ??????? ? ???????? ?????????????? ?????? ? ?????? ?? ???????????? ????
????? // ??????? ?????. ? ?., 2010. ?.5, ? 5. ?. 102-105.
10. ??????? ?.?., ??????? ?.?., ??????? ?.?. ? ??. // ?????????. 2005. ? 8.
?. 58?64.
11. ????? ?. ?, ??????? ?. ?. ????????? ?? ????? ??????: ????. ???????. ? ?: ???-??
????. ??-??, 1981. 272 ?.
12. ????? ?.?. ????????? ??????? ???? ? ????? ?????? ???????????. ?.: ?????, 1993.
325 ?.
13. ????? ?.?. ????????? ????????: ????????, ????????, ??????????? / ??? ???. ?.?. ????????. ???.: ???-?? ?.-??????. ??-??, 2004. 248 ?.
# 149 #
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?.?. ??????????, ?.?. ?????????. ???????? ????????? ?????? ??? ??????? ?????????? ??? ????????????????
14. ????????? ?.?., ????????? ?.?., ?????? ?.?., ?????????? ?.?. ?????????? ??????
??????????? ???????? ????????? ????????????? ????????? ? ??????????????? ?????: ??????? ?????????? ???????? ???????????????????? ????. ?., 2012. ? 6. ?. 53-55.
15. ??????? ?.?., ????????? ?.?., ??????? ?.?., ??????? ?.?. ??????? ????????? ????????? ?? ?????????????? ?????? ?? ???????????? ????? // ??????? ?????. ?., 2013. ?.8,
? 1. ?. 106-111.
The Structure of Humic Acids
as a Function of the Performance
of Ecoprotective Role for Heavy Metals
Tatiana A. Korelskayaa and Tatiana I. Rumyantsevab
a
Northern State Medical University,
51 Troitsky, Arkhangelsk, 163000 Russia
b
Northern ( Arctic) Federal University
named after M.V. Lomonosov,
4 Lomonosov, Arkhangelsk, 163002 Russia
Research of structural and functional features of humic acids in the urban soils, peat and lignin is
conducted by methods of the element analysis, IK-Fourier-spectroscopy, spectrophotometry.
The assessment of possibility of performance of tread functions by them concerning heavy metals is
given.
Increasing the size of acid molecules occurs in a number of fulvic < Himatomelanic < humic acid. The
majority of preparations of humic acids have the same degree of formation of aromatic and aliphatic
component and a high degree of oxidation (W = +3,34 ... +10,48). The maximum degree of benzenoid
characteristic of humic (a = 42,3) and Himatomelanic acid (a = 43,2) lignin and fulvic acids (a = 43,2)
of natural soil.
Urban soil, which have a sufficiently low degree of oxidation of humic acids and very high ? fulvic,
have low tread function in relation to heavy metals. However, lignin and peat contain a humic acid
composition with a high benzenoid, oxidation and developed peripheral portion, which indicates
the possibility of the barrier function for heavy metals. Therefore, these natural materials can be
recommended for use in the making lawns to improve tread function of urban soils.
Keywords: humic acid, tread function, soil, lignin, peat, heavy metals.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 1 (2014 7) 151-158
~~~
??? 661.72.886
????? ???????????? ?????? ?????????
?.?. ????????*, ?.?. ????????
????????? ???????????? ?????????????????
??????????????? ???????????
??????, 420015, ?????????? ?????????,
??????, ??. ?. ??????, 68
Received 21.10.2013, received in revised form 05.11.2013, accepted 24.12.2014
??????? ?????????????? ??????? ????????? ? ?????????????? ???????? ???????. ?
?????????? ??????-?????????? ???????????? ???? ??????????? ???????? ????????? ????
?????????? ???????.
???????? ?????: ?????? ?????????, ????????????, ????????? ????????? ?????, ??????????
???????????.
????????
?????? ????????? (??) ??????? ? ????? ??????????? ?????????, ??????? ??????
???????-????????????? ????????. ?? ???????? ??????? ????????? ???????, ??????, ????? ?
????????????? ?????????? ???????? ??????????. ???????????????? ???????? ?????????????
??, ??????? ???????? ?????, ??????????????? ??????????? ??????????????? ??????????????, ? ??????? ??????? ?????????? ????? ????????????? ???????? ?????????? ??????? ???????????? ?????????? ??????????, ?????????? ?? ?????? ?????????????? ? ?? ???????????
[1, 2].
? ????????? ???? ????????? ???????? ????????????? ?? ????????? ??????-??????????
? ???????????????? ??????? ???????? ????????? ????????????? ??? ????? ????????? ???????? ?????????? ???????????.
??????????? ????????? ???????????? ???? ?? ????? ??????? ?????????????????? ?????????? ? ?????? ???????????? ???????????. ??? ???????, ?????????? ?? ???????????
????? ????????? ? ??????, ? ??????? ???????? ??????? ???????????? ?????????? ??? ?????????? ????????????, ? ?????????? ???? ?? ???????????? ? ??????? ????? ??????????? ????????. ????? ???????, ??????????? ????????? ???????? ?????? ????????????? ???????, ??????????? ? ??????? ????????? ???????? ? ???????? ??????????? ?????????? ? ??????????
???????? ?????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: romsvetlana80@mail.ru
# 151 #
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? ????????????????.
? ?????? ?????? ????????? ???????????? ?????????????? ????????????? ???????? ??????? ? ?? ? ???????? ????????????? ????? C6H7O2(OH)0,46(ONO2)2,54.
???? ?????? ???????????? ? ???????? ??????????? ?????????? ??????????? ?? ?????????????? ??? ?????????? ????????????? ? ??????? ??????-?????????? ? ???????????????? ???????? ?????????? ??????????.
???????? ????????????
????????? ?????????. ? ???????? 1 ? ?? ? 25 ?? ???????? ? ?????????? ????? ???????
250 ??, ?????????? ????????, ???????? ????????????? ? ?????????????? ??????? ? ???????????, ????????? ??????? ????????????? ? ???????? ?? ??????? 1 ???? ????????????? ???????? ??????? ?? ?????? ????????? ?????? ????????? ????????.
??????? ????????? ??? ????????? ???????????? ? ????????? ??????? ???????? (????. 1).
??? ????????? ???????? ???????????????????? ?????????????????? ???????? ??????????
?????????? ??????? ?????????? ? ???????????????? ???? ??? ?? ???????????, ??? ???????
????????? ???????, ???????? ??????? ?????? ??????????????? ?? ??????? ????? ? 2, ????????? ??????? ????? ? ?????? ?? ?????????? ?????.
????????? ????????? ? ??????????. ?? ?????????, ??????????? ????? ?????????? ?? ????
????????, ??????? ??? ???????? ??? ?????????? ???????? 20 ?? ??. ??. ???????????? ? ????.
????????? ????????? ?? ??????????? ????????? ???????? ??? ??????????? 100 °?. ?? ????????? ???????? ?? ?????????? ????? ????????? ?????-?????????? ??????????? ???????, ??????? ????????? ?????????? ??????? ?? ?????????? ??????????? ???????, ????? ?????????? ? ?????????? ??? ???????? ??????? ?? ?????????? ????? (????. 2).
?????????? ? ?? ??????????
? ??????? ?????????? ???????????? ???????? ? ?????????????? ?? ? ???????????????
?????????? ?????? ?????????????? ? ?????????????? ????? ? ??????????? ????????????? ?
?????? ?????? (SnCl4, AlCl3, SbCl5, TiCl4, ZnCl2, BF3?O(C2H5)3) [3?6]. ?? ????????????? ? ???????? ????????????? ????????????? ????????? ??????? ? ??????? ?????????????? ?????? ??
?? ???? ? ???????????, ??????? ? ?????? ?????? ?????????? ????? ?????????? ???????????
?? ?????????????? ???????? ??????? ??? ?????????? ????????????? ? ????? ????????, ??????? ???????? ? ???????? ?????????????? ???????? [?5?5NCOC2H3]Cl. ?????????? ?????????
???????????? ????????? ???????? ??????? ??????????? ???????? ????? ?? ? ?????????????
?????????, ??? ????????? ????????? ??????? ? ????????, ?? ????????? ??????? ??????????
? ??????????? ??????? ????????. ????? ???????, ??????? ? ???????? ?????????????? ???????? ?????????????? ???????????.
??????? ????????? ??? ??????????? 20, 30, 40, 60 °C ? ??????? ???????? ?? 2 ?? 6 ?. ?
?????????? ???????? ??????? ???????? ?????-??????????? ?????, ??? ??????. ?? ?????????,
??????????? ????? ?????????? ?? ???? ????????, ???????? ??????????????? ????????? ??
??????? ?????.
# 152 #
21
20
6
4
2
60
30,91
1
18
19
22,39
23,64
27,46
33,06
34,92
34,19
36,19
36,89
6
17
4
2
15
40
1
14
16
6
13
37,16
38,01
4
2
12
30
41,66
38,47
6
1
9
10
11
46,87
49,13
51,32
56,85
61,12
67,39
70,41
4
2
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20
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8
6
5
4
2
3
2
1
2
4
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0,12
0,13
0,16
0,21
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0,36
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0,53
0,65
0,76
0,89
1,09
1,25
1,45
2,65
2,78
2,84
2,96
3,03
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0,48
0,49
0,50
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1,24
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2,48
2,49
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?
52,89
52,93
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53,35
53,11
52,88
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49,07
48,84
47,77
46,91
45,38
44,04
42,24
40,41
26,89
26,74
26,62
24,46
26,23
5,83
5,83
5,82
5,79
5,88
5,85
5,82
5,79
5,44
5,39
5,32
5,22
5,02
4,85
4,76
5,02
2,92
2,88
2,84
2,75
2,73
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4,68
4,81
4,89
5,30
C6H7O2(OH)0,57(ONO2)1,24(??2?3)1,19 40,43
42,18
C6H7O2(OH)0,39(ONO2)0,93(??2?3)1,68 44,98
47,11
C6H7O2(OH)0,53(ONO2)1,12(??2?3)1,35
C6H7O2(OH)0,37(ONO2)1,04(??2?3)1,59 44,01
C6H7O2(OH)0,43(ONO2)0,80(??2?3)1,77
2,71
2,71
2,77
2,83
2,55
2,66
2,76
2,87
3,95
4,12
4,26
4,59
5,26
5,82
6,38
7,03
5,98
5,99
5,97
5,98
C6H7O2(OH)0,06(ONO2)0,48(??2?3)2,46 52,82
C6H7O2(OH)0,07(ONO2)0,48(??2?3)2,45 53,15
C6H7O2(OH)0,06(ONO2)0,45(??2?3)2,49 53,97
C6H7O2(OH)0,07(ONO2)0,50(??2?3)2,43 52,58
5,99
C6H7O2(OH)0,05(ONO2)0,47(??2?3)2,48 52,49
C6H7O2(OH)0,05(ONO2)0,49(??2?3)2,46 52,69
5,79
5,87
C6H7O2(OH)0,04(ONO2)0,49(??2?3)2,47 53,01
5,47
5,66
C6H7O2(OH)0,26(ONO2)0,71(??2?3)2,15 49,09
C6H7O2(OH)0,04(ONO2)0,51(??2?3)2,45 52,72
5,19
2,79
5,79
2,77
12,67 C6H7O2(OH)0,47(ONO2)2,48(??2?3)0,05 26,63
12,66 C6H7O2(OH)0,45(ONO2)2,47(??2?3)0,08 26,86
C6H7O2(OH)0,42(ONO2)0,74(??2?3)1,84 47,67
2,77
C6H7O2(OH)0,22(ONO2)0,73(??2?3)2,05 48,62
2,86
12,68 C6H7O2(OH)0,48(ONO2)2,49(??2?3)0,03 26,98
H
12,66 C6H7O2(OH)0,48(ONO2)2,48(??2?3)0,04 26,57
?
2,78
12,75
C6H7O2(OH)0,46(ONO2)2,54
N
2,68
2,66
2,69
2,87
2,46
2,55
2,67
2,89
4,03
4,19
4,26
4,47
5,24
5,79
6,33
6,98
12,56
12,63
12,64
12,77
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40
40
60
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3
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5
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27,62
19,33
16,12
14,76
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6
4
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0,38
0,45
0,50
0,54
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40,12
39,84
38,18
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4,59
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N
3,48
3,79
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5,33
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C5H6(OH)2,14(ONO2)0,50COOH0,36
C5H6(OH)2,03(ONO2)0,54COOH0,43
C5H6(OH)1,75(ONO2)0,71COOH0,54
C5H6(OH)1,64(ONO2)0,74COOH0,62
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C
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40,51
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4,78
4,74
4,50
4,48
3,57
3,94
4,24
5,39
5,62
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H
N
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?.?. ????????, ?.?. ????????. ????? ???????????? ?????? ?????????
??????? ???????????? ????????? ? ???????? ????????????? ????? (C6H7O2(OH)0,05
(ONO2)0,47(??2?3)2,48), ??????????????? ??? ??????????? 40 °? ? ??????? ???????? 4 ?, ?????
??????? ????????? ???????? ????????? 2,48.
??????????? ????????? ??????????? ????????? ? ????????????? ????????? ????????? ???????, ??? ????????????????? ? ?????????? ???????????????? ????.
??? ????????????? ???????????? ????????? ?????????? ????????? ????????? ??????:
??-?????????????, ??? 1? ? ?????????????, ??????????????? ????????????? (??? ??????????? ???????????-???????? ?????????????: ????????????? ???????? ???????????????,
?????????????, ??????? ???????????? ????, ??????????? ????????????????), ???????????
??????????????? ??????????? ? ?????????? ??????.
? ??-???????? ?????????? ????????? ???????????????? ?????? ????????? ?????????
?????????????? ?????, ??????????? ?? ?????? ??? ???????? ??, ?? ? ??? ????????? ?????????????, ??? ?????????? ?????????? ??????? ??????????????: ?, ??-1: 701, 752, 860 (?C?ONO2);
1061 (?????); 1073 (??????????????? ??????); 1284, 1650 (?ONO2); 1385 ?1355 (???3); 1420 ?
1450 (?CH2?ONO2); 1707 ? 1727 (??=?); 1715 ?1757 (?????); 2930, 2980 ? ????? ?? ? ??????????? ???????????; 3500-3800 (??H).
??????? ??? 1? ??????????????? ? ????????? ?????????????? ????? ?? ????????
???????. ???? ???????? ?? ????? ???????, ??????????????? ???????? ????????????????
?????? (?. ?.): 4,1 (1,5?), 4.8 (6?), 5,15 (2,4?), 5,75 (3?), ?? ? ??????? ??? 1? ????????? ??????? ?????? ????????, ??????????????? ???????? ????????? ????????????? ????? ?????????, ???????????? ??????? 0,8012 ? 0,8525 ?. ?. (???3).
??? ??????????? ??????? ???????????? ????? ????????? ??????? ?????? ????????? ?
?????? ???????????-???????? ????????????? ???????????? ????? ??????????????? ????????????? (????. 3).
?????? ?????????? ?????? ??????????????? ? ???????????? ??????????????? ????????????? ????????, ?????????????? ??? ??????????? ???????. ?? ???? ??????? ??????????
???????? ??????????????? ? ????????????? ???????????? ????. ????????????? ????????????
????? ????????? ??????? ????????? ? 128281 ??, ??? ??????????? ????????? ???????? ????????????? ???????????? ????? ???????????????? ???????. ?? ???? ?????????? ??????????????????? ????????? ?????????? ????????? ???????????? ???????????-????????? ???????.
???? ??????????? ???????????????? ??????? ????????? ?? ? 8,16, ?? ??????????? ???????????????? ??????????? ?????????? ? 2,5 ???? ??????.
??????? 3. ?????????????? ???????????-???????? ?????????????? ????????? ??????? ????????? ?
????????, ??????????? ?? ??? ??????
??????????
C6H7O2(OH)0,46(ONO2)2,54
C6H7O2(OH)0,05(ONO2)0,47
(??2?3)2,48
(? ?????.=4?, t ????? =40 oC)
?, ??
M?, ??
Mz, ??
M? / Mn
15725
128281
1030000
8,16
1322
4219
13782
3,19
# 155 #
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