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34.Журнал Сибирского федерального университета. Сер. Химия №3 2008

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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Журнал Сибирского федерального университета
2008
Journal of Siberian Federal University
1 (3)
Химия
Chemistry
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Editorial Advisory Board
Chairman:
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Members:
Kirill S. Alexandrov
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Gennady L. Pashkov
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Veniamin S. Sokolov
Editorial Board:
Editor-in-Chief:
Mikhail I. Gladyshev
CONTENTS / СОДЕРЖАНИЕ
Valentina V. Simonova, Tatyana G. Shendrik,
Nikolai V. Chesnokov, Boris N. Kuznetsov
Influence of Copper Acetate on the Thermochemical Transformations
of Hydrolytic Lignin and its Mixtures with Oil Slimes
? 215 ?
Boris N. Kuznetsov, Vladimir I. Kovalchuk,
Nadezhda M. Mikova, Nikolai V. Chesnokov,
Liliya V. Naimushina
Properties in CO Hydrogenation of the Nano-Catalysts Produced
by Supporting Iron Carbonyls on SiO2
? 225 ?
Анатолий В. Чубаров, Наталья В. Белоусова,
Алла С. Казаченко, Владимир В. Максименко
p=?2"%!??,? .?????2?%L ??!/ " ?,?2??=. S - H2O - OH- - S2-
? 235 ?
Александр А. Кузубов, Мария А. Раимова,
Мария В. Сержантова, Татьяна А. Кожевникова,
Александр С. Федоров
??%!?2,???*%? ,?????%"=?,? C!%????= ?,??%?,=2,"?%L
.??%?%!K?,, "%?%!%?= ?=?%2!3K=?, ?%?2="= MgB2
? 242 ?
Руслан Ф. Мулагалеев, Сергей Д. Кирик,
Николай Н. Головнёв
`??2=2/ C=??=?, : ?%??*3? !?=
?.??=
C!?"!=???,
"?=,??%?%
? 249 ?
Founding Editor:
Vladimir I. Kolmakov
Managing Editor:
Olga F. Alexandrova
Executive Editor for Chemistry:
Boris N. Kuznetsov
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????????? ? ?????? 27.08.2008 ?. ?????? 19?27. ???. ???. ?. 10,6.
??.-???. ?. 10,1. ?????? ???. ?????? ????????. ????? 1000 ???. ????? 1/063.
?????????? ? ??? ???. 660041 ??????????, ??. ?????????, 79.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Editorial board for Chemistry:
Nikolai V. Chesnokov
Lubov? K. Altunina
Natalia G. Bazarnova
Vasiliy A. Babkin
Vicente Cebolla
Viktor M. Denisov
Zinfer R. Ismagilov
Sergey V. Kachin
Sergey D. Kirik
Wolfgang Klose
Vladimir I. Kovalchuk
Vladimir A. Likholobov
Yuri L. Mikhlin
Gennady L. Pashkov
Anatoly I. Rubailo
Tatyana V. Ryazanova
Vladimir A. Sobyanin
Valeri E. Tarabanko
Tatyana G. Shendrik
Maxim L. Shchipko
Jean V. Weber
Юлия Н. Зайцева, Елена Н. Лындина,
Игорь С. Якимов, Сергей Д. Кирик
n?%K???%?2, *!,?2=??,?=?,, *=???,L?%??!?=?,. -=? "
%.?=?????/. C!%K=. .??*2!%?,2= C!%,?"%??2"= =???,?,
? 260 ?
Лидия Г. Бондарева, Ольга П. Калякина
h?3???,? ?=*%C???, Fe(III) C%?!3????/? ?=*!%-,2%?
Elodea canadensis =?=?,2,???*,?, ??2%?=?,: ,%??%L
.!%?=2%?!=-,,, ,%?%??2!,, , ?C?*2!%-%2%??2!,,
? 269 ?
Татьяна Б. Хлебникова, Зинаида П. Пай,
Борис Н. Кузнецов, Юлия В. Матцат,
Светлана А. Кузнецова, Полина В. Бердникова,
Галина П. Скворцова
j=2=?,2,???*%? %*,????,? K?23?,?= , ?,=??2=2= K?23?,?= ?
,?C%???%"=?,?? .*%?%?,???*, K?=?%C!, 2?%?% %*,??,2??
? 277 ?
Евгения В. Веприкова, Светлана А. Кузнецова,
Галина П. Скворцова, Максим Л. Щипко
q"%L?2"= , C!,?????,? ?%!K?,%??/. ?=2?!,=?%" ,? ?3K=
*%!/ K?!??/
? 286 ?
????????????? ? ??????????? ???
?? ? ??77-28-726 ?? 29.06.2007 ?.
Анна И. Бутылкина, Владимир А. Левданский,
Галина С. Калачева, Борис Н. Кузнецов
u!%?=2%-?=??-?C?*2!%??2!,???*%? ,?3???,? .,?,???*%?%
?%?2="= ??*?=?%"%?% .*?2!=*2= *%!/ *??!=
? 293 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
Journal of Siberian Federal University. Chemistry 3 (2008 1) 215-224
~~~
??? 546.652
Influence of Copper Acetate
on the Thermochemical Transformations
of Hydrolytic Lignin and its Mixtures with Oil Slimes
Valentina V. Simonovaa, Tatyana G. Shendrika,
Nikolai V. Chesnokovb,c* and Boris N. Kuznetsovb,c
a
The Institute of Physical and Organic Chemistry and Coal Chemistry, NAS
70 R. Luxemburg st., Donetsk, 831114 Ukraine
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
c
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
By using various physical and chemical methods there were studied the thermochemical transformations
of hydrolytic lignin modified with copper and its mixtures with oil slimes. As a result at the accomplished
study there was carried out the selection of the conditions for modifying and thermal activation this
industrial waste providing the production the active carbons with the yield 18-19 wt% and specific
surface area of 620 m2/g.
Keywords: hydrolytic lignin, modification, copper acetate, oil-slime, thermal transformation, active
carbon, structure, propeties.
Introduction
The traditional vegetable raw material
for production porous carbon-based materials
(PCM) is birch wood [1]. The low yield of the
carbonic product (not more than 12 % of the
initial raw material mass) encourages the studies
aimed at broadening the raw material sources of
production PCM at the expense of using wood
waste. These are also aimed at developing more
perfect ways of carrying out the pyrolysis and
raw material activation.
To regulate the structure and properties
of carbonic sorbents, there is widely used the
*
1
chemical modification of vegetable polymers.
In particular, the processing of lignocellulose
materials by using various chemical reagents,
such as the acids (H3PO4, H3BO3, H2SO4) [2-4],
the alkalis (KOH and others) [5], the salts (ZnCl2,
AlCl3 and others) [6, 7], allows to increase the
yield and the specific surface of the formed
PCM.
The perspective direction in production
porous carbonic materials is modifying the
vegetable polymers with the compounds of
transition metals [8-10]. During the pyrolysis of
the modified vegetable materials, at the same time,
Corresponding author E-mail address: bnk@icct.ru
© Siberian Federal University. All rights reserved
# 215 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
there take place the processes of carbonation and
chemical activation.
The large-capacity waste of the wood
chemical processing is hydrolytic lignin (HL)
[11]. The most perspective directions of the
hydrolytic lignin processing is production
of enterosorbents [12] and active carbons
[13, 14]. By way of the combined thermal
activating HL and oil slimes (OS), there
were obtained the mechanically strong active
carbons (AC) having a higher specific surface
as compared to the powder AC of hydrolytic
lignin [15].
In the given work, by using various physical
and chemical methods, there were studied the
thermochemical transformations of hydrolytic
lignin modified with copper and its mixtures with
oil slime.
Experimental
To obtain AC, there was used the hydrolytic
lignin of the Krasnoyarsk biochemical plant
(Russia) having the following characteristics (%):
Wa ? 3,6; Ad ? 1,8; Vdaf- 63,4; C ? 60,2; H ?
6,0; O ? 33,0; (S+N) ? 0,8.
As the oil slime (OS), there was used the
waste formed during the cleaning of the tanks
at the washing and steaming station (Odessa,
Ukraine). It is a water emulsion of heavy oil
fractions (the water content is 50 ± 10 %) with
the additions of surface-active substances. The
organic mass of OS is presented by alkanes (80
%) and arenes (18 %). The average molecular
mass is 750-1100 [16].The emulsified oil slime
was dehydrated by means of settling for 3 hours
at a temperature of 80 єC [17].
There were prepared the mixtures of lignin
and OS in the ratios 1:1 and 4:1 as calculated
by mass. Part of the samples obtained in this
way, was mixed with the Cu(AcO)2 solutions in
amounts of 2,5 and 10 wt%. The samples were
dried out till the air ? dry state.
The AC were obtained in the vertical
tubular reactor having the volume of 50 cm3,
which was placed into the electric furnace
providing the heating till reaching the activation
temperature (ta) at a speed of 50±5 °C/min. and
the thermostatic control of the reactor at ta with
an accuracy of ±5 °C. The weighed portion of the
dried sample (5 g) was charged into the reactor.
The system was blown through with argon at a
speed of 2 dm3/h for 10 min. Then the reactor
was heated to the temperature of 200 °C and
the argon flow was switched over to the steam
generator (the efficiency by water was 60 cm3/h).
The heating was continued till reaching the
activation temperature. On expiring the given
activation time ?a, the AC were cooled in the
argon atmosphere. There was determined the
activation product yield (Y, %) (the determination
error was ±0,4 %).
The value of the specific surface (SBET, m2/g)
was determined based on the low-temperature
argon desorption [18] using the ?Sorptomatic
?1900?.
The study of the AC permolecular structure
was carried out with the diffractometer DRON ?
1UM (the emission CuK?, 4 kV, 20 mA). There
were determined the following parameters of the
AC permolecular structure: the interlayer distance
d002 (the measurement error is ±0,002 nm), the
height Lc(±0,02 nm) and the average diameter
La(±0,2 nm) of the crystallites. There was also
determined the extent of their space ordering h/l
which is the ratio of the reflex height 002 (h) to its
half width (1) and the number of the layers in the
crystallite n=Lc/d002+1 [19].
The values of the adsorption activity based
on the methylene blue (MB) and iodine were
determined according to GOST 4453 ? 74 and
GOST 6217-74.
The thermogravimetric studies were carried
out with the derivatograph Q-1500D of the PaulicPaulic-Erdei system having a linear temperature
# 216 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
rise (10 °C/min.) from 20 °C to 950 °C. The
weighed portion of the sample is 300 mg, there
is the ceramic crucible. The processing of the
derivatograms was carried out according to the
method [10].
The infrared spectra of the diffuse reflection
were registered on the spectrometer BIORAD
FTS ? 185 having the attachment GRASEBY
SPACAC ?Selector?. The spectra were obtained
for the mixtures of the carbon sample (5 %) with
the powder-like KBr (95 %) by the addition of 256
scans in the range of the wave numbers 4000-400
cm-1. The contents of the functional groups in
the samples heated to 150 °C, were determined
according to Boem [21].
Results and discussion
To understand the mechanism of the
thermal destruction of lignin and its mixtures
with oil slimes in the presence of copper acetate,
there were studied the thermal transformations
at various temperatures under the conditions
of non-isothermic heating (DTA), pyrolysis
and water-steam and gas activation. There
were also studied the structural characteristics
of the initial materials as well as the products
of their thermolysis by using the methods
of IRC, XRD, the functional analysis and
microscopy.
Lignin thermolysis and activation. By using
the method of IR spectroscopy, there were studied
the transformations of the lignin structure during
its treatment with copper acetate and during the
thermolysis (Table 1).
The lignin spectrum is characterized by a
set of absorption bands which are identified in
the following way [22]: 3385cm-1 is the hydrogen
bond, 2930, 2850 cm-1 are the fluctuations of
the C?H bond in the methyl and methylene
groups, 1710, 1667 cm-1 are the fluctuations of
the C=O bond in ?? and ?? carbon-containing
acids respectively, 1603 and 1512 cm-1 are the
fluctuations of the bonds in the benzene ring, 1470,
1420 cm-1 are the fluctuations of the C?H bonds
in the groups CH2 and CH3 in methoxyls, 1365
cm-1 are the fluctuations of the C-O bond in the
phenol OH?group, 1220 cm-1 are the fluctuations
of the C?O?C and C?OH bonds of the ethers and
phenols, 1132 and 1072 cm-1 are the fluctuations
of the C?O bonds in methoxyls.
The addition of the 2 % copper acetate to
lignin, leads to increasing the intensity of the
absorption bands in the range of 1600 and 1420
cm-1. As for the intensity of the rest of the bands,
Table 1. The relative intensity of the main absorption bands of the lignin IR spectra
Sample
L
L+2 % ?u
L+5 % ?u
L+10 % ?u
L, 370 ??
L+2 % ?u, 230 ??
L
L+2 % ?u
L+5 % ?u
L+10 % ?u
L, 370??
L+2 % ?u, 230 ??
3630
0,07
1420
0,53
0,71
0,70
1,00
0,70
0,68
3510
0,16
0,17
1370
0,59
0,67
0,65
0,66
0,73
0,67
3350
0,39
0,65
0,51
0,33
0,15
0,19
1220
0,92
0,91
0,85
0,87
1,01
0,94
The absorption band, cm-1
3050
2950
2860
1700
0,36
0,22
0,45
0,46
0,29
0,54
0,34
0,22
0,43
0,28
0,16
0,38
0,14
0,19
0,11
0,59
0,10
0,25
0,15
0,44
1155
1125
1060
1033
0,89
0,89
0,99
1,33
0,83
0,84
0,92
0,96
0,80
0,83
0,92
0,95
0,86
0,88
1,00
1,11
0,91
0,77
0,60
0,90
0,86
0,83
0,90
# 217 #
1600
0,47
0,67
0,69
1,08
0,76
0,66
870
0,45
0,36
0,35
0,4 3
0,48
0,48
1510
0,80
0,95
0,91
0,93
0,70
0,82
815
0,46
0,39
0,38
0,49
0,45
0,49
1460
0,68
0,79
0,72
1,04
0,76
0,75
750
0,44
0,46
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
it changes slightly. As the concentration of copper
acetate in the lignin increases (5 and 10 %),
there decreases the portion of the OH?groups,
connected with the hydrogen bond (the intensity
of the band 3340 cm-1 decreases). There are also
reduced the contents of the free carboxylic groups
(there decreases the intensity of the absorption
band in the range of 1700 cm-1, and there increase
the intensities of the bands in the range of 1600
and 1420 cm-1, corresponding to the fluctuations
of the C=O bond in the ionized carboxyl group).
The changes observed in the IR-spectrum,
are evidently the result of substituting a hydrogen
ion of the carboxylic groups for a copper cation.
The addition of the 2 % copper acetate to lignin,
leads to appearing a new speed maximum of
the decomposition on the DTG curve at 193 °C.
Maybe this corresponds to the decomposition
of the copper carboxylates. During this process,
there decreases the temperature of the beginning
of the main thermal decomposition from 195 to
174 °C. And there decreases the decomposition
rate in the maxima corresponding to the main
thermal decomposition of lignin at 230 and
370 °C.
In the IR spectrum of the sample heated to
230 °C (Table 1), there appears the absorption
band in the range of 3055 cm-1. There are also
strengthened the intensities of the bands 870,
815, and there appears the band of 760 cm-1,
which testifies that in the thermally treated
mixture, there increases the portion of aromatic
structures having various types of substitution
in the ring. One can also observe the decrease
of the absorption bands intensity in the ranges of
2950, 2860 and 1700 cm-1, corresponding to the
fluctuations of the bonds in the methyl, methylene
and carboxylic groups, which probably takes place
due to removing the low-molecular hydrocarbon
gases. There also decreases the absorption band
intensity of 1060 cm-1, which may indicate
breaking the ether bonds.
The differences observed in the character of
the lignin thermal decomposition in the presence
of Cu(AcO)2, are connected first of all, with the
influence of the copper on the composition of the
functional groups both at the preparation stage,
and during the process of thermodestruction. The
data of the functional analysis, given in Table 2,
to a certain degree confirm this supposition. It is
established that adding copper acetate to lignin
decreases the percentage of the carboxylic and
phenol groups contained in the sample which
is connected with the formation of copper
carboxylates and phenolates.
By using the method of X-ray diffraction,
there were studied the changes of the lignin
permolecular structure, caused by introducing
copper acetate into its structure (Table 3).
The addition of copper acetate to lignin leads
to decreasing the interlayer distance value d002,
as well as to the substantial increase of the stack
extent in the longitudinal and cross-sectional
directions. And the degree of ordering in the
stack decreases almost twice. Such changes of the
permolecular structure are characteristic of the
low-metamorphized coals in which a hydrogen
ion of the carboxylic and phenolic hydroxyl
groups is substituted for a transition metal cation,
capable of forming the chelate structures [23].
One can also observe the decrease of the ?
bands number, whereas the number of the layers
in the stack increases by one unit.
The thermolysis and activation of the L-OS
mixture. The general appearance of the lignin
IR-spectrum when oil slime is added, practically
does not change (Table 4). There increases only
the intensity of the absorption bands in the range
of 2930, 2850 cm-1, as the OS contain a great
number of aliphatic hydrocarbons.
According to the functional analysis data
(Table 2), the addition of OS to the lignin, leads to
the decrease of the contents of the acidic phenolic
and carbonyl groups.
# 218 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
Table 2. The functional analysis of lignin, oil slime and their mixtures
Functional groups
Sample
COOH
Lactones
O? phen.
?-C=O
mg-equiv/g
Lignin (L)
2,45
0,5
1,2
1,10
L + 2 % Cu
2,45
0,5
1,2
1,10
OS
0,20
0,27
0,23
0,36
L ? OS
1,91
0,80
0,19
0,27
L ? OS + Cu
1,83
0,53
0,19
3,48
Table 3. The X-ray diffraction characteristics of the initial and modified lignin
Sample
Parameters
d002, ??
La, ??
Lc, ??
h/l
n
The number of ?-bands
Lignin (L)
0,446
4,7
1,50
2,69
4,4
2
L + 2 %Cu
0,419
11,1
1,86
1,40
5,4
1
The addition of copper acetate to the
L+OS mixture, reduces the number of lactone
groups and substantially increases the carbonyl
groups contents. The decrease in the lactone
groups concentration may be connected with the
formation of hydroxyl acids salts. The significant
increase in the carbonyl groups contents may
be explained by oxidizing the alcoholic groups,
which are present in the mixture components. It
is known that the metallic copper, when heated,
catalyses the oxidation of the alcoholic groups
to aldehyde ones [24]. According to the X-ray
diffraction data, during the thermolysis of the
L-OS mixture in the presence of the copper
acetate, there is observed the partial reduction of
the copper to Cu0 [25].
Using the DTA method, it is established that
adding copper acetate to the L+OS mixture, leads
to broadening the temperature range of the main
decomposition of the organic mass.
In the IR?spectrum of the copper-containing
sample (Table 4), there is observed the decrease
of the absorption band intensity in the range of
1700 cm-1, and also in the frequency interval of
1460-1033 cm-1 and 870-750 cm-1, which testifies
about the decrease in the contents of the carboxyl,
methoxyl, phenol and ether groups as well as the
portion of aromatic structures having a different
substitution type. This may be the result of the
interaction of copper acetate with both the oil
slime and the lignin components.
Adding the copper acetate to the lignin and
the L-OS mixture has a substantial effect on the
results of activating these samples with steam
while varying the time and speed of heating
(Table 5).
Activating the lignin with 2 % copper
acetate at a heating speed of 40 °C/min. to the
end temperature of 800 °C, is accomplished by
decreasing the AC yield. It is also accompanied by
the substantial decrease of its specific surface and
the adsorption activity based on the methylene
blue (MB) and iodine as compared to the AC from
lignin . These results may be the consequence of
increasing the rate of the interaction of the lignin
organic mass with the steam in the presence of
the copper cations, which leads to the intensive
burning out of the material forming macropores.
The activation of the L+OS mixture (1:1)
with the addition of 2 % Cu(AcO)2 carried out at
# 219 #
0,08
0,12
-»-, 240 ??
-»-, 370 ??
# 220 #
0,56
0,36
0,40
0,52
0,57
-»-+2 %?u,400 ??, 3 h
L+OS (4:1)
-»-, 240 °C
-»-, 370 °C
-
-»-+2 % ?u
-»-, 400??, 3 h
-
L+OS (1:1)
1420
-
0,14
-»-,2 %?u, 400??, 3 h
L+OS, (4:1)
0,16
-
-»-+2 % ?u
-»-, 400??, 3 h
-
3630
L+OS (1:1)
Sample
-
0,52
0,39
0.37
0,57
0,37
0,49
1360
0,14
0,12
-
-
-
0,23
-
3510
0,68
0,63
0,61
0,41
0,67
0,43
0,59
1220
-
-
0,27
-
-
0,36
0,35
3350
0,67
0,61
0,58
0,41
0,68
0,39
0,56
1155
0,18
0,12
-
0,16
0,17
-
-
3050
-
-
0,58
-
-
0,39
0,54
1125
0,16
0,12
0,33
0,15
0,18
1,16
1,10
2950
-
-
0,66
-
-
0,47
0,63
1060
0,16
0,10
0,22
0,14
0,16
0,67
0,70
2860
Absorption band, cm-1
Table 4. The relative intensity of the main absorption bands of IR?spectra of the initial and thermally treated samples
-
-
0,71
0,31
0,48
0,51
0,54
1033
0,57
0,34
0,31
0,27
0,37
0,36
0,42
1700
0,42
0,37
0,29
0,36
0,57
0,07
0,18
870
0,65
0,61
0,32
0,37
0,58
0,35
0,38
1600
0,44
0,38
0,3
0.38
0,62
0,12
0,20
815
-
0,42
0,54
-
-
0,45
0,60
1510
0,46
0,33
-
0,36
0,60
0.03
-
750
-
0,53
0,48
-
-
0,55
0,69
1460
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
Table 5. The characteristics of the active carbons from the lignin and the L-OS mixture (1:1), produced by steam
activation at 800 °C
Parameters
Sample
L
Activation
time, h
2
V heating,
?/min
Yield,
%
SBET,
m 2/g
? mb,
mg/g
?iodine,
mg/g
40
31,2
370
233
918
?
L + 2 %?u
-»-
-»-
24,1
120
71
458
L ? OS
-»-
-»-
27,6
250
137
529
L ? OS +2 %?u
-»-
-»-
13,9
341
134
798
L
0,5
90
15,1
631
232
1056
L + 2 %?u
-»-
-»-
19,0
535
224
937
L + 5 %?u
-»-
-»-
17,2
450
188
-
L + 10 %?u
-»-
-»-
11,3
151
56
-
L ? OS
-»-
-»-
14,1
739
137
727
-»-
-»-
18,6
620,5
126
951
L ? OS +2 %?u
the heating speed of 40 °C/min., is accompanied
by reducing the AC yield almost twice. During
this process, there increases the specific surface of
the active carbon as well as its adsorption activity
based on iodine as compared to the AC from the
unmodified mixture. But the adsorption activity
based on MB, practically does not change. As a
result, the presence of the oil slime and copper
acetate in the mixture makes for the primary
formation of micropores in the active carbon.
The activation of the lignin containing 2 %
copper acetate at 800 °C for 0,5 h at a heating
speed of 90 °C/min., is accompanied by the
increase in the AC yield, by the decrease of its
specific surface value and its adsorption activity
based on MB as compared to the activation of the
unmodified lignin. The adsorption capacity of the
AC samples from the initial and copper-containing
lignin is comparable. Thus, due to the high heating
speed, the lignin thermoreactivity in the presence
of copper decreases, which leads to increasing
the AC yield. During this process, there is formed
PCM with a great number of micropores. With
the increase in the copper acetate contents to 5,
10 % in the lignin, the AC yield sharply decreases.
There substantially decreases its specific surface
and adsorption activity based on the methylene
blue. The activation of the L+OS+2 %Cu(AcO)2
mixture, carried out under the similar conditions,
is accompanied by increasing the AC yield and
the small decrease of the specific surface area.
However, its adsorption activity based on MB and
iodine, practically does not changed as compared
to the AC from the L+OS mixture. So, the high
heating speed of lignin as well as its mixture with
the oil slime in the presence of 2 % copper acetate,
leads a high yield of AC having good adsorption
characteristics.
According to the XRD data (Table 6), the
permolecular structure of AC, obtained by the
high speed activation of the lignin containing
2 % of the copper at 800 °C for 0,5 h, differs from
the AC structure, obtained from the unmodified
lignin under the same conditions in the large
interlayer distance, the smaller stack size in the
longitudinal and cross-sectional directions, in the
smaller number of the layers and the lower degree
of ordering in the stack.
The structure of AC, obtained from the
L+OS mixture in the presence of copper, is
characterized by a higher interlayer distance, a
smaller thickness and degree of ordering in the
# 221 #
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Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
Table 6. The influence of copper acetate on the parameters permolecular structure of the active carbons from
lignin and the L+OS mixture obtained by the activation with steam at 800 °C for 0,5 h
Sample
Parameters
d002, ??
La, ??
L
0,340
6,6
L + 2 % ?u(??)2
0,374
5,0
L ? OS
0,384
6,8
1,95
0,73
6,1
L ? OS + 2 % ?u(??)2
0,407
5,5
1,99
0,57
5,9
stack as compared to the AC from the L+OS
mixture. Still the stack diameter and the number
of the layers in the stack for these AC samples,
are the same.
Conclusion
There were determined the peculiarities
of the thermochemical transformations of the
hydrolytic lignin and its mixtures with oil slimes
modified with copper acetate as well as the
structure and properties of the active carbons
produced by using the methods of IRS, DTA,
XRD, BET and the functional analysis.
It was established that the interaction of
copper acetate with the oxygen-containing lignin
functional groups, leads to forming carboxylates
and copper phenolates as well as to changing the
permolecular structure and the lignin reactivity
during the thermochemical transformations.
The indicated changes develop in decreasing the
values of the interlayer distance of d002, increasing
the crystallites size, the number of the layers in
the crystallite and the substantial lowering of
their ordering degree.
Lc, ??
h/l
n
3,27
1,04
10,6
2,83
0,89
8,6
The AC yield from the lignin samples and
its mixture with the oil slime, is determined by
the speed of the temperature rise during their
activation.
At the heating speed of 90 °C/min., there
increases the AC yield from the lignin, containing
2 %Cu and its mixtures with the oil slime as
compared to the AC yield from the unmodified
lignin samples and the lignin-oil slime mixtures.
During this process, there is formed the carbon
material having a great number of micropores.
The further increase of the copper contents in
the lignin is undesirable, since there is intensified
the reaction of the burning out of the organic
mass with the formation of macropores, which
substantially decreases the active carbon yield,
its specific surface and sorption activity.
As a result of the accomplished study, there
was carried out the selection of the conditions for
modifying and thermal activating the hydrolytic
lignin and its mixtures with the oil slime providing
the production from this industrial waste the
active carbons with the yield of 18-19 wt% and
the specific surface of 620 m2/g.
References
1.
2.
3.
Kozlov V.N., Nimvitsky A.A. The Technology of the Wood Pyrogenetic rocessing. M.: Lesnaya
Promyshlennost, 1954.
Yu J.-S., Yoon S.B., Chai G.S. Ordered uniform porous carbon by carbonization of sugars. Carbon.
2001. V. 39. P. 1442-1446.
Benaddi H., Bandosz T.J., Jagiello J., Schwarz J.A., Rouzaud J.N., Legras D., Beguin F. Surface
functionality and porosity of activated carbons obtained from chemical activation of wood.
Carbon. 2000. V. 38. P. 669-674.
# 222 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
Domburg G.E., Skripachenko T.N., Rossinskaya G.A. The Wood Chemistry. 1982. ?3. P. 76.
Moreno-Castilla ?., Carrasco-Marin F., Lopez-Ramon M.V., Alvarez-Merino M.A. Chemical and
physical activation of olive-mill waste water to produce activated carbons. Carbon. 2001. V. 39. P.
1415-1420.
Caturla F., Molina-Sabio M., Rodriguez-Reinoso F. Preparation of activated carbon by chemical
activation with ZnCl2. Carbon. 1991. V. 29. P. 999-1007.
Ahmadpour A., Do D.D. The preparation of activated carbon from macadamia nutshell by
chemical activation. Carbon. 1997. V. 35. P. 1723-1732.
Kryazhev Yu. G., Kalashnick A.T., Khokhlova G.P., Petrov I.Yu. The Solid Fuel Chemistry. 1998.
?3. P. 28.
Alvim M.C.M., Cabral Monteiro G.L. Structure of impregnated active carbons produced with
almond shells-influence of impregnation methodology. Fuel. 2000. V. 79. P. 645.
Kuznetsov B.N., Chesnokov N.V., Mikova N.M., Naimushina L.V., Pavlenko N.I., Selyutin G.E.
Preparation of copper-modified porous parbon materials from plant polymers. Chemistry for
Sustainable Development. 2002. V. 10. P. 431-440.
Kholkin Yu. I. The Technology of Hydrolytic Productions. M.: Wood Industry, 1989. 496 p.
Babkin V.A., Levanova V.P., Isayeva L.V. Medicaments from the Waste of Hydrolytic Production.
Chemistry for Sustainable Development. 1994. V. 2. P. 559-581.
Kuznetsov B.N., Shchipko M.L., The conversion of wood lignin to char materials in fluidized bed
of Al-Cu-Cr oxide catalysts. Bioresource Technology. V.52. 1995. P. 13-19.
Baklanova O.N., Plaksin G.V., Drozdov V.A., Duplyakin V.K., Chesnokov N.V., Kuznetsov B.N.,
Preparation of microporous sorbents from cedar nutshells and hydrolytic lignin. Carbon. V. 41.
2003. P. 1793-1800.
Simonova V.V., Shendrik T.G., Kucherenko V.A., Chesnokov N.V., Kuznetsov B.N. Study of
thermochemical transformations of hydrolysis lignin and the properties of the produced active
carbons. Journal of Siberian Federal University: Chemistry. V. 1, N 2. 2008. P. 107-117.
Shendrik T.G., Pashchenko L.V., Khabarova T.V. Lyubchik S.B., Krzton A., Simonova V.V. Porous
carbon materials from wood wastes and blends. Catalytic and Thermochemical conversion of
Natural Organic Polymers: Proc. 4th Int. Symp. May 30 ? June 14, 2000. Krasnoyarsk, Russia. P.
104 ? 113.
Yatsenko A.M., Procopik Z.V., Chebenko Yu.N., Vorobyov A.A. The Utilization of the Waste of
Petrochemical and Petroleum Processing Productions. Ecotechnologies and Resources Saving.
2000. ?3. P.47-50.
Phenelonov V.B. Porous Carbon. Novosibirsk: The Russian Academy of Sciences Siberian Branch,
1995. 518 p.
Saranchuck V.I., Airuny A.T., Kovalyov K.E. The Permolecular Structure, and the Carbon
Properties. Kiev: Nauk. Dumka, 1988. 192p.
Belyayev E. K. The Calculation of Kinetic Parameters on the Basis of Derivatographic
Measurements. Russ. J. Phys. Chem.. 1976. V. 50. ?3. P.790-793.
Boem Kh. P. The Surface Groups Identification / Collection Catalysis. Stereochemistry and
Organic Reactions Mechanisms. ? M.: Mir, 1968. P.186-288.
Kin G. Lignina chemia I wykorzystanie. Wydawnictwa Naukowo-Techniczne. Warscawa, 1971. 295 p.
# 223 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valentina V. Simonova, Tatyana G. Shendrik? Influence of Copper Acetate on the Thermochemical Transformations?
23. Shendrick T.G., Saranchuck V.I. Salt-bearing Carbons. Donetsk: ?Skhidny vidavnichy dim?,2003.
295 p.
24. Nesmeyanov A.N., Nesmeyanov N.A. The Fundamentals of Organic Chemistry. ?.: Chemistry,
1974, V.1. 624 p.
25. Shendrik T.G., Pashcenko L.V., Simonova V. et al. // Proc. of 4th.Int. conf. ?Catalysis and adsorption
in fuel processing and environmental protection?. Kudowa. Poland. 2002. ?. 63-68.
# 224 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
Journal of Siberian Federal University. Chemistry 3 (2008 1) 225-234
~~~
??? 554.478.32
Properties in CO Hydrogenation of the Nano-Catalysts Produced
by Supporting Iron Carbonyls on SiO2
Boris N. Kuznetsova,c, Vladimir I. Kovalchukb,
Nadezhda M. Mikovac, Nikolai V. Chesnokova,c*
and Liliya V. Naimushinad
a
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Pittsburg University, PA 15261 USA
c
Institute of Chemistry and Chemical Technology SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
d
Krasnoyarsk State Institute of Economics and Trade,
2 L. Prushinskaya st., Krasnoyarsk, 660075 Russia 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
There have been studied the catalytic properties in the reaction of CO hydrogenation of nano-catalysts
produced by supporting on silica the iron carbonyl compounds containing various numbers of metal
atoms. It was determined that the catalytic activity of the supported carbonyls increases with the rise
of the number of the metal atoms in their composition. Some of them have a very high selectivity in
respect to the C2-C3 olefins.
Keywords: nano-catalysts, preparation, iron carbonyls, silica, ?O hydrogenation, products, olefins.
Introduction
For the past years, again there increases the
interest in the catalytic synthesis of hydrocarbons
from the synthesis gas (CO and H2 mixture)
produced from the carbon containing raw
materials [1-6]. The most important task of the
conducted research is creating selective catalysts
of transforming the synthesis gas into the basic
chemical products.
A high activity and a comparatively low cost
of the supported iron catalysts is the reason why
they are used in CO hydrogenation reaction [7-11].
There is the information that the supported iron
*
1
catalysts with nanosized metal particles possess a
higher activity and selectivity in respect to olefins
as compared to the massive catalysts [12]. The
traditional methods of iron catalyst preparation
are based on impregnating the oxide carrier with
salts and their subsequent reduction to metal.
Since the iron cations supported on the surface
of the oxide carriers, are difficult to be reduced
to a metal [13], it is necessary to use the high
treatment temperatures, which does not allow to
reach a high dispersion of the supported metal.
To
make
selective
catalysts
for
hydrocarbons synthesis from the mixture of
Corresponding author E-mail address: bnk@icct.ru
© Siberian Federal University. All rights reserved
# 225 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
CO and H 2 , it is promising to use nanosized
catalysts prepared by supporting metal
carbonyls on the oxide carries. The specifics
of the composition of surface-active centers in
these catalysts, may give them new catalytic
properties in comparison with the traditional
heterogeneous catalysts [14-16].
The supported catalysts prepared with using
iron carbonyls, were studied in many papers [17-20].
Earlier the authors studied the mechanism of the
thermochemical transformations of the supported
on the silica iron carbonyls which contained
from 1 to 6 metal atoms [21]. It was shown that
during the process of supporting the carbonyls
on the SiO2 surface at room temperature, there
takes place only their physical adsorption and the
supported clusters do not undergo any chemical
changes. There were determined the supported
iron carbonyls thermal stability thresholds. It was
established that for the supported iron carbonyls
of Fe1-Fe3, practically the complete loss of the
carbonyl ligands takes place at the temperatures
of ?425 K. The supported clusters with a higher
number of metal atoms preserve in the indicated
temperature range about two thirds of the
carbonyl ligands coordinated with the Fe atoms.
Their complete decarbonylation takes place after
the heat treatment at 523 K. On the basis of the
established regularities of the thermochemical
transformations of the iron carbonyls on silica
surface, there was carried out the selection of
the conditions for their heat decomposition. They
provide the formation of the metal particles with
the size of 0.5 ? 1.0 nm, which are distributed
along the support surface rather uniformly. Such
systems can be used as nanodsized iron catalysts
in different reactions.
In the present paper there were compared
the catalytic properties in the reaction of the CO
hydrogenation of the nano-catalysts prepared by
supporting on the silica surface the iron carbonyls
with different numbers of iron atoms.
Experimental
The catalysts were prepared by supporting
on the silica the carbonyl iron compounds [TEA]
[HFe(CO)4], Fe2(CO)9, [TEA]2[Fe2(CO)8], Fe3(CO)12,
[TEA][HFe3(CO)11], [TEA]2 [Fe4(CO)13 ], Fe5C(CO)15,
[T EA] 2 [ Fe 5 C(CO) 14 ], [T EA] 2 [ Fe 6 C(CO) 16 ]
(TEA ? (C2H5)4N+). The characteristics of the
used compounds and the ways of the catalysts
preparation are described in [21].
The kinetics of the CO hydrogenation reaction
was studied in the flow-type catalytic installation
under the pressure of the reaction mixture of 0.1
MPa, the ratio of H2 : CO=1, the volume speed
of 200-1000 h?1 in the temperature range of 298623 K. To carry out the research, there was used
a glass quartz reactor with a catalyst fixed bed.
The degree of the CO conversion did not exceed
0.5%. This allows to calculate the reaction rate
without considering the concentration gradient
on the catalyst bed. The catalyst sample (0.2-1.0g)
was charged in the counterflow of the inert gas.
On reaching the given temperature, there was
measured the dynamics of changing the catalytic
activity for 5-10 hours. Then a higher temperature
was set. The applied anion iron clusters having
tetraethylammonium as a counterion, which
were not subjected to the preliminary reduction,
were blown off with helium with each rise in
temperature. It was carried out till the complete
disappearance of the cation decomposition
products. Then there was measured their catalytic
activity. The measuring time of 5-10 hours was
sufficient to reach the catalyst fixed activity. The
analysis of the initial mixture and the reaction
products, was carried out chromatographically
(katharometer and FID) using the columns filled
with the zeolite of NaX and Al2O3.
Results and Discussion
Table 1 and Fig. 1-2 demonstrate the influence
of the temperature on the catalytic properties in
the CO hydrogenation reaction of the supported
# 226 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
Table 1. The catalytic properties in the reaction of CO hydrogenation iron carbonyls supported on SiO2
Supported carbonyl
1
[TEA][HFe(CO)4]
Fe2(CO)9
[TEA]2[Fe2(CO)8]
Fe3(CO)12/SiO2
[TEA][HFe3(CO)11]
[TEA]2[Fe4(CO)13]
Fe5C(CO)15
Selectivity,wt %
Temp, ?
Total
activity*
?H4
C2H4
C2H6
C3H6
C3H8*
C 4+
2
373
3
1.69.10 ?6
4
>99
5
?
6
?
7
?
8
?
9
?
423
1.57.10 ?5
12
88
?
?
?
?
473
2.21 10
?5
5
95
?
?
?
?
523
1.22 10
?4
6
78
12
4
?
?
573
5.07.10 ?4
2
62
30
<1
<1
5
623
7.30 10
9
41
18
13
1
18
523
1.79.10 ?6
>99
?
?
?
?
?
573
2.61 10
?5
36
35
?
29
623
1.48.10 ?4
33
31
7
423
2.78.10 ?6
3
97
473
1.30.10 ?5
?
?
523
6.0 10
17
83
?
?
?
?
573
2.01.10 ?4
46
24
7
21
2
?
623
1.81.10 ?3
.
.
.
?4
.
.
?5
>99
?
?
23
6
?
?
?
?
?
?
33
38
12
16
1
?
373
1.04 10
?5
traces
?
?
99.5
?
?
423
1.06.10 ?5
traces
?
?
99.5
?
?
.
473
4.59 10
9
32
?
59
?
?
523
4.56.10 ?4
15
62
?
23
?
?
573
4.86.10 ?3
40
32
5
19
1
3
623
8.61.10 ?3
40
32
4
18
1
5
.
?5
373
2.32 10
76
24
?
?
?
?
423
1.19.10 ?6
>99
?
?
?
?
?
473
7.5 10
?6
64
29
?
7
?
?
523
9.6.10 ?6
12
17
?
71
?
?
573
1.38.10 ?4
42
14
?
43
<1
<1
623
5.4 10
34
17
?
46
<1
2.5
373
2.18.10 ?5
28
72
?
?
?
?
423
2.66 10
?5
1
99
?
?
?
?
473
5.24.10 ?4
?
99
1
?
?
?
523
9.32 10
?
73
27
?
?
?
573
1.52.10 ?3
20
44
22
12
?
?
623
6.04 10
15
45
22
12
2
4
373
5.55.10 ?5
2
?
?
98
?
?
423
2.4 10
473
6.21.10 ?5
523
2.6.10 ?4
573
4.99.10 ?4
623
7.05 10
13
.
.
.
?4
.
.
.
.
.
?6
?4
?3
?5
?3
traces
2
?
98
?
?
?
35
?
65
?
?
45
30
?
25
?
?
29
28
8
29
?
6
11
7
16
3
50
# 227 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
Table 1
1
[TEA]2[Fe5C(CO)14]
[TEA]2[Fe6C(CO)16]
2
373
3
1.27.10 ?6
4
?
5
99
6
?
7
1
8
?
9
?
423
5.15.10 ?4
1
99
?
?
?
?
473
1.02 10
?3
23
58
12
4
3
?
523
1.33.10 ?3
38
26
5
22
4
5
573
1.46.10 ?3
33
36
6
22
1
2
623
7.65.10 ?3
64
22
5
8
?
<1
373
1.67.10 ?4
31
49
20
?
?
?
423
2.93.10 ?4
?
100
?
?
?
?
473
6.36 10
?4
11
80
9
?
?
?
523
4.30.10 ?3
43
32
8
14
2
1
573
1.10.10 ?2
29
29
15
21
2
4
623
8.94.10 ?3
34
33
14
15
2
2
.
.
*CO mole (cluster mole) ?1? ? ?1
iron carbonyls. Practically all iron carbonyls
start to show the catalytic activity already at a
temperature of 373 K (with the exception of the
inactive at moderate temperatures, Fe2(CO)9).
On
the
temperature
dependences
of
the
activity
of
catalysts
[TEA]
[HFe(CO)4]/SiO2,
[TEA]2[Fe2(CO)8]/SiO2,
[TEA]2[Fe 4(CO)13]/SiO2,
Fe5C(CO)15/SiO2,
[TEA]2[Fe5C(CO)14]/SiO2 , [TEA]2[Fe6C(CO)16]/
SiO2, one can observe an approximately linear
increase of the catalytic activity with the
temperature rise from 323 to 623 K (Fig. 1). The
apparent activation energy of the reaction of CO
hydrogenation varies for the supported carbonyl
catalysts in the range of 19-31 kJ/mole. Besides
the tendency being towards decreasing the
reaction activation energy when passing from
the supported carbonyls with the low number of
iron atoms (Fe1-Fe 4) to the higher ones (Fe5-Fe6)
is observed. In case of the supported trinuclear
iron clusters Fe3(CO)12 and [TEA][HFe3(CO)11],
the dependence of the logarithm of the CO
hydrogenation reaction rate on the reverse
temperature, is not of a linear character (Fig. 1,
curves 6, 7). One can observe the increase of the
apparent activation energy with the rise of the
reaction temperature from 323 K to 623 K.
Comparing the data on the catalytic activity
with the earlier obtained results on studying the
thermal stability of the iron carbonyls supported
on the silica [21], allows to make a supposition that
the observed variations of the catalytic properties
with the rise of the reaction temperature, are
connected with changing the nature of the surface
catalytically active centers in the studied nanocatalysts. With the rise in temperature, the iron
carbonyls supported on the silica surface, lose
part of the CO groups. At higher temperatures,
the formation of iron nano-particles takes place.
It is known from the literature [22], that in
the case of supported iron catalysts, prepared
by impregnating SiO2 with the water solution
of Fe(NO3)3, the activation energy of the CO
hydrogenation reaction depends on the duration
of reducing the supported iron. For the catalyst
reduced by hydrogen at 723 K for 1hr, activation
energy makes up 37 kJ/mole and it increases
to 118 kJ/mole with the rise of the duration of
reducing the catalyst to 16 hours.
The increase of the specific catalytic activity
of the supported iron carbonyls with the rise
in the number of the metal atoms from 1 to 6 in
its composition was found (Fig. 2). This effect
develops especially considerably at moderate
# 228 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
Fig. 1. The temperature dependences of the catalytic activity of the catalysts [TEA][HFe(CO)4]/SiO2 (1);
[TEA]2[Fe2(CO)8]/SiO2 (2); [TEA]2[Fe4(CO)13]/SiO2 (3); [TEA]2[Fe5C(CO)15]/SiO2 (4); [TEA]2[Fe6C(CO)16]/SiO2 (5);
Fe3(CO)12/SiO2 (6); [TEA][HFe3(CO)11]/SiO2 (7) in the reaction of CO hydrogenation
Fig. 2. The influence of the number of the metal atoms in the iron supported carbonyls on the rate of CO
hydrogenation reaction
# 229 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
reaction temperatures, in particular at 373 K. As it
was shown earlier [21], at this temperature, only the
partial decarbonylation of the supported carbonyls
may take place. This allows to suppose that the
surface carbonyl or subcarbonyl iron compounds
are catalytically active centers of the reactions of
CO hydrogenation at moderate temperatures.
The distribution of the hydrocarbon products
of CO hydrogenation on supported iron carbonyls
differs greatly from the traditional Shultz-Flory
distribution especially at the moderate reaction
temperature (Table 1). The products composition
changes when the reaction temperature varies.
As a rule, the selectivity of forming individual
hydrocarbons is the highest at the moderate
temperatures of CO hydrogenation (373-423 K),
and it decreases with the rise of the reaction
temperature to 523-623 K (Table 1).
In case of the supported carbonyls with a low
number of iron atoms the prevailing product of
the CO hydrogenation at some local temperatures
(373 K for [TEA][HFe(CO)4]/SiO2, 473 K for
[TEA]2[Fe2(CO)8]/SiO2 and 523 K for Fe2(CO)9/
SiO2) is methane. Catalyst Fe3(CO)12/SiO2 develops
in the temperature range 373-423 K, a unique
high selectivity as regards propylene (over 99%),
which decreases at higher temperatures. The main
product of the CO hydrogenation reaction on the
supported tetranuclear cluster [TEA]2[Fe4(CO)13],
is ethylene. In the temperature range of 423-473 K
the selectivity of this catalyst as regards ethylene,
makes up 99 wt %.
On the Fe5C(CO)15/SiO2 catalyst one can
observe the highly selective formation of
propylene (>99 wt %) at the temperatures of
373-423 K (Table 1). As distinguished from
the supported neutral cluster of Fe5C(CO)15, the
anion cluster of [TEA]2[Fe5C(CO)14] catalyzes
the ethylene formation in the temperature range
of 373-473 K (Table 1). Only the ethylene is
formed on the [TEA]2[Fe6C(CO)16]/SiO2 catalyst
at temperature 423 K.
The increase of the reaction temperature, as
well as the use of the reducing treatment of the
catalyst with hydrogen or CO+H2 mixture at the
temperatures of 423-573 K, leads to forming the
nano-sized iron particles on the carrier surface
[21]. The catalytic properties of these nanoparticles differ from the properties of the surface
iron carbonyl or subcarbonyl compounds. In the
narrow temperature ranges, some of them possess
a unique high selectivity in C2-C3 hydrocarbon
synthesis.
As it follows from the data given in Table 2,
concerning the catalytic properties of the reduced
catalysts in the CO hydrogenation reaction, one
can observe a sharp increase in the methane yield.
The distribution of the reaction products in a
number of cases, corresponds to the Shultz-Flory
equation [23], that is it is similar to the observed for
traditional catalysts of the Fisher-Tropsh process.
The only exception is the Fe3(CO)12/SiO2 catalyst.
Its treatment with hydrogen does not lead to the
substantial changes in the catalytic properties.
Like in the case of the non-treated catalyst it
ensures the selective propylene formation at
473 K. Also one can observe the sufficiently high
propylene contents in the reaction products (6777 wt % at 423-573 K) for the reduced [TEA]
[HFe(CO)4]/SiO2 catalyst.
So, the studies of the catalytic properties of the
SiO2 supported carbonyls with different number
of iron atoms show that in contrast to traditional
Fe-catalysts they display a unique selectivity in
respect to the individual hydrocarbons, as a rule,
in the reaction temperature range of 373-473 K.
The literature data show that during heating
the iron carbonyls supported on SiO2, there takes
place the oxidation of a definite portion of the
metal atoms with the carrier hydroxyl groups
already at room temperatures [24]. It is testified
for example, by the emission of the molecular
hydrogen during thermal decomposition of
the carbonyl Fe3(CO)12 supported on the silica
# 230 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
Table 2. The catalytic properties in the CO hydrogenation reaction of the reduced catalysts prepared by supporting
iron carbonyls on SiO2
Preliminary
reducing
treatment
523 K,
??+?2,
1.5 h
Supported
carbonyl
[TEA][HFe(CO)4]
[TEA][HFe3(CO)11]
573 K,
? 2,
1.5 h
Fe3(CO)12
423 K,
? 2,
1.5 h
[TEA]2[Fe4(CO)13]
423 K,
? 2,
1.5 h
[TEA][Fe5C(CO)14]
423 ?,
? 2,
1.5 h
*CO mole (cluster mole) ?
?1
Selectivity, wt %
Temp.,
K
Total
activity*
373
7.43.10 ?7
99
?
?
1
?
?
423
2.75.10 ?6
33
?
?
67
?
?
473
4.01.10 ?5
43
1
?
56
?
?
523
9.24.10 ?5
7
16
?
77
?
?
573
4.24 10
1
24
?
68
?
7
423
6.0 10
100
?
?
?
?
?
473
3.9.10 ?6
76
?
?
24
?
?
523
3.3.10 ?5
75
3
?
22
?
?
573
2.37.10 ?4
54
6
?
38
<1
1
623
4.2 10
?4
53
4
?
33
<1
10
373
1.17.10 ?5
71
24
5
<1
?
?
423
6.36 10
?5
9
?
5
55
?
31
473
6.69.10 ?5
?
?
?
100
?
?
523
3.72 10
?3
28
22
7
26
2
15
573
4.02.10 ?3
29
24
3
22
<1
21
.
.
.
?4
?8
.
.
?H4
C2H4
C2H6
C3H6
C3H8
C 4+
623
8.49 10
34
28
3
17
<1
16
423
6.8.10 ?5
67
33
?
?
?
?
473
4.44 10
?4
57
25
7
6
4
1
523
4.68 10
?4
57
34
3.5
5
?
?
573
1.02.10 ?3
34
39
10
15
2
<1
623
1.34.10 ?3
29
36
17
13
2
3
473
2.71.10 ?3
40
16
4
21
2
17
523
1.17.10 ?2
26
17
7
19
1
30
573
1.41.10 ?2
32
19
8
20
1
20
623
1.42.10 ?2
47
26
6
13
1
7
.
.
.
?3
?1
surface [25]. The formation of iron ions during
the thermal decomposition of the supported
Fe3(CO)12 cluster is also confirmed by the
data of the Mцssbauer spectroscopy [26]. The
concentration of the surface OH?groups of the
silica, will determine the portion of the iron ions
fixed with the carrier surface by chemical bonds.
These fixed ions are very difficult to be reduced
by hydrogen. It is known [24, 27], that even in the
bimetallic catalysts Fe-Rh, Fe-Pt, treated at the
high temperature with hydrogen, a considerable
part of the iron is in the oxidized state, in spite of
the fact that Pt and Rh can promote reducing the
iron at the expense of the dissociative adsorption
of H2 and the subsequent spilover of the hydrogen
atoms to the iron ions.
Since the products of the CO hydrogenation
reaction on the supported iron carbonyls are
chiefly the hydrocarbons C1-C3, it is possible to
conclude that the reaction does not take place in
the polymerization way, which is considered in
[23]. Within the framework of this mechanism,
there takes place the polymerization of the
carbenic intermediates on the metallic surface.
# 231 #
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Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
However, on the nano-particles, consisting of the
low number of the metal atoms, the realization of
the indicated mechanism can be made difficult.
The high selectivity of the [TEA]2[Fe2(CO)8]/
SiO2 catalyst on the C2?products, allows to suppose
that in this case the CO hydrogenation reaction may
run on the active centres consisting of the two metal
atoms situated close to each other. The high selectivity
in respect to ethylene, of the catalyst [HFe(CO)4]?/
SiO2 does not contradict to the aforesaid, because
it is known [19], that the mononuclear carbonyls on
the surface of the oxide carriers even at moderate
temperatures, are able to be transformed into the
polynuclear carbonyl clusters. It is not excluded that
the hydrocarbons C2 and C3 may be formed on the
same active centres, since it is shown for the catalyst
Fe3(CO)12/Al2O3 that ethylene is the precursor of the
propylene [25]. The change of the selectivity at
the higher reaction temperatures (523-623 K) for
all catalysts based on supported iron carbonyls, is
likely to be connected with destroying the cluster
metallic skeleton as a result of the temperature
stimulated dissociation/association processes of the
surface carbonyl particles.
The observed increase of the specific activity
of the SiO2 supported iron carbonyls with the
growth of the number of the metal atoms in their
composition (Fig. 2), may be explained either by
the influence of the so called structural factor (for
example, increasing the number of the required
active centres), or by the effect of weakening the
electron-acceptor action of the oxide carrier on
the supported iron carbonyls with raising the size
of the supported iron carbonyls.
References
1.
2.
3.
4.
5.
6.
7.
Schulz, H. Short story and present trends of Fisher-Tropsch synthesis. Appl. Catal. A: General ?
1999. ? V. ? 186. ? P. 3-12.
Takeshita T., Yamaji K. Important roles of Fischer?Tropsch synfuels in the global energy future.
Energy Policy. ? 2008. ? V. 36, N 8. ? P. 2773-2784.
Dry M.E. Present and future applications of the Fischer?Tropsch process. Applied Catalysis A:
General. ? 2004. ? V. 276, N 1-2. ? P. 1-3.
Dry M.E. The Fischer?Tropsch process: 1950?2000. Catalysis Today. ? 2002. ? V. 71, N. 3-4. ?
P. 227-241.
Geerlings J.J.C., Wilson J.H., Kramer G.J., Kuipers H.P.C.E., Hoek A., Huisman H.M. Fischer?
Tropsch technology ? from active site to commercial process. Applied Catalysis A: General, ?
1999. ? V.186, N. 1-2. ? P. 27-40.
Rostrup-Nielsen J.R. Syngas in perspective. Catalysis Today, ? 2002. ? V. 71, N. 3-4. ?
P. 243-247.
Krylov O.V., Morozova O.S., Khomenko T.I. Catalysts for syntheses from CO and H2 ? development
of catalyst structures and reaction-mechanisms. Kinetics and Catalysis. 1994.? V. 35, N. 6. ?
P. 741-755.
8. Lohitharn N., Goodwin J.G., Lotero E. Fe-based Fischer?Tropsch synthesis catalysts
containing carbide-forming transition metal promoters. J. Catal. ? 2008. ? V. 255, N. 1. ?
P. 104-113.
9. Hayakawa H., Tanaka H., Fujimoto K. Preparation of a new precipitated iron catalyst for Fischer?
Tropsch synthesis. Catal. Comm. ? 2007. ? V. 8, N. 11 ? P. 1820-1824.
10. Ning W-S., Koizumi N., Yamada M. Improvement of promoters on the Fischer?Tropsch activity
of mechanically mixed Fe catalysts. Catal. Comm. ? 2007. ? V. 8, N. 3. ? P. 275-278.
# 232 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
11. Sarkar A., Dozier A.K., Graham U.M., Thomas G., O?Brien R.J., Davis B.H. Precipitated
iron Fischer-Tropsch catalyst: Effect of carbidization on the morphology of iron oxyhydroxide
nanoneedles. Appl. Catal. A: General. ? 2007. ? V. 326, N. 1. ? P. 55-64.
12. Jung, H.J.. Walker P.L, Vannice M.A. CO hydrogenation over well-dispersed carbon-supported
iron catalysts. J. Catal. ? 1982. ? V. 75. ? P. 416-422.
13. Kaminsky M., Yoon K.J., Geoffroy G.L., Vannice M.A., Carbon-supported Fe-Ru catalysts
prepared from stoichiometric mixed-metal carbonyl clusters. J. Catal. ? 1985. ? V. 91. ?
P. 338-351.
14. Commereuc D., Chauvin Y., Hugues F., Basset J.M., Olivier D. Catalytic synthesis of low molecular
weight olefins from CO and H2 with Fe(CO)5, Fe3(CO)12, and [HFe3(CO)11]? supported on inorganic
oxides. J. Chem. Soc., Chem. Commun. ? 1980. ? N 4. ? P. 154-155.
15. Hugues F., Basset J.M., Ben Taarit Y., Choplin A., Primet M., Rojas D., Smith A.K. Surface
organometallic chemistry: formation of HFe3(CO)11? from Fe3(CO)12 and Fe(CO)5 on silica, alumina,
magnesia, and zinc oxide. J. Am. Chem. Soc. ? 1982. ? V. 104. ? P. 7020-7024.
16. Boudart M., Delbouille A., Dumesic J.A., Khammouma S., Topsoe H. Surface, catalytic and
magnetic properties of small iron particles : I. Preparation and characterization of samples. J.
Catal. ? 1975. ? V. 37. ? P. 486-502.
17. Kuznetsov B.N., Kovalchuk V.I. Carbonyl clusters of transition-metals on oxide supports as
heterogeneous catalysts for hydrocarbon synthesis. Kinetics and Catalysis. ? 1995. ? V. 36, N 3. ?
P. 320-327.
18. Bukhtiyarov V.I., Slin?ko M.G. Metallic nanosystems in catalysis. Russ. Chem. Rev. ? 2001. ?
V.70. ? N. 2. ? P. 147-159.
19. Lapidus A.L., Savel?ev M.M. Metal carbonyl catalysts of the synthesis of organic compounds
from carbon monoxide and molecular hydrogen. Russ. Chem. Rev. ? 1988. ? V. 57, N. 1. ?
P. 17-39.
20. Kou Y., Wang H.-L., Te M., Tanaka T., Nomura M. Preparation and EXAFS studies of highly
dispersed iron catalyst derived from Fe3(CO)12 precipitated on alumina. J. Catal. ? 1993. ? V. 141.
21.
22.
23.
24.
25.
? P. 660-670.
Kuznetsov B.N., Kovalchuk V. I., Mikova N.M., Chesnokov N.V., Naimushia L.V. Formation of
iron nanoparticles by thermal transformations of iron carbonyls on silica surface. J. Siberian
Federal University: Chemistry. ? 2008. ? V. 1, N2. ? P. 124-135.
Vannice, M.A. The catalytic synthesis of hydrocarbons from H 2/CO mixtures over the group
VIII metals. V. The catalytic behavior of silica-supported metals. J. Catal. ? 1977. ? V. 50. ?
P. 228-236.
Storch G., Golambik N., Andersen R. Synthesizing hydrocarbons from carbon monoxide and
hydrogen.M.: Foreign literature publishing house,1954.-516p.
Kovalchuk V.I.,Mikova N.M.,Chesnokov N.V.,Naimushina L.V., Kuznetsov B.N. Mixed ironrhodium carbidocarbonyl clusters on oxide supports: ?hemistry and catalysis of syn-gas reactions.
J. Mol. Catal. A.Chemical. ? 1996. ? V. 107, N 1-3, ? P. 329-337.
Basset J.M., Besson B., Choplin A., Hugues F., Leconte A., Rojas D., Smith A.K., Zanderighi
G.M. Supported cluster and mechanism of CO reduction. in Fundam. Res. Homogeneous Catal.
New-York ? London. ? 1984. V. 4. ? P. 19-53.
# 233 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Boris N. Kuznetsov, Vladimir I. Kovalchuk,.. Properties in CO Hydrogenation of the Nano-Catalysts Produced?
26. Brenner A., Hucul D.A. The remarkable decarbonylation of chromium, molybdenum, and tungsten
hexacarbonyls supported on silica and the nature of these materials as heterogeneous catalysts.
Inorg. Chem. ? 1979. ? V. 18. ? P. 1478-1484.
27. Fukuoka A., Kimura T., Kosugi N., Kuroda H., Minai Y., Sakai Y., Tominaga T., Ichikawa M.
Bimetallic promotion of alcohol production in CO hydrogenation and olefin hydroformylation on
Rh-Fe, Pt-Fe, Pd-Fe and Ir-Fe cluster ? derived catalysts. J. Catal. ? 1990. ? V. 126. ? P. 434-450.
# 234 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ???????, ??????? ?. ?????????,.. ??????????? ?????????? ???? ? ???????? S - H 2O - OH- - S2-
Journal of Siberian Federal University. Chemistry 3 (2008 1) 235-241
~~~
??? 544.016.4; 542.61
??????????? ?????????? ???? ? ???????? S - H2O - OH- - S2???????? ?. ???????*, ??????? ?. ?????????,
???? ?. ?????????, ???????? ?. ??????????
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
??????????? ???????? ??????????? ?????????? ???? ? ???????? S ? H2O ? OH- ? S2- ?
????????, ???????????? ??????????? ???????????????????? ????????????. ? ???????????
?????? ????????-??????????? ???????????? ???????????? ???????? ????????? ?????????
? ????????? «?????? ???????????? ? ?????????? ???????????? S». ??????? ?????????????
???????????? ???????? ???? ???? ? ??????????? ???????? ?????????.
???????? ?????: ?????????? ????, ????????, ???????? ????????, ???????????, ???????????????? ??????, ????????-?????????? ???????????? ????????????.
????????
?????????? ???? ???????? ????? ??
???????? ????????, ???????????? ??????????? ???????????????? ??? ? ????????????
?????????????????????? ???????? [1, 2].
????????? ???????? ??????????? ???????
?????????? ?????? ? ???????????? ? ?????????? ? ???????? ?????, ? ????? ?????????????? ???????????, ??? ???????, ?????????
?????????? ???????. ??? ?????????????????? ??????????? ? ?????????? ????? ?????????? ?????????? ???????? ? ?????????
?????????? ???? ? ???????? ????????, ?
??????? ?????? ? ??--?????? ????????????
???????- ? ???????????-???? ??? ????????
??????????? ????, ????????? ???????? ??????? ????????? ? ?????? ???? ? ???????????
?? ?????????????. ?????? ????????????
?????????? ????????? ????????, ??? ??????????????? ????????????? ????? ?????? ??
*
1
???????????. ??????????? ???? ?????????
?????? ? ?????????????, ? ????? ????????
? ????????????? ??????????? ??????????
???? ? ????????? ??????????? ?????????
???????? [3, 4].
????? ?????? ?????? ???? ???????????? ????????? ?????????? ???? ? ????????
S ? H2O ? OH- ? S2-, ???????????? ????????
??????????????? ????????, ????????????, ?
?????????, ??? ??????????? ?????????? ???
?? ?????????????? ????????????????????
???????.
????????????????? ?????
? ?????? ?????????????? ????????
??(??)2, NaOH ? Na2S, ?????????????? ?? ????????? ????? «?.?.», «?.?.?.» ? ?????????????? ????????????? ???????????????? ????, ?
?????????? ????, ?????????? ?????????????? ?? ????????? ??????????????? ????????
Corresponding author E-mail address: avchem81@yandex.ru
© Siberian Federal University. All rights reserved
# 235 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ???????, ??????? ?. ?????????,.. ??????????? ?????????? ???? ? ???????? S - H 2O - OH- - S2-
[5]. ??? ?????????????? ???????????? ???
1000 °C. ????????? ???????????? ????????
??????????? ??? ????????, ????? ???????
?????????? ????????????? ??? ???????? ??????????????? ??? ????????? ???????????? ??????? [6, 7]. ????? ??????????? ? ?????????????????? ??????? ??? ??????????? 25 °C
(???????? ????????? ?????????? ±0,01 °C) ?
?????????? ????????????? ? ??????? 48 ????? (? ???? ?????? ???? ???????????, ??? ???????????? ???????????? ?????????? ???? ?
?????? ???? ? ???????? ? ??(??)2 ??????????? ?? 7 ?????, ? ????????? ?????????, ?????????? NaOH, ?????????? ???? ?? ?????????
24 ?????). ?????????? ?????????? ?????????????? ?????? ???????????? ??????.
?????? ??????????? ? ???????????
????????-??????????? ?????? ????????????
???????????? [8]. ?????? ????????? ?????????
? ???????????? ? ???????? ???????????? ???
???????? ?????????? ?????? (????. 1), ???????????? ??? ???????? ??????????? ???????.
???????? Y ???????? ?????????? ????, ??????? ??????? ? ???????, ?????????? ? ??/?.
?? ????????? ?????? ?????? ???? ?????????? ?? ???????????????? ?????????? ????
? ???????????? ??????? ???????? ???????-
???? ? ??????-??????????? ????????????? ?
??????????-????????? ??????? ?? ???????????? «IRIS» ??? ??????????? ????? ???????????? ????. ?????????? ????????? ?????????????? ??????? ? ?????????-????? ????????????
????????????????? ???????? [6, 7].
?? ?????????? ?????? ??????????????
???????????? ????????? ???????? ???????
???????, ??????? ???? ???????????? ???
?????????? ????????, ??????????????
?????????????? ??????????? ???????? ?????????? ???? ?? ?????????? ?????????- ?
???????-????? ? ???????? (???.1, 2). ???????? ???????????????? ????????????? ????????????? ????????? ??????????.
??? ?????? S ? H2O ? OH- ? S2- ? ????????
?????????????? ???????:
?1 ? ?2? ????????????????,
?2 ? ??????? NaOH (???????? ????????????
0,1 ????/?),
?3 ? ??????? Na2S (???????? ????????????
0,06 ????/?).
??? ?????? S ? H2O ? OH- ? S2- ? ??????? ???????????? ???????:
?1 ? ?2? ????????????????,
?2 ? ??????? Ca(OH)2 (???????? ????????????
0,025 ????/?),
??????? 1. ??????? ???????????? ??? ?????? ???????? ??????? ???????
?
?????
???????? ????
??????????
?1
?2
?3
S ? H2O ? NaOH ? Na2S
(24 ????)
Y????, ??·?-1
Y????, ??·?-1
S ? H2O ? Ca(OH)2 ? Na2S
(14 ?????)
Y????, ??·?-1
Y????, ??·?-1
1
1
-
-
68,0
68
68,0
68
2
-
1
-
195,0
195
257,0
257
3
-
-
1
3150,0
3150
1200,0
1200
4
0,5
0,5
-
140,0
140
177,0
177
5
0,5
-
0,5
1050,0
1050
427,0
427
6
-
0,5
0,5
3300,0
3300
1455,0
1455
7
0,33
0,33
0,33
2173,2
2136
788,0
777
8
0,15
0,15
0,7
2916,5
2931
1120,5
1126
9
0,15
0,7
0,15
1500,4
1493
681,0
681
10
0,7
0,15
0,15
705,3
701
269,0
269
# 236 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ???????, ??????? ?. ?????????,.. ??????????? ?????????? ???? ? ???????? S - H 2O - OH- - S2-
???. 1. ????????? ??????????? ?????????? ???? ? ??????? S ? H2O ? NaOH ? Na2S
???. 2. ????????? ??????????? ?????????? ???? ? ??????? S ? H2O ? Ca(OH)2 ? Na2S (????? ???????????
7 ?????)
# 237 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ???????, ??????? ?. ?????????,.. ??????????? ?????????? ???? ? ???????? S - H 2O - OH- - S2-
?3 ? ??????? Na2S (???????? ????????????
0,03 ????/?).
????????? ?????????? ????????? ??
?????? ??????????? ?????? 8 ? 10 (????. 1)
???? ???????????, ??? ??? ????????? ????????? ??????????? ??????? ? ?????????????
???????????? 0,97. ?????????????????? ?????????? ?? ????????? 3 %.
???????? [9], ??? ??????? ???????????
???? ???????? ??? ???????????????? ??????:
????????? ??--????? ?? ??????????? ????, ????? ?????? S ? ??????? ?? ? ??????? ? ???? ?????
?8(S ? ??)?, ????????????? ??? ?????? ???? ??? ??????????? ???????????? ?? ?????
3(???S???) ? SO32- + 2S2- + 3H2O.
??? ?????????? ?????? ????. 2, ? ????????? ?????????? ?????? ?????????? ??????????? ??????????????? ??????????????
??????????, ??? ???????, ????????, ? ???????
?????? ?????, ?????????????? ???????????
?????? S??? ?? ????????? ?????? ???????????, ? ????? ??????????? ????? ????????????
?????????????? nS + S2- ? Sn2-. ?????????? ?????????? ??--????? ? ?????? ?????? ? Ca(OH)2
???????? ? ?????????? ???????????? ?????????????????? ??????? ?? ???? ????????
????? ???????????? ???? ? ?????? ????. ????????? ??? 25 °C ????????????? S ?? ????????? ?????????? ??????????? ?????????????
???????????? ???????? ????, ???????????
???? ????????? ?? 35, ? ????? ? 50 °C. ??? ????
??????????? ???????????? ?????????? ?????????? ???????????? ???? ?, ??? ?????????,
???????????? Sn2-, S2-, SO32- ? S2O32- ? ????????. ?????? ????. 2 ????????? ???????? ? ???,
??? ?????? ???? ??????? ???? ? ??????????
???????????? ???????????? ??????? ??? ????????? ????????? ??????????????.
?? ???. 1 ???????????? ?????????
??????????? ?????????? ???? ? ???????
S ? H2O ? NaOH ? Na2S.
?????, ??? ??????? ??????? ?? ???????
S ? ??????? ????????? ??????????? ???????? ??????. ?????? ??????????? ???????????
?? ??????????? ?????? ???? ? ???????????
????? ?? ?????? S?S. ??? ???? ??????????
?????????-????? ? ??????? S ? H2O ? Na2S
????????? ??????????? ??????????? ????.
???, ??? ?????????? ?????????? S2- ? ??????
???? ?????????? ???????????? ????????????
???? ? ? ????? ? ???????????? ???????????
Na2S 0,06 ????/? ?????????? 3150 ??/?, ???????? ?? ??????????? 3631 ??/? ??????????? ?
?????, ??????????????? ????? ? ????????
?????????? ??????????? ????????? Na2S ?
NaOH 0,72 : 0,28 ??????????????. ?????????
?????????, ??????????? ???????, ????? ????????? ???:
Y = 68?1 + 195?2 + 3150?3 + 34?1?2 ?
? 2236?1?3 + 6510?2?3 + 15035?1?2?3.
??????? 2. ???????????? ????????? ???????? ???? ????, ???????????? ??? ??????????? S ? ????????
???????????, °?
???????????? ? ????????
S???, ????·?-1
S2-, ????·?-1
S2O32- + SO32-, ????·?-1
Sn2-,????·?-1
25
0,057
0,001
0,006
0,05
25
0.0018
?.?.?.*
?.?.?.
?.?.?.
35
0.0035
50
0,009
0,0005
0,003
?.?.?.
0.001
0,005
0.003
NaOH
Ca(OH)2
*
?.?.?. ? ???? ??????? ???????????
# 238 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ???????, ??????? ?. ?????????,.. ??????????? ?????????? ???? ? ???????? S - H 2O - OH- - S2-
?????????? ????????????? ? ??????????? ?????????-????? ????? ???? ????????? ?????????? ??????? S8 ??? ???????????
?????????????? ? ????????? Sn2-. ?????????????? ??????? ??????? ?????????? ?????? ??????? ? ???????????? ??- ? ?????????
Na2S ?????????? ????????? ??????????, ? ???
??????????????? ? ??? ????, ??? ??? ??????
????????????? ???????? ???????? NaOH ????????? ??? ????? ?????? ??????? ?? ????????????? ??-?? ?????????? ??????? ?????????
S2- ??? ??????? ???????????.
???? ??- ????????? ????? ?????? ???????, ??? ????????, ?? ??????????? ?????????? ???? ? ?????? ?????????, ????????,
?????????? ????? ???????? ????????? ??????????????, ?????????? ??????? ??????
???????, ? ????????? ?? ?????? ?????? S?S.
??????? ????????, ??? ? ???? ?????????? ???????????? ?????????? ???????????? ???? ??
?????????? ???????????? ????????? ??????????? ? ??????? 24 ?????.
?????????? ???????????? ??? ??????????????, ??? ? ???????-????? ? 2 ???? ????????
? ???????? ???????? ?????????? ???? ? ???????, ??? ????????????????? ?? ???. 2, ?????????????? ????????? ??????????? ???? ?
??????? S ? H2O ? Ca(OH)2 ? Na2S.
?????????? ?????????, ????? ????????
? ???, ??? ? ????? ????????? ???????????,
?????? ? ????? ???????????? ?????????, ???
??????????? ????, ??????????? ?????????????? ??????? ?????????-????? ?? ??????? ?????????? ???? ? ?????? ????. ?????????? ????????, ??? ? ??????? ??????? ????
(???. 3) ??????? ??- ?? ??????????? S ? ????????? Na 2S ??????????? ?? ?????????????? (???????? ?????????? ???????????? ????
??????????? ??????????? ???????, ??????????????? ??????? S ? H 2O ? Ca(OH)2), ???
????? ???? ?????????? ????????????? ?????????? ??????? (? ????????? ??????? ???
?????????? ? 2 ????, ??? ??? ???? ?? ????????? ????? ??????? ?????????? ?????????
???. 3. ????????? ??????????? ?????????? ???? ? ??????? S ? H2O ? Ca(OH)2 ? Na2S (????? ???????????
1 ???)
# 239 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ???????, ??????? ?. ?????????,.. ??????????? ?????????? ???? ? ???????? S - H 2O - OH- - S2-
????? ?????) ??? ????????? ???? ???????????????. ??? ???? ?????????? ??????? ???????? ??? ?? 7 ? ???? ????? (???. 2) ????????
? ????????? ???????, ???????? ???, ??????? ??????????? ? ?????????, ??????????
????????? ??????.
???????????, ??? ???????????? ???????????? ???????????? ???? ? ??????????? ????????? ????????? 1530 ??/? ? ?????, ???????????????
????? ? ???????? ?????????? ???????????
????????? Na2S ? ??(OH)2 0,66 : 0,34 ??????????????. ?????????, ??????????? ?????????
???????, ????? ????????? ???:
Y = 68?1 + 257?2 + 1200?3 + 58?1?2 ?
? 828?1?3 + 2906?2?3 + 1143?1?2?3.
??????
1. ??????????? ????????? ??????????
???? ? ???????? S ? H2O ? OH- ? S2-, ???????????? ???????? ??????????????? ????????
???????????????????? ???????????.
2. ???????? ????????? ?????????, ?????????????? ??? ?????????? ???????? ??????????? S ? ??????????? ????????.
3. ????????, ??? ? ????????? NaOH ???
??????????? ???? ?????????? ? ???????? ?????????? Sn2- ? S2- ? ??????? ?? ?????? ? ??(??)2,
??? ????????? ?????????? ??????????????
???????? ?????????????????? ??????, ?
????????? S?32-, S2?32-. ??? ???? ???????????? ???????? ?? ??????? ??????? ???????, ?
??????? ?????????? ??- ? S2- - ?????.
4. ???????????, ??? ??????? ???????
?? ????????????? S ? ????????? ?????????
????????? ??????????? S2--?????. ??????????
?????????-????? ?????? ?? ??????????? ????
? ??????? ??????? ??-?? ??????????? ??- ?
????????? ????????? ?????????? ?????????
????????? ? ??? ??????, ??? ????? ?????????
???????.
5. ???????? ???????????? ??? S2-, ??? ?
??-, ???????? ? ?????????? ?????????????.
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
9.
?????????? ?.?. ?????????? ?????????? ?????? ? ??????? ?? ??????? ???. ???????: ???
«??????????», 1999. ? 786 ?.
?????? ?.?., ?????????, ?.?., ??????? ?.?. ??????????? ??????????? ????????. ??.1. ?.: ?????, ???????????? ??? «???? ? ???????», 2005. - 432 ?.
??????? ? ????????????????? ???????, ???????????? ??????????????? ??????????:
?????????? ?? ?????????????. ?. 3. ??. 1, 3. ?.: ?????, 1969, 1970.
?????? ?.?. ??????-?????????? ?????? ??????????? ????????? ? ????? ?????????????
??????????: ???????. ???. ?-?? ????.????. ??????????, 1987. ? 368 ?.
??????? ?.?., ??????? ?.?. ?????? ?????????? ????????. ?.: ?????, 1974. ? 407 ?.
????? ?. ?????? ????????????? ?????. ?????????????? ?????? ?????????????? ??????????. ?.: ?????, 1965.
???????? ?.?. ?????????????? ??????. ?.: ?????, 1972. ? 504 ?.
?????????? ?.?., ??????? ?.?. ??????????? ???????????? ? ????? ? ?????????? ??????????. ?.: ????. ??., 1978. ? 319 ?.
??????? ?. ?. ??????????????? ????????? ??????????? ? ?????????????. ????-???: ?????, 1975. ? 326 ?.
# 240 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???????? ?. ???????, ??????? ?. ?????????,.. ??????????? ?????????? ???? ? ???????? S - H 2O - OH- - S2-
Dilution of Elemental Sulfur in Systems S ? H2O?OH- ? S2Anatoly V. Chubarov, Natalya V. Belousova,
Alla S. Kazachenko, Vladimir V. Maksimenko
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Processes of elemental sulfur dilution in systems S ? H2O ? OH- ? S2- was investigated under conditions
modeling industrial technologies. Regression equations and diagrams ?solvent composition ? amount
of dissolved sulfur? was obtained with simplex-lattice method. Formation of sulfur anions and their
distribution in alkaline solutions was studied.
Keywords: sulfur, sulfides, alkaline solutions, dilution, hydrometallurgy of gold, simplex-lattice
planning of experiment.
# 241 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????? ?. ???????, ????? ?. ???????,.. ????????????? ???????????? ???????? ?????????????? ????????????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 242-248
~~~
??? 546.2
????????????? ???????????? ???????? ??????????????
??????????? ???????? ??????????? ??????? MgB2
????????? ?. ????????*, ????? ?. ????????,
????? ?. ???????????, ??????? ?. ????????????,
????????? ?. ????????
????????? ??????????? ???????????,
??. ?????????, 79, ??????????,660041 ??????
?
???????? ?????? ??. ?.?. ?????????? ?? ???,
?????????????, ??????????, 660036 ?????? 1
?
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
????????????? ???????????? ???????? ?????????????? ??????????? ???????? ?? ??????? ?
?????????? ???????????? ???????? ??????? MgB2 ???????? ??????????? ?????????? ???????
????????? ? ???????? ???????????? ???????? ????????.
???????? ?????: ????????? ?????, ??????????, ??????????? ????????, ?????????? ??????????.
????????
? ????????? ????? ??????? ????????
????????? ?????????? ??????????. ????? ?? ??
???????? ?????????? ???????? ?????? ???????????? ???????? ????????. ? ??????????,
????????? ??? ???????? ????????, ????????????? ??????? ?????????? [1]: ?????????????, ??????????? ?????? ??? ??????????
???????? (? ???????, ??????????? ?????????? ??? ??????????? ?????????? ?????????? ?????????? ?? ????? 6,5 % ???. ? >62 ??/
?3 ???????? ?????????? ??? ????????? ???????????, ?????????, ? ??????, ???????????
????????), ????????????.
???????????, ??????????? ??????
??????????? ??????? ??????, ????? ?????
?????????? [2] ? ???????? ????????? ??????? ?g?2, ?????????????? ????? ?????????
*
1
???? ??????????? ????? ?????? ??????? ? ??????????????? ????? ?????? ????. ????? ???????????? ????? ????????? ? ??????? ???????? ?????????? ??????????? ?? ????????? ?
??????????????? ?????????? ??????. ???????
???????? ???????? ????? ? ?? ?????? ????.
? ?????? ?????? ????????? ?????????????????? ????????????? ???????? ???????????? ? ????????? ??????? ???????? ?? ?????????? ??????? MgB2, ??????????? ???????
???????? ?????? ????????????? ???????????
????????????? ?????? ???? ? ???????? ????????? ????????.
???????????????? ?????
???????? ???????
??? ??????? ??????????? ? ?????? ?????????? ??????????? ????????? ?????????
Corresponding author E-mail address: kaa@iph.krasn.ru
© Siberian Federal University. All rights reserved
# 242 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????? ?. ???????, ????? ?. ???????,.. ????????????? ???????????? ???????? ?????????????? ????????????
(DFT) ? ?????????????? ?????? VASP (Vienna
Ab-initio Simulation Package) [3, 4]. ??????
????????? ??? ????????-?????????? ???????? ?????????? ????? ????????????????
? ?????????? ???????? ??????? ?? ??????
??????? ????. ??? ???????????? ?????????? ?????????? ???????? ??????? ? ?????????? ???????? ???????? ? ????????? ??? ????
?????? ?????????????? ????????????????
???????????? (Vanderbilt) [5-11].
????????????? ????????? ??????? ??? ???????? ??????????? ????????? ??????? ? ??????? ?????????? ??????? ?????, ? ??? ????? ? ?
?????????? ??????????? ??????? [12-14].
?? ????????? ????? ?????? ???? ????????? ????????????? ???????? ??????????
????????, ???????????, ? ????? ??????????? ???????? ???????????? ?????????????
????? (?????? ??? ??????? ?????????????).
??? ?????????? ???????????? ???????????
?????????? ????????????? ????? ????????
?????????. ????????????? ????????? ?????? (????? ????? ??????????) ? ????? k-?????,
??????????? ??? ???????? ???????. ????????? ?????? ? ?????? ?????? ??????? ???????????? ??????? ??????? ??? ?????????
??????????????? ?????????? ? ???????
???????? ?? ???????. ?????????? ???????????? ???????????????? ??????? ????????, ???
??????????? ??? ????????????? ? ????????
???????? ??????? ?????? ???????? ?? ??????????? ????????? ???????? ?????????
??????????? (10,10), ????????? ?? ???? ?????
??????????, ? ??????? ????????????? ?????. ???????? ???????????? ??????????? ?? 3
k-????? ????? ??????????? ??? ?????.
?????????? ? ??????????
????????? ????????
?? ??????? ??????????? ?????
????? ??????, ????????????? ?? ?????
?????? ????, ???????? ????????????? ?????-
????, ? ????????? ??????? ????? ???????????. ????? ???????, ????????? ?????????
?????????? ???????? ????? ????????? ???????????? ?????????? ???????? ??? ????????? ?????? ??????????? ?????????. ??????
?? ????? ??? ??????? ??????????? ?????????
??????? ? ?????? ???????? ??? ?????? ???
????????? ??? ??????? ???????????? ????????? (???. 1, ????????? ? ? ?).
?????????? ???????? (????. 1) ????????,
??? ???????? ???????? ???????? ?????????,
??? ??????? ???? ???????? ?????????????
????? ???????? ? ??????????? ??? ?????
(???. 1, ?) ? ?????????, ??? ??????? ???? ????????? ?? ????? ????????????, ????????????
??????? ?????? (???. 1, ?). ????? ? ????? ??????? ?????????? ?????????????? ?? ???????
E Bond
? Tube H E Tube nE H2 / 2n ,
??? ? Tube H ? ??????? ????? MgB2 ? ?????????; E Tube ? ??????? ????? MgB2; E H2 ? ??????? ???????? ????????; n ? ?????????? ??????? ????????.
????? ? ?????? ??????????? ??????? ???????? ? ??????, ????? ??? ????? ???????? ???????? ??? ???????? ????????? ?? ??????????? ????????? (???. 1, ? ? ?). ?????? ???????
??????????? ? ????? ??????? ????????? ??????? ????? ????? ???????? ? ??????????????
??? ?????????? ????? ?????????? ????????
??????? ???????. ??????? ???????? ????????? ? ?????? ??????? ??????????, ???????
??????????????? ???????? ???????? ?????????? ? ?????? ???????????? ?????? ????? ???????? (???. 1, ? ? ?, ?). ????????? ????????
???????, ? ??????? ??? ?????????? ?????? ??
??????? ???????, ?????????? ????????? ??????? ? ??????????? ????????? ????????, ????????????? ?????????? ????????. ??????? ??
??????????? ????????? ????????? ???????
?????????? ???????-????????? ? ??????, ?????
??? ????? ? ??????? ???????????? ??? ??????
# 243 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????? ?. ???????, ????? ?. ???????,.. ????????????? ???????????? ???????? ?????????????? ????????????
?????????? ?????? ?????????? ????? ?? ?????? ????, ???????? ? ?????????, ???????????? ??????? ??????, ????????? ?????? ???????? ???????? ????????????
???.1. ???????? ???????????? ?????? ? ???? ?????? ???????? ?? ??????? ??????????? ?????????
??????? 1. ??????? ?????????? ???????? ? ??????? ???????????? ????? MgB2
????????? ?????? ???????? (???. 1)
??????? ?????????? (?), ??
?
0,120
?
-0,044
?
-0,414
?
0,562
?
-0,710
?
1,104
?
-0,803
?
0,095
?
-0,263
?
0,314
?????????????? ????????, ???? ? ??? ???????, ????? ??????? ????? ?????????? ????????
???????????? (??? ????? ???????? ???????????? ??? ??????? ??????, ???. 1, ?, ? ).
???????? ???????????? ???????? (?,
?, ?, ???. 1) ?????????????? ?????????????? ?????????? ??????? ?????????? (????. 1).
????????? ????????
?? ?????????? ??????????? ?????
????????? ?????? ????? ???????? ??????????? ??? ???? ????????? ?????????
???????? ?? ?????????? ??????????? ?????????, ???????????? ????? (???. 2, ?-?),
??????? ????? ???????????? ? ????. 2. ???????? ???????? ??????????????? ????????
??????, ????? ??????? ???? ?? ??????, ???????????????? ? ?????????????????? ???
????? (???. 2, ?, ?).
????? ???? ?????????? ???????????
????????? ?????? ? ????? ??????? ????????,
?????????????? ?? ???????? ????? ?????????? ??????????? ????????? (???. 2, ?-?), ??????????????? ??????? ?????????? ????????? ? ????. 2.
?????? ?? ???????? ???????? ???????
???????????? ???? ?????? (???. 1 ?, ?), ????
????????? ??????? ? ?????? ???????????
????????? ??????? ??????????? ?????????
(???. 3, ?). ? ?????? ??????? ?? ???? ?????????? ??????? ????? (MgB2) ?????????? ??
?????? ????? ????????. ??????? ?????, ???-
# 244 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????? ?. ???????, ????? ?. ???????,.. ????????????? ???????????? ???????? ?????????????? ????????????
?????????? ?????? ?????????? ?????????, ???????????? ??????? ??????, ???????? ? ????? ?????? ????, ????????? ?????? ???????? ???????? ????????????
???. 2. ???????? ???????????? ?????? ? ???? ?????? ???????? ?? ?????????? ??????????? ?????????
??????? 2. ??????? ?????????? ???????? ? ?????????? ???????????? ????? MgB2
????????? ?????? ???????? (???. 2)
??????? ?????????? (?), ??
?
-0,020
?
-0,396
?
-0,297
?
-0,344
?
-0,398
?
-0,214
?
-0,613
?
-0,650
?
-0,561
?
-0,699
????????? ?? ???? ???? ????????, ?????????
-0,140 ??. ?????????? ???????? 2,15 ????. %.
?? ?????? ?????????? ???????? ??????? ??????????? ????, ????????? ??????
?????????? ? ??????? ?????????? ???????
???????? ?????????? ??????????? ????????? (???. 3, ?, ?). ??? ?????????? ??????????
????????? ??????? ????? ????????? -0,159 ??
(????? ?????? ????????, ???????????? ??
???? ?????????? ???????, ????? 1), ?????????? ???????? 2,15 ????. %. ??? ???????
?????????? ????? ??????? ???????? ???????
????? ????? 0,167 ?? (????? ?????? ????????,
???????????? ?? ???? ?????????? ???????,
????? 2), ?????????? ???????? 4,2 ????. %.
? ?????????? ???? ?????????? ???????
???????, ? ??????? ??????? ?????????? ???
??????, ??? ? ??????? ????? (???. 3, ?). ??????? ????? ?????? ??????? ????? -0,018 ??,
????? ?????? ???????? ????? 3, ??????????
???????? 6,18 ????. %.
???? ?????????? ?????????? ????????
? ?????? ??????? ?????????? ????????? ??????????? ????????? (6,18 ???? %) ??????,
??? ????????? ????????????? ??????????
???, ?????? ?? ???????? ???????? ????????
??????? ?????? ???? ?????? ?? ???? ???-?????????????? ?????????????? ??????? ???????? ? ???????? MgB2, ??????? ?? ???????????
? ?????? ????????, ? ????? ?? ???? ??????-
# 245 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????? ?. ???????, ????? ?. ???????,.. ????????????? ???????????? ???????? ?????????????? ????????????
? ? ?????? ?????????? ??????? ??????????? ?????????; ? ? ?????? ?????????? ??????? ? ?????????? ????????????
????????? ?????????; ? ?????????? ?????????? ?????????? ??????????? ????????? ??????? ????????; ? ? ??????
?????????? ?????????? ??????????? ????????? ??????? ????????
???. 3. ???????? ?????????? ????????? ??????? ????????
????? ??????????? ???????? ?? ??????????
???????.
????????? ? ?????? ??????????? ???????
????? ? ?????? ?????????????? ???????????
????????, ???????????? ???? ?????? ???????????? ????????? ?????? ???????, ? ????????? ???????? ?????????????? ???????. ???
?????????? ??????????? ????????? ? ????????????? ???????? ??? ???????????? ???????? ?? MgB2 ??? ???????? ????? ??????? ?????
(nudged elastic band) [15]. ???? ?????? ????????
? ????, ??? ????????? ???????? ?????????? ?????? ???????? ?? ??????????? ??????????????
? ?????? ??????? ?0 ??????? ????????? ???
E??????
??? ? ????????? ?i ?? ??????? k Ae kT
. ????????? ?????????? ???????? ???????, ?
??????? ???????? ???????? ????????????? ??
???????? ?? ??????????? ?? 5?, ???????? ?????????? ? ???????, ? ??????? ???????? ???????? ?????????????? ? ?????, ?????????? ??,
????????????? ? ??????????? ?????????? ??
???????????. ??? ??????? ???????? ?? ?????????? ??????????? ????? ???????? ??????????????? ??????? ????????? 0,693 ??, ? ???
??????? ?? ??????? ??????????? 1,130 ??. ???
????? ?? ??????? ????????????? ????????, ??
?????????? ??????? ??????????? ??? ?????????? ?????????????? ???????????.
??????????
?? ????????? ???????????? ?????????????? ???????????? ????? ????????????,
??? ?????????? ??????? MgB2 ???????? ????????????? ??????????? ?????????? ?
????????? ????????.
# 246 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????? ?. ???????, ????? ?. ???????,.. ????????????? ???????????? ???????? ?????????????? ????????????
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Shiraishi, M. Hydrogen adsorption and desorption in carbon nanotube systems and its mechanisms/
M. Shiraishi// Appl. Phys. A. ? 2004. ? Vol. 78. ? P. 947?954.
??????????????, ?.?. ??????????? ? ??????????? ?? ????????? // ?????? ????. ?
2001. ? ?6. ? ?. 369.
Kresse, G. Efficiency of ab?initio total energy calculations for metals and semiconductorsusing a
plane?wave basis set/ G. Kresse, J. Furthmuller//Comput. Mat. Sci.- 1996.- Vol. 6.- P.15-50.
Kresse, G. Efficient iterative schemes for ab initio total-energy calculations using a plane?wave
basis set/ G. Kresse, J. Furthmuller//Phys. Rev. ? 1996. ? Vol. 54. ? P.11169.
Laasonen, K. Car-Parrinello molecular dynamics with Vanderbilt ultrasoft pseudopotentials/ K.
Laasonen, A. Pasquarello//Phys. Rev. ? 1993. ? Vol. 47. ? P. 10142.
Pasquarello, A. Ab initio molecular dynamics for d-electron systems: Liquid copper at 1500 K/ A.
Pasquarello, K. Laasonen//Phys. Rev. Lett. ? 1992. ? Vol. 69. ?. 1982.
Kresse, G. Norm-conserving and ultrasoft pseudopotentials for first-row and transition elements/
G. Kresse, J. Hafner// J. Phys.: Condens. Matter. ? 1994. ? Vol. 6. ? P. 8245.
Kohn,W. Self-Consistent equations including exchange and correlation effects/ W. Kohn, L.J.
Sham//Phys.Rev. ? 1965. ? Vol.140. ? P. 1133.
Vanderbilt, D. Soft self-consistent pseudopotentials in generalized eigenvalue formalism/ D. Vanderbilt// Phys.Rev. 1990. ? Vol. 41. ? P. 7892.
Blцchl, P.E. Generalized separable potentials for electronic-structure calculations/ P.E. Blцchl //
Phys.Rev. ? 1990. ? Vol. 41. ? P. 5414.
Moroni, E.G. Ultrasoft pseudopotentials applied to magnetic Fe, Co, and Ni: From atoms to
solids/E.G. Moroni, G.Kresse//Phys.Rev. ? 1997. ? Vol.56. ? P. 15629.
Ab-initio study of hydrogen chemical adsorption on the platinum surface/carbon nanotube join
system / A.S. Fedorov, P.B. Sorokin, A.A. Kuzubov // Physica Status Solidi B. ? 2008. ? V.245,
?8. ? P. 1546-1551.
???????????? ????????? ???????? ?????? ? ?? ??????????? ????????? ??????????. /?.?.
???????, ?.?. ???????, ?.?. ?????????? // ????. ? 2008. ? ?.134. ? ?7. ? ?.1-8.
????????????? ???????????? ???????? ?????????????? ??????????? ???????? ?? ?????????? ?????????? / ?.?. ???????, ?.?. ???????, ?.?. ?????, ?.?. ??????????? // ??????
?????????? ?????. ? 2008. ? ?. 82. ? ?.1-5.
G. Henkelman and H. Jonsson, Improved tangent estimate in the nudged elastic band method for
finding minimum energy paths and saddle points, J. Chem. Phys. 113, 9978 (2000).
# 247 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????? ?. ???????, ????? ?. ???????,.. ????????????? ???????????? ???????? ?????????????? ????????????
Theoretical Study of Dissociative Hydrogen Chemisorption
on MgB2 Nanotubes
Alexander A. Kuzubova, Maria A. Raimovaa, Maria V. Serjantovaa,
Tanya A. Kozhevnikovaa and Alexander S. Fedorovb
a
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
b
Institute of Physics, SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
The dissociative chemisorption of hydrogen on the external and internal surfaces of MgB2 nanotubes
is investigated by the ab-initio DFT method. It was shown that this material may be effective sorbent
of hydrogen for the hydrogen energy industry.
Keywords: quantum chemistry, nanotubes, chemisorption of hydrogen, hydrogen energy.
# 248 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 249-259
~~~
??? 546.636
??????? ????????: ???????????? ?????
????????? ???????????
?????? ?. ???????????*, ?????? ?. ??????,
??????? ?. ?????????
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
???????? ??????? ????? ? ?????? ????????? ???????? ?? ??????? ? ???????? ????????
????????. ???? ????????????? ?????????, ???????????? ??? ??????????? ?????????
?????????? ???????? ?? ??? ???????. ?????????? ????? ??????????? ???????? ????????.
???????? ?????: ?????? ????????, ????????? ?????????, ????????.
????????
?????? ???????? ???????? ????? ?? ?????????? ????????, ?????? ??????????? ???
? ???????????? ????????, ??? ? ??????????????. ?? ?????? ? ?????? ????????????? ???
?????? ???????????? ??????? [1-10], ???????????? ??? ????????? ??? ??????? ????????????? ?????????? ?????????? ? ?????????????
[10-18], ??? ????????? ????????? ??????????
[19-24]. ?????? ????????? ??????? ????????
?? ?????????? ??????? ???????? ???????????? ????????? ?????????. ??? ?? ?????????
???????? ?????????? ??????? ??? ????????,
? ?????????, ??????? ?????? ??? ?????????
????????? ? ????? ??????????, ????????, ?
?????? ??????????????.
? ?????? ??????????? ????????? ???????? ?? ???????, ???????????????? ???????? ? ?????????? ???????????? ?????
*
1
??????????? ????????? ???? ??????? ????????.
????? ???????? ?? ???????????????
?????????? ???????? ????????
???????? ??? ??????????????? ??????????? ??????? ????????: ???????????? ???????? [Pd3(CH3COO)6] [25, 26] ? ??????-????????? [Pd(CH3COO)2]n [27]. ????????????
?????? ???????? [Pd3(CH3COO)6] ???????????? ????? ?????????? ?? ???? ?????? ????????, ?????????? ??????????? (???. 1). ?????
?????? ??????? ???? ? ???? ?????????
???????????? ??????????? ????????? ?????? ???, ??? ??? ????? ????????? ?????????
? ??????????? ?????? ? ????????? ???????
???????? ?, ????? ???????, ???????? ?????????? ?????????. ????? ?????? Pd-O ?????
? ????????? 1,96-2,02 ?. ????????? ??????
Corresponding author E-mail address: rusfaat@mail.ru
© Siberian Federal University. All rights reserved
# 249 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
???. 1. ???????? ????????? [Pd3(CH3COO)6]
??????????? ?? ????????, ?????????? C-O
?????????? 1,23 ?. ? ?????????? ????? ??????????? ?????? ???????? ?????? ????????
??????? ?????????, ?????? ????????? [O4]
??????????????? ????????? ????????????
?????? ????????. ?????????? ???????????
?????? ???????? ?????? ?? ?????????? 0,23 ?
?? ????????? ??????? ?????? ?????????. ?????????? Pd...Pd ?? ????? ????? ????? ? ????????? ? ????????? 3,10-3,20 ?, ?? ???????
????????? 3,14 ?. ????????? ? ????????????
??????????? ????????? ????? ??????? ??
???? ?????????? ??? ??????? ? ???????????? ?????????.
?????? ??????????????? ?????????
??????-[Pd(CH3COO)2]n (???. 2) ??????????
?????????-??????????????????[Pd(CH3COO)4/2]
[27], ? ??????? ????? ???????? ???????? ?????? ???? ? ??????????? Pd...Pd 2,92 ?. ?????? ??????? Pd?Pd ???????????? ?? ??? ?????????? ????????? ??????, ??????????? ?
???-????????? ???? ? ?????. ???????????
???????? ?????? ? ?????????-?????????. ???????????? ????????? ???????? ?????? ???????? ??????? ????????? ??? ?????? ??????-
?? 30 °. ??? ?????????, ? [Pd3(CH3COO)6] ????
???? ?????????? ????? 60 ° [25].
??????????????? ??????????? ??????? ???????? ?????????? ?????????????? ?
???????????? ?????????????: ????????????
?????? ???????? ??????????????, ?????????? ?????? ??????????? ???????????.
????????? ??????? ?????????
???????? ????????
????????? [Pd3(CH3COO)6] ???????? ?????????? ?????? ?????????, ? ??????????
??? ?????? ?????????? ???????? ????????.
??????-????-????? - ????????????? ???????,
??????? ????? ?? ????? ????????????????.
? ?????????? ??????? ??? ?????? ????????? [Pd3(CH3COO)6]. ? ?????? [28] ?????? ???????? ???????? ?? ???????? ??????? ???????? (?????-[Pd(NO3)2(OH2)2]) ??? ??????????
?? «???????????????» ????????????? ???????? ????????. ??? ???? ?????????? ?????????
????????? ??????, ?? ?????????:
# 250 #
{Pd(NO3)2(OH2)2}solv. + 2CH3COOH
{Pd(CH3COO)2}solv. + 2HNO3 + 2H2O
(1)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
???. 2. ???????? ?????????? ??????-[Pd(CH3COO)2]n
? ??????????? ???????????? [Pd3(CH3COO)6]:
3{Pd(CH3COO)2}solv. {Pd3(?2-CH3COO)6} solv.
[Pd3(?2-CH3COO)6]solid.
(2)
?? ?????? ?????? [29] ???????? ????????
????????????? ????????. ?????? ?????????
????????????? ???????? ?????????? ?? ?????????? ? ???????????????. ??????? ???????
???????????? ??? ?????????? ??????????????
???????? ? ????????? ? ???? ??????? ?????. ?
????? ???????? ???????, ??????????? ????????? ?????????? ??????????? ??????? ????????. ???????, ? ???????????? ? [30], ?????
??????????? ????? ??????????:
Pd + 2HNO3 + 2CH3COOH
{Pd(CH3COO)2}solv. + 2NO2 + 2H2O
(3)
??? ???????? ? [29-31], ???????????
[Pd3(CH3COO)6] ?????????? ?????? ? ???????????? ????? ????????? ???????, ??? ?????????? ?? ??????? ?????????? ??????[Pd(CH3COO)2]n [27] ?/??? [Pd3(CH3COO)5NO2]
[30, 32].
??????????? ??????-????-????? ??????? ????????, ?? ?????? [27], ??????????????
??? ???????????? 50-140 ?? ?? ?????????????????? ???????? ????????????? ???????? ?
??????????? ????????????????? ????????
??????? ? ??????? ????? (II-IV) ??? ?? ?????????????? ???????? [Pd3(CH3COO)6] ? ??????????? ????? ????????? ??????? ??????? ? ??????? ????? (II-IV). ?????????, ??-????????,
?????? ???? ???????????? ????????.
?????????????? ???????????? ?????
??????????? ????????? ??????????
????????
??????? ?? ??? ??????? ??????? ? ????????? ?????? ????????????? ???????
???????? ? ???? ??????????????? ??????:
[Pd3(CH3COO)6] ? ??????-[Pd(CH3COO)2]n..
????????? ? ???? ????????? ??????????????
?????? ? ???, ?????? ???????????? ??????
???????? ?????????? ? ???? ????????????
??????? ? ?????????? ? ???? ????????, ?????? ??? ????????? ???????.
??????????????? ???????????? ??????, ? ????? ??????????? ????????????????? ?????????? [27] ?? ??????? ? ????????
????????? ?????????? ???????? ?????????
# 251 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
?????????????? ??? ???????????? ???????
? ?????????? ?? ??????????? ? ????????
????????????? ????????. ??? ????????????
????????????? ????????, ????? ????? ??????????????? ??????? ???????? ? ?????????
??????, ?? ???????? ?????????? ???????
????????????? ??????????? ??? ?????????
????????????.
????? ??????????? [Pd3(CH3COO)6]
????????, ??? ??????? ???????????
????????????? ??????? ???????? ?? ???????????? ??????????, ? ???????? ???????? ?????
????????????? ?????-[Pd(NO3)2(OH2)2] [33],
????? ?????????????? ????????, ??? ??????
???????? ?? ?????????? ??????? ?? ???????????. ??? ?? ?????, ???????? ?????????????? ????????????? ? ????????????? ???????
????????? ??????????, ? ????? ????????????
(???. 3). ??????????? ? ??????? ?????????????? ?????????? ?????????, ??????? ????????
????????? ? ????????? ???? ????????????
???????? ????? ??????????? ? ???? ??????
????????. ????????? ????????????????, ????????? ??????????? ?????????? ????????,
?????????? ?????? ??????? ? ??????????,
????????, ? [34-39]. ???????????? ????? ??????????? ? ???????? ???????? (II) ????????
???????? ?????? ??????????????? ?????????? ???? ???????? ?????? ??????? ??-?? ??????????? ???????????, ????????? ?????????? ????????? ?????. ????????? ?????????
?????? ??????????????? ???????????? ??????????? ???????? ? ???????? ??????????. ?
??????????????? ????????? ????? ?????????
?????????? ???????? ? ?????????? ??????????? ??????????, ?????? ? ?????????? ??????? ??????????, ?????????? ?? ?????????
??????. ???, ? [40-43] ??????????, ??? ??? ???????? ? ???????? ??????? ???????? ? ????????
??????? ????????? ????? ?????????? ????????? ?????, ? ? ?????? ??????????? ? ??????-
?????? ????????? ????? ??????????? ???????
?? ????????????? ????????? ? ????????? ?
????? ? ???????????. ??-????????, ????????
?????????????? ? ????????? ? ?????????????? ????? ????????? ????????-??????????
?????????? ???????? (II) ??????? ? ????????????? ??????????? ???????????, ???????????????? ?? ???????? ???????? ?????????,
??? ??????????? ?????????? ???????????????
??????? (???. 3).
????????????? ????????????? ? ???????? ????- ? ????????? ?????????? ?????????
?? ?????????????? ? ???????????? ??????????? ??????? (???. 3). ????? ??????? ????? ??
??????? ???? ??? ???????? ????????: (?)?????????? ??????? ??????? ????? ????????????? ?????????? ?????????, (?)-?????? ??
???????????? ? ??????????? ???????? (???????? ???????) ? (?)-????????? ? ??????????? ????. ??????????? ? ??????????? «??????????» (????????? ? ??????????? ????)
?? ??????????, ????????? ??? ???????? ?????? ??? ?????. ???????? ??????? ??????????
??????????? ?? ?????????? ?????? ???????,
????????? ? ?????? ?? ????? ????????? ?????? ??????? ??????. ?????? ?????????? ???????? ? ??????????????????? ????????????? ??????????? ? ????????? ??????????, ???
????????? ????????? ???????? ??????????
????????? ??????. ??????? ????????, ??? ?
???????? ??????????? ??????????? ?????????????? ?d?Pd, ? ??? ????? ??????, ??-??????,
?? ????????? ????????????? ??????????
(3,1-3,2 Е), ??-??????, ?? ???????? ???? ????????? ?? ????? ? ???????? [Pd3(CH3COO)6],
??????? ??????????????????? ? ???????????? ?????????, ?, ?-???????, ?? ???? ?????
???????????????? ??????????? ?????? ????????. ??? ??? ????????? ???????????????
? ???, ??? ?? ???? ??????????? ??????????
??????????? ???????? ??????????? ????????? ? ????????, ?? ???? ?????????????? ?????-
# 252 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
???? 1. ??????????? ????????????
?????????? ????????? ????????
O
S
OH2
O
O
N
+ 2CH3COOH '
Pd
H
O
O
O
C
H
N
C
??? S ? H2O
?/??? CH3COOH
O
H
???? 2. ??????????? ??????????
?????????? ????????? ????????
H
C
S
C
O
H
2 {Pd(CH3COO)2S2}solv.
+ 2HNO3 + 2H2O
S
O
H
OH2
Pd
O
O
'
H
H
C
C
C
H
C
C
C
S
H
O
H
{Pd2(P2-CH3COO)2(CH3COO)2S2}solv.
+
H
'
{Pd(CH3COO)2S2}solv.
H
H
C
CH3COO
H
H
O
Pd
O
H
+ 2S
H
O
???? 3. ???????????
????????????? ?????????
?????????? ????????? ????????
H
H
O
Pd
O
H
C
C
O
C
H
H
H
C
'
C
O
O
Pd
O
O
S
S
O
O
+ 2S
Pd
Pd
O
O
C
C
OOCCH3
H
H
C
H
C
H
H
H
????. 4. ???????????
????????????? ????????????
?????????? ????????? ????????
CH3
O
O
{Pd3(P2-CH3COO)4(CH3COO)2S2}solv. '
C
CH3
C
O O
Pd
O
CH3
C
CH3
+ 2S
Pd
O
O O
C
O
O
???. 3. ?????????????? ????? ??????????? [Pd3(CH3COO)6]
# 253 #
C
Pd
O
O
C
CH3
CH3
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
?????? ?????????? ?????????. ???????????????????? ??????? ??????????? ????????
??????? ?????? ?????????? ?? ???????????
????? ????? ??????????????. ???????? ???????, ??? ??????????? ?????????????? ?????? ?????????? ?????????, ????? ????? ?
??????? ?????? ????? ?????????? ??????????????? ???????? ??? ?????????? ?????????? ??????????????? ???????. ?????????
?????????? ?????????? ??????????? ???
??????? ? ?????? ?????, ??? ???????? ? ????????. ???????? ??????? ????? ?????????
???????????????? ???????? ???????? ????,
??????? ????? ?????????? ??????????????.
?????????? ????????? ???????????? ??????????? ? ????? ???????? (??., ???????? [44,
45]), ?????? ???????????? ??????? ?? ???????? ???????? ??, ??? ? ???? ???????? ??????????? ????????? ??????????? ???????.
????, ?? ???? ??????????? ????????
[Pd3(CH3COO)6] ????? ???????? ?????? ?????, ?????????? ?? ???. 3. ?????? ?????? ?????????????? ???????? ??????????? ?????????
????????? ????? ? ?????-[Pd(NO3)2(OH2)2].
?????? ???? ? ??????????? ??????????? ????????? ?????????? ???????? ? ?????????,
? ???????????? ?????????? ?????? Pd-O-CO-Pd (???. 3). ?? ??????? ????? ???????????
??????????? ????- ? ????????? ?????????
?????????? ? ?????????????? ????????????
????????????? ????????? ?????????. ?????
?????????? ??? ??????????, ??????? ????????
????????? ? ?????????????? ?????? ??????????? [Pd3(CH3COO)6].
????? ??????????? [Pd3(CH3COO)5NO2]
???? ? ???????? ???????? ?????????????
???????? ? ???????? ??????? ????????????
?????? ????? ??? ?????? ?????????????
??????, ?? ???????? ????????? ?? ?????????????? ? ????????????? ????????? 15-50 ??
???????? [Pd3(CH3COO)5NO2]. ????????? ???-
???????????? ???????? [Pd3(CH3COO)6] [25,
26] ? [Pd3(CH3COO)5NO2] [30, 32] ??????????,
??? ??????? ?? ???????? ???????? ???? ? ???
?? ??????? - ???? ?? ???? ?????? ????????,
????? ???????? ?????????????? ?????????? ????????? ??????. ????? ???? ??
???????????? ????????????? ?????? ????
?????????? ??????? [Pd3(CH3COO)6-n(NO2)n],
?????? ?????? ???? ???????????????? ?? ???????????. ???????, ??-????????, ??????? ?
????????? ??????????? [Pd3(CH3COO)5NO2].
???????? ??????????? [Pd3(CH3COO)5NO2],
?????????? ?? ????????? ?????????? ????????? ?????? ?????????, ?????????????? ??
????? ????????????. ??-??????, ??? ????????? ?????? «??????????» ??????????? ?????
??????????, ??? ??? ?????????. ??-??????,
????????????? ? ????? ????????? ?? ????
???????????????? ?????? ?? ?????? ?? ?????????? ??????????????? ???? ??????????.
?? ????????? ?????????????? ?????
????????? «??????????» ????? ?????????
??????? ?????????????? ?????????? ???????
[Pd3(CH3COO)6-n(NO2)n] (??? n>1). ???? ?????
???????? ???????? ???????????? ??????????
????????? ??????? ???? ?? ???? ?????????
??????, ?? ?????, ??-????????, ??????????
??? ????????? ?????. ????? ?????? ??????,
?????????????? ? «??????» Pd?Pd, ?????
???? ?????????. ????????? ??? ????? ????????? ?????? ???????? «??????????» ??
???????????????. ?????????????? ????????
[Pd3(CH3COO)5NO2] ??????????? ?? ?????????? ?? [Pd3(CH3COO)6] ?? ????????? ??????
????? ??????? ?????. ???????? ????? ?????????? ? ??????? ????? ?????????? ?? ??????????? ????? ??????????? ??????????????.
????? ??????????? ??????[Pd(CH3COO)2]n
??? ????????? ??????????? ???????????????????? ???????? ???????? ?? 50-140 ??,
# 254 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
??????????? ??????????? [Pd(CH3COO)2]n. ??????? ????????, ??? ?????????? [Pd3(CH3COO)6]
? [Pd3(CH3COO)5NO2], ?????????? ? ????? ??
???????, ???????????? ? ??????-????-?????,
?????? ??????? ???????? ???????????.
????????????? ???????? ??????????? ???????????? ???????????????? ??????????
????, ????????????? ??? ????????????. ?
?????? ????????? ????????????????? ???????????? ????? ??????????? ?????????. ????
????????? ?????? ? ??????-[Pd(CH3COO)2]n
??-???????? ???????? ?????????? ?????????, ?????????? Pd?Pd ??????????? ?? ???????? 2,89 Е, ????????? ???????????????
????????? ?????????????? ???? ? ?????, ????? ???????? ????????????? ?? ?????? ?????.
???????????? ??????????? ????????? ?????
??????????????? ??? ????????????? Pd?Pd
??????????????, ??????? ???????????? ?????
?????????? ?????????.
??? ??? ??????? ???????? [Pd3(CH3COO)6]
? ??????-[Pd(CH3COO)2]n. ?????????? ? ?????
??????? ????????????? ? ?????????????
????????, ??? ????? ????????????? ???????,
????? ????????? ??????????? ?????????
????????? ?????? ???????? ? ????????????
?????????????? ??????????, ???????????
????? Pd (IV). ????????? ????? ???????????
??? ??????? ?????????????? [Pd3(CH3COO)6]1,
?????????? ? ?????????? ?????.
?????? ????????, ??? ???????? ????
?????????? ? 4d-?????? ???????? (II) ??????????? ????????? ??? ?????????? ??????????
? ???????? ? ??????????? ????????????????
??????????????? ????? ? ??????????????.
???? Pd (IV) ????? ??????? ? ??????????
?????????????? ? ???????????? ????? ???????? ?? ??????? ???? ???????? ? ???????? ??
???? ????????? ? ??? 4d-??????. ??? ????????
1
? ????????? ?????? ???????? ?? ???? ??????????? ?????????????? Pd?Pd ? ????????
?????? ????? ???????. ???? ??????? ??????????????? ??????, ?? ????? ??????????????? ??????? ???????? ???? ???????? ? ?????????? ?????????? ???????????. ????? ????
????? ????? ???????? ??????? ??? ?????????????? ? ???????? ?????????? ?, ? ?????????, ? [Pd3(CH3COO)6]. ??????? ????????,
??? ???????? ???????? [Pd3(CH3COO)6] ?????? (???. 1), ??? ?????? ???????? ?????????
?? ??????? ??????? ????? «??????????» ??????????? (??????????? dz2-????????). ???
?????????????? ??????????? ????????? ??????????? ??????????? ??? ???????? ? ????????? ????? ?????????? ??????????. ????????
????? ?????????????? ???????? ????????
????? ???????????? ?? ?????????? ?????????? ? ?????? ?? ?????? ???????? ???????????
???????? [Pd3(CH3COO)6]. ????? ??????????
??????? ??????????? ?????????? (???????
?????????), ????????? ?????, ???????? ?? ?????????? ?????????? ?????????????? ??????,
??????????? ????? ? ?.?. ????????, ??? ?????
n-?? ????? ???? ?????????? ???? ??????????? ??????????????? ???????? ?????? Pd (IV)
?? Pd (II). ????????????? ??????? ????? ?????????????? ???????? ? ???????????? ?????????? ???????? ?????????????? ????????.
????? ???????, ? ?????? ?????? ?????????? ??? ?????????????? ? ????????? (II)
????????? ???????????? ????????, ???????
?????????? ????? ????? ????? ???????
????????. ??????????? ??????? ?????????
????? ?? ??????? ? ?????????????? ? ????
???????? ??-?? ??????? ?? ??? ??????, ???
?????????? ??????????? ??????????? ???
??-?? ??????????? ???????????????? ???????? ??????? ????. ?????? ???????????
??????????? ?? ????????? ??????????? ??????????? ??????????? ??? ????????? ?????????????? ? ??????
????? ? ????????? Pd (II) ? Pd (IV), ????????, ??????????? ? [46], ????? ???????????? ??????????? ??????????
????? ???????.
# 255 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
????????? ? ???? ??? ??? ????? ??????
???????, ?????? ????, ????? ? ???????????
??????????? ? ????????? ???????, ???????
????? ????????? ?? ???????? ????? ??????????????, ????? [Pd 3(CH3COO)6]. ??? ?????????? ???????????? (????? 50 ??) ???????
?????????? ??? ?? ???????? ????????????
?? ????????? ? ???????????? ???????? ????????? ?????????? ????????, ??? ???????
?????????? ????? ?????????? ??????-????????????? ????? ??????? ????????. ????-
????
???????????
??????-[Pd(CH3COO)2]n
????? ???? ???????? ?????????????? ?????????, ???????? ?????? ???????? ???????
?: (?) ????????? ????????? ?????? ????????
? ????????? [Pd 3(CH3COO)6], (?) ?????????
????? ? ??????????? (?????????) ??????
???????? ?? ???????????? ??????????????
Pd?Pd, ???????? ?????? ?? ?????? ????? ???????? ? ????????????? ????????? ??????,
(?) ?????????????? ????????? ?????? ? ?????? ????????? [Pd 3(CH3COO)6].
?????? ??????????
1.
2.
3.
4.
Hayashi M., Yamada K., Nakayama S.-Zo, Hayashi H., Yamazaki S. Environmentally benign
oxidation using a palladium catalyst system // Green Chemistry. 2000. V. 2. P. 257?260.
Hayashi M., Yamada K., Nakayama S.-Zo. Catalytic hydrogen-transfer reactions of benzylic and
allylic alcohols with palladium compounds in the presence of vinyl acetate or under an ethylene
atmosphere // J. Chem. Soc., Perkin Trans. 2000. V. 1. P. 1501?1503.
Nishimura T., Kakiuchi N., Onoue T., Ohe K., Uemura S. Palladium(II)-catalyzed oxidation of
terminal alkenes to methyl ketones using molecular oxygen // J. Chem. Soc., Perkin Trans. 2000.
V. 1. P. 1915?1918.
Yao Q., Kinney E. P., Yang Zhi. Ligand-Free Heck Reaction: Pd(OAc)2 as an Active Catalyst
Revisited // J. Org. Chem. 2003. V. 68, N 19. P. 7528-7531.
5. Leadbeater N.E., Marco M. Rapid and Amenable Suzuki Coupling Reaction in Water Using
Microwave and Conventional Heating // J. Org. Chem. 2003. V. 68, N 3. P. 888-892.
6. Wegner H.A., Scott L.T., Meijere A. A New Suzuki-Heck-Type Coupling Cascade: Indeno[1,2,3]Annelation of Polycyclic Aromatic Hydrocarbons // J. Org. Chem. 2003. V. 68, N 3. P. 883-887.
7. Zhao F.Y., Shirai M., Arai M. Palladium-catalyzed homogeneous and heterogeneous Heck
reactions in NMP and water-mixed solvents using organic, inorganic and mixed bases // J. Mol.
Catal. A: Chem. 2000. V. 154, issues 1-2. P. 39-44.
8. Bedford R.B., Blake M.E., Butts C.P., Holder D. The Suzuki coupling of aryl chlorides in TBAB?
water mixtures // Chem. Commun. 2003. P. 466-467.
9. Wolfe J.P., Singer R.A., Yang B.H., Buchwald S.L. Highly Active Palladium Catalysts for Suzuki
Coupling Reactions // J. Am. Chem. Soc. 1999. V. 121, N41. P. 9550-9561.
10. Hiller A.C., Nolan S.P. Palladium/Nucleophilic Carbene Catalysts for Cross-Coupling Reactions
// Platinum Metals Rev. 2002. V.46, ?2. P.50-64.
11. Kadnikov D.V., Larock R.C. Palladium-catalyzed carbonylative annulation of terminal alkynes:
synthesis of coumarins and 2-quinolones // J. Organomet. Chem. 2003. V.687. P.425-435.
12. Willans C.E., Mulders J.M.C.A., Vries J.G., Vries A.H.M. Ligand-free palladium
catalysed Heck reaction of methyl 2-acetamido acrylate and aryl bromides as key step
in the synthesis of enantiopure substituted phenylalanines // J. Organomet. Chem. 2003.
V.687. P.494-497.
# 256 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
13. Arcadi A., Cacchi S., Fabrizi G., Marinelli F., Parisi L.M. Palladium-catalyzed reaction of aryl
iodides with tertiary propargylic amides.: Highly substituted allenes through a regioselective
carbopalladation/?-N-Pd elimination reaction // J. Organomet. Chem. 2003. V.687. P.562-566.
14. Astruc D. Palladium Nanoparticles as Efficient Green Homogeneous and Heterogeneous CarbonCarbon Coupling Precatalysts: A Unifying View // Inorg. Chem. 2007. V. 46. P. 1884-1894.
15. Nair D., Scarpello J.T., Vankelecom I. F. J., Santos L.M.F.D., White L.S., Kloetzing R.J., Welton
T., Livingston A.G. Increased catalytic productivity for nanofiltration - coupled Heck reactions
using highly stable catalyst systems // Green Chemistry. 2002. V. 4. P. 319?324.
16. Roca F.X., Motevalli M., Richards C.J. Synthesis of Planar Chiral Phosphapalladacycles by Highly
Enantioselective Transcyclopalladation // J. Am. Chem. Soc. 2005. V. 127. P. 2388-2389.
17. Kamiya I., Nishinaka E., Ogawa A. Palladium(II) Acetate in Pyridine as an Effective Catalyst for
Highly Regioselective Hydroselenation of Alkynes // J. Org. Chem. 2005. V. 70. P. 696-698.
18. Ebitani K., Choi K.-M., Mizugaki T., Kaneda K. Novel Preparation of Palladium Nanoclusters
Using Metal Nitrates and Their Catalysis for Oxidative Acetoxylation of Toluene in the Presence
of Molecular Oxygen // Langmuir. 2002. V. 18. P. 1849-1855.
19. Dhas N.A., Gedanken A. Sonochemical preparation and properties of nanostructured palladium
metallic clusters // J. Mater. Chem. 1998. V. 8. P. 445-450.
20. Winkler K., Noworita K., Bettencourt-Dias A., Sobczak J.W., Wu C.-T., Chen Li-C., Kutner
W., Balch A.L. Structure and properties of C60 ?Pd films formed by electroreduction of C60 and
palladium(II) acetate trimer: evidence for the presence of palladium nanoparticles // J. Mater.
Chem. 2003. V. 13. P. 518-525.
21. Wysocka M., Winkler K., Balch A.L. The electrochemical formation and properties of bilayers
composed of polypyrrole and C60Pd films // J. Mater. Chem. 2004. V. 14. P. 1036-1042.
22. Mayer B.R., Mark J.E. Transition metal nanoparticles protected by amphiphilic block copolymers
as tailored catalyst systems // Colloid Polym. Sci. 1997. V. 275. P. 333-340.
23. Mallick K., Witcomb M.J., Dinsmore A., Scurrell M.S. Fabrication of a Metal Nanoparticles and
Polymer Nanofibers Composite Material by an in Situ Chemical Synthetic Route // Langmuir.
2005. V. 21. P.7964-7967
24. Cheng C., Gonela R.K., Gu Q., Haynie D.T. Self-Assembly of Metallic Nanowires from Aqueous
Solution // Nano Letters. 2005. V.5, N 1. P.175-178.
25. ?????? ?.?., ??????? ?.?., ??????? ?.?., ???????? ?.?., ???? ?.?. ????????? ? ????????
????????? ???????? (II) ? ??? ?????????? // ??????????????? ?????. 1993. ?.19, ? 1. ?.
57-63.
26. Scapski A.C., Smart M.L. The Crystal Structure of Trimeric Palladium (II)
Acetate // Chemical Society. Section D. Chemical Communications. 1970. N 11.
P. 658-659.
27. Kirik S.D., Mulagaleev R.F., Blokhin A.I. [Pd(CH3COO)2]n from X-ray powder diffraction data //
Acta Crystallogr. Sect. C, Cryst. Struct. Commun. 2004. c 60. m449-m450.
28. ??????????? ?? ??????????????? ??????? / ???. ?. ??????. ?.: ???, 1985. ?. 5. ?. 1832.
29. Stephenson N.A., Morehous S.M., Powell A.R., Heffer J.P., Wilkinson G. Carboxylates
of Palladium, Platinum and Rhodium, and their Adducts // J. Chem. Soc. 1965. N 6.
P. 3632-3640.
# 257 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
30. Bakhmutov V.I., Berry J.F., Cotton F.A., Ibragimov S., Murillo C.A. Non-trivial behavior of
palladium (II) acetate // Dalton Trans. 2005. P.1989-1992.
31. Tsutomu T. Preparation of palladium acetate // Patent ?f Japan ? JP61047440, 1986.
32. Chiesa A., Ugo R., Sironi A., Yatsimirski A. Isolation and characterisation by X-ray studies of
palladium ?2-nitrosyl clusters in the reduction of nitric acid by carbon monoxide mediated by
palladium acetate // J. Chem. Soc., Chem. Commun. 1990. V.4. P. 350-351.
33. Laligant Y., Ferey G., Le Bail A. Crystal structure of Pd(NO3)2(H2O)2 // Materials Research
Bulletin. 1991. V.26. P. 269-275.
34. Vicente J., Saura-Llamas I., Cuadrado J., Arellano M.C.R. Ortho-Metalated Primary Amines.
6. The First Synthesis of Six-Membered Palladacycles from Primary Amines Containing
Electron-Withdrawing Substituents: End of the Limiting Rules of Cope and Friedrich
on Cyclopalladation of Benzyl- and Phenethylamines // Organometallics. 2003. V.22.
P. 5513-5517.
35. Fernandez A., Vazquez-Garcia D., Fernandez J.J., Lopez-Torres M., Suarez A., Castro-Juiz S., Vila
J.M. The First Crystal and Molecular Structure of a syn-Acetato-Bridged Dinuclear Cyclometallated
Complex [Pd{2,3,4-(MeO)3C6HC(H)=NCH2CH2OH}(?-OAc)]2 // Eur. J. Inorg. Chem. 2002.
P.2389-2401.
36. Zaitsev V.G., Shabashov D., Daugulis O. Highly Regioselective Arylation of sp3 C-H Bonds
37.
38.
39.
40.
41.
42.
43.
44.
Catalyzed by Palladium Acetate // J. Am. Chem. Soc. 2005. V.127. P. 13154-13155.
Thu H.-Y., Yu W.-Y., Che C.-M. Intermolecular Amidation of Unactivated sp2 and sp3 C-H Bonds
via Palladium-Catalyzed Cascade C-H Activation/Nitrene Insertion // J. Am. Chem. Soc. 2006.
V.128. P.9048-9049.
Calmuschi B., Englert U. (R)-Di-?-acetato-? 2O:O?-bis{[2-(1-aminoethyl)phenyl-? 2C1,N]
palladium(II)}, (R)-di-?-chloro-bis{[2-(1-aminoethyl) phenyl-? 2C1,N]palladium(II)} and [SP-44]-(R)-[2-(1-aminoethyl)phenyl-? 2C1,N]chloro(pyridine-?N)palladium(II) // Acta. Crystallogr.,
Sect. C: Cryst. Struct. Commun. 2002. V. 58. i.11. m545-m548.
O?Keefe B.J., Steel P.J. Cyclometallated compounds. XV. // Acta. Crystallogr., Sect. C: Cryst.
Struct. Commun. 2000. V.56. i.12. P.1440-1441.
Pandey R.N., Henry P.M. Interaction of Palladium(II) Acetate with Sodium and Lithium Acetate
in Acetic Acid // Canad. J. Chem. 1974. V.52. N 8. P.1241-1247.
Pandey R.N., Henry P.M. Equilibria between Palladium(II) Acetate and Olefins in Acetic Acid
containing Sodium Acetate // Canad. J. Chem. 1975. V.53. N 12. P. 1833-1841.
???????? ?.?., ??????? ?.?., ???????? ?.?., ??????? ?.?., ????????? ?.?.,
???????? ?.?., ??????? ?.?. ?????? ? ??????????? ??????????? ??????????
???????? ? ?????????? ??????????????. ??????????????? ????????? ????????[S(+)-2-?????????????] ???????????(II) // ????. ???????. ?????. 1990. ?. 44. ? 11.
?. 1920-1927.
???????? ?.?., ????????? ?.?., ?????? ?.?., ??????? ?.?. ????????? ?????????
???????? ???????? (II) ? ????? CO2 ??? ????????????? ????????????? // ????. ???. 1996.
?. 346. ? 4. ?. 486-489.
Barton D.H.R., Khamsi J., Ozbalik N., Reibenspies J. Phenyl-phenyl coupling in triphenylantimony
catalysed by palladium(0) // Tetrahedron. 1990. V.46. P. 3111-3122.
# 258 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
?????? ?. ??????????, ?????? ?. ?????, ??????? ?. ????????. ??????? ????????: ???????????? ??????
45. Fuchita Y., Takahashi K., Kanehisa N., Shinkimoto K., Kai Y., Kasai N. The crystal structure
of the unique diaryltripalladium (II) complex, [Pd3(C6H3Me2)2(?-O2CMe)4{S (CH2CHMe2)2}2] //
Polyhedron 1996. V.15. P. 2777-2779.
46. ????????? ?.?., ????? ?.?. ??????? ?????????? ??????????. ?????. 1977. C. 296, 306.
Palladium Acetates. Hypothetical Scheme of Production
Ruslan F. Mulagaleev?, Sergey D. Kirik?
and Nikolay N. Golovnevb
?
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
The analysis of accessible data on synthesis and crystal structure of palladium acetate is carried out.
The chemical circuit of reception of palladium acetate from its nitrate solution is offered. The schemes
of production of palladium acetate compounds are offered.
Keywords: palladium acetate, acetate complexes, palladium.
# 259 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 260-268
~~~
??? 544.016.2+669
??????????? ?????????????? ????????????????? ???
? ??????????? ?????? ???????????
???????????? ????????
???? ?. ????????*, ????? ?. ????????,
????? ?. ???????, ?????? ?. ??????,?
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ????? ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
????????? ????????? ??????? ?????????????? ????????????????? ??? ? ????????
????????????? ???????????, ?????????? ??? ???????? ??????? ??????? ????????????????
???????. ??????????? ??????? ????????? ?????????? ? ???????? ???????????? ????????? (??)
?? ??????????????. ??????? ?????????? ? ??????? ???????? ?? ???????? ? ?????????????
? ??????? ??????? ???? NaCaAlF6. ???????????, ??? ??????? ??????????? ?????????????
??????????????? ???? NaCaAlF6 ????????? ? ????????????? ????????? 640-740 °?. ????
Na2Ca3Al2F14 ????????? ???? 610 °?. ??????????? NaCaAlF6 ? Na2Ca3Al2F14 ??? ??????????
?????????? ?? ??????? ??????? ? ?????????? NaAlF4 ? ??????? ?????????? 640-610 °?.
??? ??????????? ? ???????????? ???????? ?????? ?????????? ?? ?????????. ???????????
??????????????????? ??????????????????? ???????????? ??? NaCaAlF6 ? Na2Ca3Al2F14
???????????? ???? ???????????????? NaCaAlF6 ??? ?????? ???????????. ??????????????
???????????? ?? ???????????? ??????????? ? ????? ???????? ??????? ???????????.
???????? ?????: ???????????? ????????, ???????????? ???????????, ????????? ?????????
??????? NaF-AlF3-CaF2, ??????? ???????-??????-??????????? ???????, ???????????????
??????.
?????? ??????? ? ???????? ???????????????? ???????, ??????????? ??? ????????? ??????????? ?????????????? ???????????? ??????????? ? ?????????????????
???????????? ????????. ?????????? ??????? ??????? ? ??????????? ?????????? ??
3 ?? 10 ????.%. ?????? ??????????? ?, ? ???
?????, ?????????? ??????? ??????? ???????????? ??????????? ????????. ????????*
1
??? ??????? ??????????? ???????? ???????
???????????????? ??????? (???), ?????????
??????????? ?????, ? ??????? ??????????
??????????? ? ???? ?????? ???????????????
(Na 3AlF6 (???????), Na 5Al3F14 (??????) ? ??.) ?
???????? (Al 2O3 (????????), NaCaAlF6) ???.
?? ??????? ??????????? ????????????? ???????????? ???????? ???????????? ??????
?? ?????????????? ???, ??????? ???????-
Corresponding author E-mail address: jnz@icct.ru
© Siberian Federal University. All rights reserved
# 260 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
?????? ? ???????????? ?????????? ??????????? ? ????????? ???????? ??????????????? ???????? ? ??????????? ?????????
(??) ? ??????? ????????? ??????? ?????? ?
??????? ????????.
?????? ??????? ???????? ?????????
? ???????? ?????????????? ??????? ???????? ? ?????? ? ?????? ????????????.
???? ????? ??????? ?????, ????????? ???
????????? ???????????? ??????? ?? ???????? ??????????? ??. ??????????????
??????????? ??? ? ????????????, ?????????? ???????, ???????????? ????? ???????????? ????????. ??-??????, ??? ??????? ?
??? ??? ? ???????? ?????????????? ??????
??????? ???????? ??? ????: CaF2 (???????), NaCaAlF6 ? Na 2Ca 3Al 2F14 (??????????
????????). ??-??????, ???? NaCaAlF6 ???-
??????? ????????? ????????????????? ?????? [1] ? ???????? ??????? ? «???????????» ?????, ??? ??? ??????? ????????????
??????????? ?????????????? ????????. ???
???????? ??????? ??????????? ??????? ???
??????? ???????? ????? ????????????? ???????. ????????? ?? ????? ??????? ????????
????????? ? ?????????????.
??????? ??????? Na3AlF6-AlF3-CaF2,
?? ?????? ????????????????????, ??? ???????? ???????? ?? ?????????. ?-???????,
??????????? ?????? ???????? ?? ?? ?????????????? ? ??????????? ?? ?????????
?????????? (???????? ??, ????????? ???????????).
? ????? ?? ?????????? ???????? ???????????? ??????? ????????????? ???????
??? ???????????? ? ?????????????? ??????????????????? ????? ??????? ???????????
????????? ????????????????????? ?????????? ?????? ?????????? ???????. ??????
??? ???? ?? ?????? ???????? ????? ?????????? ????????? ? ???????? ???????? ??????
? ????????. ??????? ??? ??????? ????????
??????? ??????? ????????, ??? ??????????
???????? ??????????????? ? ??????????
????????????, ? ??? ?? ????????? ? ?????????????????. ? ????? ????????? ????????
??????? ??? ???????? ??????? ??????? ???????????? ???????? ? ???????? ??????? ????????????, ???????????? ? ??????????? ???
????????? ???????????, ? ???????? ????????????? ???????? ???????.
?????? ?????????????. ???????? ?????????, ???????????? ???????????? Na3AlF6AlF3-CaF2, ??????????? ??????? ? ???????
[4] ? 1980 ????. ???? ??????? ?? ????????????? ???? ?????????? ??????? ? ????????
NaCaAl2F9 ? NaCaAlF6. ? ????? ??, ? ???????
????? ????????????????? ????????? ????:
CaF2, Na3AlF6, Na5Al3F14, Ca2AlF7, CaAlF5, AlF3,
NaCaAl2F9. ?????? [5] ? 1985 ???? ???? ???????? ? ?????????, ??? ?????? ???? NaCaAl2F9 ??
????? ???? ?????? ? Na2Ca3Al2F14. ?????????
?.?. ? ?????????? [6] ? 1985 ???? ???????????? ????????? ??????? NaF-AlF3-CaF2, ? ???????????? ? ??????? ?????????? 7 ??????????
??????????, ??????? 3 ??????????? ?????????? ??????????: Na3AlF6, NaAlF4, CaAlF5
? 4 ????????????? ?????????? ? Na5Al3F14,
NaCaAlF6, NaCaAl2F9, Ca2AlF7.
?? ????????? ?????? ??????????????????????????? ??????? ??? ??????? Na3AlF6
- NaCaAlF6 ????? ? ????? [4] ?????, ???
NaCaAlF6 ?????????? ? ???? ???????????
???????????? ? ????????????? ????????
610 °C ? 722 °C. ???? NaCaAlF6 ???????????
?????????? ?????? ????? ????? ???????
??????? NaF-AlF3-CaF2, ??????????? ?? ?????????? ?????????? ???? ???????? ?.?. ?
????????? ?.?. [2] ??? ? 1922 ????, ????????? ?????? ???????????????????? ???????,
???? ?????? ???????? ???????, ?????????
? ??? ??????????????? ????: NaF, Na3AlF6,
Na5Al3F14, AlF3, CaF2. ????? ? ????????? [3]
?????????? ????????????? NaCaAlF6, ?????-
# 261 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
??? 600 °C ? ??????? 20 ?????, ?????? ???
?????????? ????????????????? ???????????? ?? 100 ????? NaCaAlF6 ????????? ?
NaCaAl2F9 (??? ???? ????????, ??????????
NaCaAl2F9 ????????????? ?????????? ??????
Na2Ca3Al2F14). ??????? ???????? ????????????? ??????? ????????? ?????????? ?? ????.
???????? ??????? ?????? ???????????? ???????????? ??????????? ????? ????????????, ??? ????????? ???????? ????????? ??????? ??????????, ??????? ?????
???? ???????????? ?? ?????? ?????????
???????????? ??????. ????? ??????? ????????, ??? ?????????? ??????? ?????????????? ?????????? NaCaAlF6, Na 2Ca 3Al 2F14,
Ca 2AlF7 ? CaAlF5, ? ????? ????????????? ?
??????????????? ?????, ??????????? ? ?????????????? ??????? [4, 6], ?? ??????
??????? ?? ?????????. ?????????? ?????
??????????????? ??? ?????????? ????? ????????? ?????????? ??????????????? ?? ??
????????? ?????????, ? ?? ?????????, ??????????? ????????????? ??????????????
?? ?????????????? ???.
? ????????? ?????? ????????? ????????? ??????? ?????????????? ????????????????? ??? ? ???????? ?????????????
???????????, ?????????? ??? ????????
???????, ? ????? ????????? ????????????
?? ????????? ???????? ????????? ??????????????? ?????????????. ??? ?????????? ????? ???? ??????? ??????? ?????????
?????????? ?? ?????????????? ????????????????? ??? ? ???????????? ? ??????
?? ??? ? ???????????? ????????, ??? ?
??????????????? ? ???????????? ????????; ??????? ??????????? ??????????????
?????? ? ????????????? ??????? ?? ??????? ???????? ????????????????? ??? ?
????????????; ????????? ??????????????????? ??????????????????? ????????????
????????????????? ???.
????????????????? ?????
??????????? ?????? 10 ? ????????? ? ???????? ?????????? ????? ? ??????? ???? ?
????????? ??????? ??? ???????????? ?? 960
?? 1000?? (? ??????????? ?? ???????? ??)
? ??????? 20 ???. ? ?????????? ??????????
?????????? ????????? ???????? ??????????
(??????? ? ????????? ????????????? ?????????, ??????? ????????? ???????????,
?????????? ? ????? ?? ??????? ??? ?????????? ?????? ? ?????). ?????????? ???????????
? ???? ????????? ?? ????????? 8 °C /??? ??
????????????? ?????????? 560, 610 ? 710 °C,
??????????? ??? ???? ???????????? ? ??????? 30 ???, ????? ????????? ?? ???????.
??? ??????? ??? NaCaAlF6 ? Na2Ca3Al2F14
? ???????? ???????? ??????????? ????? AlF3,
NaF, CaF2 ???????????? «?.?.». ?????? ????????? ? ???????? ?????????? ????? ? ??????? ???? ?? ???????? ???????????, ??????
? ??????????????? ????????????????? ????????????. ???? NaCaAlF6 ???? ???????? ??? 720 °C, ????? ??????? ? 1 ???. ????
Na2Ca3Al2F14 ???????? ??? 560 °C , ????? ??????? ? 30 ?????.
???????????? ?? ???????????? ????????? ???????? ??????????? ? ???????? ?????????? ????? ? ??????? ???? ? ?????????
??????? ??? ???????????? 560, 610 ? 710 °C ?
??????? 30 ???. ????? ??????? ?????????? ??
5 ?? 10 ?.
?? ???? ??????? ?????????? ????????
?????? ????? ? ????????? ± 0,001?.
?????? ????????????? ?????????? ???????? ??????????? ?? ????????????? X?Pert
Pro (PANalitical), ????????????? ??????????
PIXel ? ?????????? ??????????????, ? ?????????????? CuK?-?????????, ? ?????????
?? 10? ?? 80? ? ????? 0,026? ?? 2?, ? ??????
???????? ???????????? 12 ???. ??????? ????????? ??????? ?????? ??????? ? ??????
????????? 27 ??.
# 262 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
??????????????????? ??????????????????? ???????????? ???? ????????? ?? ????????????? X?Pert Pro (PANalitical) ? ??????????????????? ??????? N?K1200N «Anton
Paar» ? ???????.
?????????? ? ??????????
?? ???. 1 ??????????? ??????????? ???????? ??????? NaF-CaF2-AlF3 [6] ? ???????????? ??????? ???????? «??????? ????????????»,
? ??????? ???? ????????? ????????????, ?
???????? ????????????????? ???, ????????????? ? ??????????? ?????? ????????????.
CaF2
0,0
1,0
0,8
0,2
0,6
0,4
Na2 Ca3 Al2 F14
0,4
0,6
NaCaAlF6
0,2
0,8
0,0
1,0
0,0
NaF
0,2
0,4
Na3 AlF6
0,6
Na5Al3F14
0,8
NaAlF4
1,0
AlF3
???.
1.
???????????
????????
???????
NaF-CaF2-AlF3. ???????? ????????? ????????
???, ????????????? ? ???????????. ???????
???????? «??????? ????????????», ? ???????
????????? ????????????, ???????? ??????
????? ?????????? [7, 8], ??? ????????
?????????? ?????? ?? ????????????? ??????? ????? ?????? NaCaAlF6 ? Na2Ca3Al2F14.
??????? ?????????? ???? ?????? NaCaAlF6,
?????? ???????? ????? ??????? ?? ??????????. ???????????? ?? ?????????? ? ??????? ?????????? (?? ???????, ??????????
???????? ? ????????? ? ?????????? ? ????)
????????? ? ?????????, ?????????????? ?
???? ????????? ???????? ???????? ? ??????-
??? ??????????? ??????????. ??????????????????? ?????? ????????? ???????, ???
????????????? ????????? ???????? ???????
??? ????????? ???????? ?????????????? ??
??????????. ??????????? ????????? ????:
Na3AlF6, Na5Al3F14, NaCaAlF6, Na2Ca3Al2F14 ?
CaF2. ???????? ?????????? ????????? ??????? ?? ?????????????? ????????? ??? ???????. ? ??????????? ???????? ?????????? ????? ???????? ????????? ???????? ?? 10 %.
?????????????? ?????? ??? ?????????? ?????????????. ??????? ????????????? ? ????
???? ???: NaCaAlF6, Na2Ca3Al2F14 ? CaF2. ????
NaCaAlF6 ???????????? ? ???????? ? ??>2,6,
? ???? Na2Ca3Al2F14 ? ? ???????? ? ??<2,3.
?????????? ?????????????? ??????? ?
????, ?????????? ????? ??? ????? ?? ?????????? 710, 610, 560 °C , ? ?????????? ????????
? ??????? ???????? ???????. ???, ????? ???
710 °C ???????? ? ?????????????? ??????????????? NaCaAlF6. ??? ?????? ??? ???????????? 610 ? 560 °C ? ??????? ????????????
??????????????? Na2Ca3Al2F14.
??? ?????????????? ??????????? ?? ??????? ??????? ??????????????? ? ???? ????? NaCaAlF6, Na2Ca3Al2F14, ? ?????????????
?????? ???? (?????? ?????????????? ???. 2).
??? ?????????????? ??????????? ? ???? ? ??????? ??? 560 °C ??????? ??????????????? ?
???? Na2Ca3Al2F14, ???? NaCaAlF6 ? ?? ?????????????? (??????? ?????????????? ??? 2).
??? ?????????????? ??????????? ? ???? ? ??????? ??? 710 °C ??????? ??????????????? ?
???? NaCaAlF6, ???? Na2Ca3Al2F14 ? ?? ?????????????? (??????? ?????????????? ??? 2).
???? Na3AlF6, Na5Al3F14 ???????? ??????????? ??? ?????????.
????????? ?????????? ??????? ????????? ? ??????? ?????????, ???????? ????????? ?????????, ?????????? ? ???????????
????? ????, ????? ???? ?????? ??? ??????????? ????? 610 °C :
# 263 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
I, c o u n
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
7 000
N a 5A l 3 F 1 4
6 000
5 000
N a 2 C a 3 A l 2 F 14
N a 3 A lF 6
N a C a A lF 6
4 000
3 000
o
w ith fu r n a c e 7 1 0 C
2 000
o
w ith f u rn a c e 5 6 0 C
1 000
o n a ir
0
22
24
26
28
30
32
34
2 T h e ta , d e g .
???. 2. ?????????????? ??????????? (?? - 1,9, Al2O3 ? 2 ????.%, CaF2 ? 8 ????.%), ?????????????
????????? ???????? ?????????? (?? ???????, ? ???? ?? 560 °C , ? ???? ?? 710 °C). ???????? ???????????
?????, ????????? ??????? ????????????? ????????? ?????????? ????
3NaCaAlF6 ? Na2Ca3Al2F14 + NaAlF4.
(1)
?????????? NaAlF4 ????? ??????????? ?
?????????? [1, 6, 9-12]. ?? ?????? ??????? [9],
NaAlF4 ?????????? ?? ??????????????? ??????? ??? 710 °C ? ??????????? ??? ??? 680 °C
?? ??????? NaAlF4 (?) ? 1/5 Na5Al3F14 (?) + 2/5
AlF3 (?). ???? ?? ???? ???????? ?????? ????????????? ??????????? NaAlF4. ??? ?? ????? ????????, ??? ??? ?????????? ??? ??????????, ?? ??????? ??? ???????????, ?????
????????????????? ? ??????? ????????????
???????, ????????:
Na3AlF6 + 2NaAlF4 ? Na5Al3F14.
(2)
??? ?????????? ???????????? ??????????? ??????????? ???? ?????????????
???? NaCaAlF6 ? Na 2Ca 3Al 2F14. ??????? ??????? ????????? ? ????????????????? ?????.
? ???????? ??????? ?????????? CaF2 , ?????
???? ?????????? ????????? ??????????
??????? ? ????????. ????? ??? 610 °C ??????? NaCaAlF6 ???????????? ?????????
????????????? ? ??? ??????? ? ?????????? Na 2Ca 3Al 2F14. ?????????????????? ???????????, ??? ?????????? ???? Na 2Ca 3Al 2F14,
?????????? ??????? ? ???????? ??????
?????????????, ??????? ? ??????? ????????????? ??????? (???. 3). ??? ????????? ??????????, ??? ??????? NaCaAlF6 ?
Na 2Ca 3Al 2F14 ?????????????? ???????????
??????? ???????.
?????????? ??????? 2NaCaAlF6 + CaF2
? Na2Ca3Al2F14 ??????????? ?? ??????????? ??? ?????? ???????? ??????, ?????????
??????? ??????????? ????????????? ?????
???? Na2Ca3Al2F14 ?? ????????????? ???????
???????? ????????????? ????? ??F2.
????? ?????? ??? 610 °C (?????? ?????????????? ???. 3) ?????????? ??????????
?????????? ???? NaCaAlF6. ????????? ????? ???? Na2Ca3Al2F14. ??????????? ?????????? Na5Al3F14. ??????? ????? ???? Na3AlF6.
??????????? ?????????? CaF2.
???????????? ?? ???????????? ??????????? ??????????? ???? Na2Ca3Al2F14 ????????, ??? ??? ???????????? ??? 560 °C ? ???????
20 ????? ??????? ???? Na2Ca3Al2F14,????????
??? ?????????. ??? ?????????? ?? 610 °C ?
???? ???? Na2Ca3Al2F14 ???????????? ???????:
????????????? ?????????? CaF2 ? ????????.
# 264 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
R e l.in t en s it y
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
N a C aA lF 6
N a 2C a 3 A l 2 F 14
N a 5A l 3F 1 4
N a 3A lF 6
C aF2
o
N a C aA l F 6 - 2 5 C
o
N a C a A lF 6 - 6 1 0 C , 2 h .
22
24
26
28
30
32
2 T he ta , d e g.
???. 3. ?????????????? ??????? NaCaAlF6 ????????? ? ????? ?????? ??? 610 °C ? ??????? 2 ?????.
???????? ??????????? ?????, ????????? ??????? ????????????? ????????? ?????????? ????
????? ?????? ??? ??????????? 710 °C ?????????? ?????? ?????? ????. ? ??????? ??????????? ???????, ??????? ? ?-Al2O3. ???????
R e l.in ten s ity
?????????? ????? ????????? ????????? ????????????? AlF3 ??? NaAlF4. (???. 4).
????? ?????? ??? 610 °C ??????????
?????????? ?????????? Na2Ca3Al2F14. ??????? ????? ???? Na5Al3F14, ??????????? ?????????? CaF2, ????????? ????? ???? Na3AlF6
(??????? ?????????????? ???. 4). ????? ?????? ??? 710 °C ? ??????? 16 ????? ?????????
??????? ????? ???? Na2Ca3Al2F14, ??????????? ?????????? Na3AlF6, ????????? ?????
???? Al2O3.
???????????? ????????? ????? ???????
?????????? ?????????:
Na2Ca3Al2F14 ? 2NaAlF4 + 3CaF2;
(4)
C aF 2
N a 2C a 3A l 2F 1 4
N a 5 A l 3 F 14
N a 3 A lF 6
A l 2O 3
o
N a 2 C a 3 A l 2 F 14 -56 5 C , 2 0h .
o
N a 2 C a 3 A l 2 F 14 -610 C , 17h.
o
N a 2 C a 3 A l 2 F 14 -7 10 C , 16 h.
22
24
26
28
30
32
34
2 Theta, deg.
???. 4. ?????????????? ??????? Na2Ca3Al2F14 ????? ?????? ??? 565 °C ? ??????? 20 ?????, ????? ??????
??? 610 °C ? ??????? 17 ????? ? ????? ?????? ??? 710 °C ? ??????? 16 ?????. ???????? ???????????
?????, ????????? ??????? ????????????? ????????? ?????????? ????
# 265 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
3NaAlF4 3? Na3AlF6 + 2AlF3;
(5)
2AlF3 + 3(H2O) ? Al2O3 + 6HF;
(6)
???????? ????????? ??????? ???????
Na2Ca3Al2F14 ? 2NaCaAlF6 + CaF2 ?? ?????????????.
???? ????????? ???????????????????
??????????????????? ?????? ???? NaCaAlF6.
??????? ???? NaCaAlF6 ????????? ? ??????? ?? 600 °C ? ?????????????? ????????
??? 100, 300, 400, 500, 550, 570, 600 °C . ??
400 °C ???? NaCaAlF6 ?????????? ?????????
??????????? ????????? ??? ?????????? ???????? ???????. ??? 500 °C (???. 5) ?????????? ??????? ??????? NaCaAlF6 ? ????????????
Na2Ca3Al2F14 ?? ????????? (1). ??????, ???????, AlF3, NaAlF4 ????? ????????? ?????????? ?? ????, ??? ??????? ? ??????? ?????????? ????????? ??????? ? ???????? ???????.
??? 500 °C ????????? ?????? ???????????
NaCaAlF6 ? Na2Ca3Al2F14. ????????? ???? ??-
R e l. in te ts ity
??? ????????? ?? Na3AlF6 ? CaF2
?? ??????????????, ?????? ??? 500 °C ,
?????, ??? ????????? ????????? ??????????? ????????? ???? NaCaAlF6; ?????????
????? ???? Na2Ca3Al2F14 (??????? ????????-
??????). ????? ???????? ? ??????? ???? ???
500 °C ??????? ????? ???? NaCaAlF6, ??????????? ?????????? ??? Na2Ca3Al2F14, CaF2 ?
Na3AlF6
?? ??????????? ??????????? ????????????? ????? ??????? ????????? ??????????. ???????????? ? ??????? NaF-CaF2-AlF3
?????????? ???????? ????????? ? ???????????? ???????? ??????????. Na2Ca3Al2F14
???????? ?????, ??????????? ? ??????????
????????? ???? 610 °C . ??????? ????????????????? ???????????? ???????????????
???? NaCaAlF6 ????????? ? ?????????????
????????? 640-740 °C . ?????????? ? ???????? ??????????? ???????????? ???? ????????? ??? ???????? ?????????? ??????????????
???????? ??????????, ??? ??????? NaCaAlF6
?? ????????? ????????? ? Na2Ca3Al2F14 ? ??????????? ??? ?????? ???????????? ? ?????????????? ?????????. ??? ??????????????
????????? ?????????? ???????????????
????????? ? «????????» ?????????????
??????? ?????? ????. ??????? ??????????
???????? ? ???????? ? ??????? ??????????????????? ???? NaCaAlF6. ????????????????
????????????? ???????????????? ???????-
N a C a A lF 6
o
N a C a A lF 6 - 2 5 C
N a2C a3A l2 F1 4
o
N a C a A lF 6 - 5 0 0 C
N a 3 A lF 6
C aF 2
o
N a C a A lF 6 - 5 0 0 C , 1 h .
22
24
26
28
30
32
2 T h e ta , d e g .
???. 5. ?????????????? ??????? NaCaAlF6, ?????? ? ??????????????????? ?????? ??? 25 °C , 500 °C,
??? 500 °C - 1 ???. ???????? ??????????? ?????, ????????? ??????? ????????????? ?????????
?????????? ????
# 266 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
??????? Na2Ca3Al2F14 ? ???????????? ???????? ?????? ???????????? ??????? ?????
?????? ???????????? ???????? ??? ????
???????????? ? ??????????????? Na2Ca3Al2F14
??????????????? ?? ????????. ???????????
NaCaAlF6 ? Na2Ca3Al2F14 ?????????? ?? ??????? ??????? ? ?????????? NaAlF4 ? ???????
?????????? 560-610 °C . ??? ?????????? ????
610 °C , ???? Na2Ca3Al2F14 ??????????? ?? CaF2
? NaAlF4, ??? ???? NaAlF4, ? ???????? ?????,
??????????? ?? ??????? ? ????????. ????????? ??????????? ????????? ?????????????
????????? ????????? ?????? ?????????? ?
??????????????? ????????? (???????) ? ????????????? ????????? 560-600 °C , ? ???????
?????????? ???????? ?????? ??????? ????
NaCaAlF6 ? Na2Ca3Al2F14 ??? ????????? ???????? ?????????? ??? ????????? ??????????????????? ??????? ??????? ????????????? ???????????.
?????? ??????????
1.
Grjotheim K., Krohn C., Malinovsky M., Matiasovsky K. Aluminium Electrolysis. Fundamentals
of the Hall-Heroult Process. 2nd Edition. Aluminum-Verlag. Dusseldorf. 1982.
2.
???????? ?.?., ???? ?.?., ????????? ?.?. ? ??. ?????????? ?????????? ?? ???????
????????. ???????????? ????????. ?.: ???????????, 1971. - C. 560.
Pfundt H., Zimmermann N. The Quasi Binary System NaF-CaAlF5, an Investigation from the
Ternary Sistem NaF-AlF3-CaF2. Erzmetall. 1972. Bd. 25. N. 11. S. 564-567.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
Craig D.F., Brawn J.Jr. Phase equilibria in the System CaF2-AlF3-Na3AlF6-Al2O3. American Cer.
Soc. 1980. N. 63. P. 254.
Baggio S., Massiff G. Calcium Cryolites. J. Appl. Cristallogr. 1985. P. 537.
????????? ?.?., ???????? ?.?., ??????????? ?.?. ????? ?????? ?? ??????? ??????????
????????? ?????? NaF-AlF3-CaF2 ? NaF-AlF3-MgF2 // ??????? ???????. - 1985. - N. 8 - C. 66-71.
Lorents Petter Lossius, Helge Hoie, Hanne Hoel Pedersen, Trygve Foosnaes. Analysis of excess
AlF3 ? Harmonization in Hydro Aluminium. Light Metals. 2000. P. 265-270.
????? ?.?., ?????? ?.?., ???????? ?.?. ??????????? ??????? ??? ??????? ???????????
? ??????????? ????????????: ??????? ?????????? ??????????? «???????? ??????».
??????????, 2001.- ?. 213-219.
Ginsberg H., Wefers K. Erzmetall. 1967. Bd. 25. N. 11. S. 156.
Bruno M., Herstad O., Holm J.L. Stability and structure of sodium tetrafluoroaluminate, NaAlF4.
Acta Chemica Scandinavica. 1998. V. 52. P. 1399-1401.
Holm J.L. The lattice energy and the thermochemical properties of the compound NaAlF4, sodium
tetrafluoroaluminate. Acta Chemica Scandinavica. 1973. V. 27. P. 1410.
Bjшrseth O., Herstad O., Holm J.L. On the physical and thermodinamic stability of solid sodium
tetrafluoroaluminate. Acta Chemica Scandinavica. 1986. V. A40. P. 566.
Le Bail A., Hemond Ribaud A., Courbion G. Structure of ?-NaCaAlF6 determinated ab initio from
conventional powder diffraction data. Eur. J. Solid State Inorg. Cem. 1998. T. 35. P. 265-272.
# 267 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ???????, ????? ?. ??????? ??????????? ?????????????? ????????????????? ????
Specific Features of the Calcium-containing Phase Crystallization
in Electrolyte of Aluminium Melting Production
Julia N. Zaytsevaa*, Elena N. Lyndinab,
Igor S. Yakimovb, Sergey D. Kirika,b
a
Institute of Chemistry and Chemical Technology,
Siberian Branch of the Russian Academy of Sciences,
42 Karl Marks st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
The specific features of calcium?containing phases crystalization have been investigated in case
of industrial electrolyte sampling for the purposes of composition control. The influence of cooling
rate on the crystalization has been studied. It was found that the phase NaCaAlF6 was stable in the
temperature range of 640-740 °C . Transformation of NaCaAlF6 into Na2Ca3Al2F14 goes with isolation
of NaAlF4 at 560-610 °C . High temperature XRD investigation of individual samples of NaCaAlF6
and Na2Ca3Al2F14 has been carried out. In the practice the decomposition of NaCaAlF6 does not fully
complete at a sampletaking procedure that induces impediments in the content determination by XRD
approach. Recommendations on an optimal sampling for XRD control procedure were formulated.
Keywords: aluminium melting production, industrial electrolites, phase-equilibria diagram in the
system NaF-AlF3-CaF2; ternary fluorides containing calcium-sodium-aluminium; XRD
# 268 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 269-276
~~~
??? 543.32/34
???????? ?????????? Fe(III) ??????????? ??????????
Elodea canadensis ?????????????? ????????:
?????? ?????????????, ?????????? ? ?????????????????
????? ?. ??????????*, ????? ?. ?????????
?
???????? ????????? ?? ???,
?????????????, ??????????, 660036 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
???????? ?????????????????, ?????? ????????????? ? ?????????? ??????? ??????????
Fe(III) ????? ?? ??????????? ?????? ???????? ?.?????? Elodea Canadensis. ???????????, ???
???????????? ?????????? ?????????? ?????????? ??????? ?? ?????? ???? ??????????? ?
??????? ?????? ????? ????? ?????? ????????????, Fe(III) ? ? 2,5 ?? 0,3 ??/?. ????????????
??????????? ?????????? Cl- (c 1,7 ?? 5 ??/?) ? SO42- (? 9,6 ?? 11,4 ??/?) ? ?????? ???? ???????.
???????????? ???????? ???????????? ?????????? ??? Fe(III) ? ??????????? ?????????
???????? ?? = 2,8 ?/?? ?????? ????. ????????, ??? ? ??????? ????? ??????? ????????????
???????????? ??????? ?????????? ??? ????? ???????????? ??????? (???????? ? ????), ???
? ????? ?????????? ??????? ???????? ?????? (???????-????????????? ???? ? ????????
????????).
???????? ?????: ??????????, Fe(III), ??????????, ?????? ?????????????, ?????????????????.
????????
???????? ?????????? ??????????? ???????? (Fe, Cu, Zn ? ??.), ? ????? ????????????? ? ????????? ??????-?????????? ??????
???????? ???????????? ???????. ??? ??????????? ? ?????????? ????? ??????? ?????????????? ? ?????? ? ?????? ??????????,
???????????? ? ????????????? ? ?????????
?????, ????????? ? ???? ?????????? ??????
? ????????????? ???????? ? ? ??????? ???????????? ?????? ?????????. ? ??????????
????????????? ??????, ????????? ???????
*
1
???????, ? ???????? ????????????????? ????????????? ???????? ??????? ??????? ?????????? ? ????????? ??????????? ??????? ?
?????????? ? ????????? ????????? ?????
?????????? [1].
?????????? ??????? ? ????? ?????? ??????????, ??????????? ? ??????????? ????????, ? ??? ????? ? ?????????????, ???????????? ?????? ????????. ????????, ??? ?
??????? ?????????????? ??????? ??????????? ???????????? ??????? ????????. ???
???? ? ?????? ? ????? ????? ???????? ?????-
Corresponding author E-mail address: l-bondareva@mail.ru
© Siberian Federal University. All rights reserved
# 269 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
?? ????? ????????? ? ???????????? ???? ???
????? ?????? ? ?????? ?? ?????? ?????, ???
? ????? ???????? ??????? ?? ?????? ????????? [1, 2].
???????? ?????????? ??? ???????? ??????? ????????? ???????? ?? ?????????????
???????? ????? ???????????? ??????????
???????? ????????? ????????????, ?????????? ? ???????????? ???????? ? ??????? ??????????, ???????????? ??? ???? ??? ?????
???????. Elodea canadensis (?????? ?????????,
????? ? ?????? ? ??????) ????????? ???????????? ? ???????????? ????????, ? ??? ????? ?
? ?.??????. ??????????? ????? ????????????
????????? ? ????????? ??? ????????? ????????????? ???????? ???????? ???????????
???????? ? ???, ??? ???????? ??????????
????????????? ? ??????? ???????? ???? ??
???????????????? ???????? ????????. ?????????????, ?????? ???????? ??????? ??????
??? ???????????? ?????????? ??????????,
????????????? ? ??. ????? ???? ?????????
?????? ? ??????? ?? ?????????? ?????????
??????????? ?????????????, ????? ??? 241Am
[3], U [4] ? ??????? ???????? [5, 6]. ?????? ?
???? ??????? ???????????? ???????? ????????? ?????????, ??????????? ? ?????? ????
????????? ???????.
? ????????? ????? ??? ??????? ?????
????????????? ??????? ???????????? ? ???????? ?????????? ?????????? ?????????????
??????? ???????? ????? ???????????? ??????????. ???, ????????, ??? ??????????? ???????? ???????? ?????? ????????????? ?????
??????????????????????? ?????????????? ?
?????????? ??????????? ??? ???????? ??????? ??? ????????????? ?????? ?????????.
??? ??????????? ??????? ?????????? ?????? ?????? ????????????? ? ?????????? ?
???-???????????? ???????????. ??????????,
?????????? ? ?????????????? ?????????
????????????? ???????, ????????? ??????-
??? ??????? ????????, ??????????? ? ?????????? ?????.
????? ?????? ?????? ??????? ???????? ?????????? Fe(III) ????? ?? ??????????? ????? ?????? ???????? ?.??????
Elodea Canadensis Mush ???????? ??????
?????????????, ?????????? ? ?????????????????.
????????????????? ?????
1. ??????? ????????????
? ???????? ??????? ???????????? ???
?????? ???????? ???????????????? ??? ???????????? ????????? Elodea Canadensis
Mush (?????? ?????????). ????? ??????
???????? ???? ??????? ?? ?????? ? ?????????????. ??? ?????????? ???????????? ???? ???????? ??????? ????? ??????
?????? 4-5 ??, ????????? ? ???????????
?????. ???????? ??????-??????????? ?
??????-?????????????
?????????????
?????????? ?????????? ????????? ? ???????????? ????????? (?/?? ?????? ????): K ? 20,
Na ? 13,5, Ca ? 20, Mg ? 3,1, Fe ? 2,1, Mn ? 1,45,
Zn ? 0,27, Al ? 1,9, Sr ? 0,39, Si ? 13,8, Ni ? 0,02,
Cu ? 0,03, Co ? 0,004, Pb ? 0,003. ????? ????,
? ????????? ??????????? ?? 0,26 ????. % S ?
0,69 ????. % P.
??? ??????????? ??????? ????????????? ??????????? ???? ?. ?????? ????
???????? ???? ?? ??????? ?? ?. ???????????. ????? ?????? ???? ???? ????????????? ????? ?????? «????????» (??????) ?
????????? ??? 0,2 ???. ?????????? ????????? ? ???????????? ????????????? ????
(??/?): K ? 0,7, Na ? 2,3, Ca ? 19,6, Mg ? 3,2,
Fe ? 0,025, Zn ? 0,014, Ni ? 0,005, Cu ? 0,002,
Mn ? 0,003, Al ? 0,16, Sr ? 0,25, Si ? 1,61,
S ? 2,56, P ? 0,13. ?????????? ??????? (??/?):
Cl- ? 1,72, NO3- ? 1,48, SO 42- ? 9,63, HCO3- ? 75.
?????????? ???????????????? ????????????? ???????? ???? ? 1,7 ??/?.
# 270 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
2. ??????????
??? ??????????? ????????? ??????? ? ?????? ???????????? ??????????? «????-3006»
? ??????????????????? ?????????? [7]. ????????? ??, ????????????-??????????????????
?????????? ? ??????????? ?????????? ????? ????????? ?? ???????? ?Radelkis? (???????) ? ???????????????? ??????????? ???
??-?????? ? ??? ????????? ?????????????????????????????? ??????????. ??? ??????????? ?????????? ????? K+, NH4+, NO3-,
Cl- ???????????? ???-??????????? ?????????
????? ???????? (??????). ??????????? ?????????? Fe(III) ? ?????? ????????? ????????? ? ?????????????? ????????????????
C?-46 (??????).
3. ???????? ????????????
? ??????? ? ????????????? ?????
(V= 700 ??) ??????? ??????? ???? Fe(NO3)3, ?????????? Fe(III) ? ??????? ????????? 1,75 ??
(??? 2.5 ??/?). ????? ????????? ?? ?? 7,0 ????????? NaOH (0,1 ?) ? ??????? ?????????
?????????????? ????????. ????? ????? ???????? ? ?????? ????? ???? ~6 ?. ?????????????? ??????? (4 ??.) ? ?????????? ????????? ??????? ? ???????? ? ?????????????
??????? ? ?????????????? ?????????????
??????? (~18 °?) ? ??????????????? ???????????? (16 ? ? ????, 8 ? ? ???????).
????? ???????????? ?????????? ??????? ???????? ????? ????, ? ??????? ????????? ??????????? ?????????? ?????????????
??????. ??? ???????? ????????????? ??????
????? ???????????? ??????????? ???????
? ???????? ??????? ?? ?????? ??????? ???????????? ???????. ??????, ???????????? ?
???????, ???????? ?? ?????? ???? ????????????? ????? ???????? ?????? «????? ?????».
?????????? ???????? ?????? ?? ??? ??????
?????, ???? ????? ?????????? ????? ?????????????? ????? ? ??- ????? (??-17), ??????
? ????? ??????????????? ????? ? ?+ ?????
(??-2). ? ??????? ????? ?????????? ?????
?????????? ????????????? ??????. ?????????? ??????, ???????????????? ?? ???????????? ??????, ?????????? ? ???????, ?????
??????????? ? ??????? ????????????????
?????????? (NaOH ??? HNO3). ??????, ?????????? ????? ???????????? ?????? ????,
?????????? ?? ??????? ??????????? ????????? 0,1 ? HCl. ? ?????????? ???????? ?????
?????????? ?????????? ??????.
??? ???????? ????????????? ?????? ??
??????????? ???????? ???????? ???????????? ????? ????????????????? ??????????? ????????????????, ?????????????? ???
???????? ? ????????? ? ?????? [3]. ?????
????????????????? ??????????? ???????????????? ???????? ??????????? ???????????
???????? ? ?????????? ?????????, ??????????????? ????????? ?????? ????????:
I ? ???????? ??????? ??? ????????? ????
(????????? 1 ? ????????? CH3COONH4 ? ??????? 24 ? ??? ?????????????), II ? ????????????? ??????? ??? ??????????? ??????????? ?? ??????????? ???????? (?????????
0.1 ? ????????? H2SO4 ? ??????? 20 ??? ???
?????????????), III ? ???????????? ????????
??????????????? ???????? ????????, ?????????? ? ????????? ???????? ? ??????????????? ???????? (??????????? ? ????????
H2O2 ? ??????????? HNO3) ? IV ? ??????????? ???????, ????????? ??????? ??????? ??
??????????, ? ???????? ?????? ??????? ????????? 0,1 ? HCl. ???????, ?????????? ???
??????????? ????????????? ????????, ????????? ?? ??????? ????? ??? ???????? ??????
H2O2 ? ?????????????? ?????????? ???????????? ? ?????????????????????? ??????????? ??????????????????? ?????????.
??????????? ????? ? ??????????????? ?????? ???? ????????? ? ?????????????? ?????? ?????? ????????????? ? ??-
# 271 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
????????????? ??????? ? ???????????
???-???????????? ???????????. ???????
??????????? ??????????? ??????? ? ????????????? ??????????? ????????? ??? ??????????? ???????????? ??????? ? ??????
[7]. ???????????? ????????????? ????????????? ???????? ? ???? ?????????? ???????
???????????? ????????? [7], ????????????
??????????????? ???????? (CO32-, HCO3-) ? ??????????? ? ?????????????? ?????????????
? ???????????? ???????? ? ???????? ??????????? [8]. ??????????? ?????????? Fe(III) ??
???? ????????? ????????? ?????????????????????? ??????? ? ???? ?????????? ???-
??????? Fe(III) ? 1,10-????????????? [9] ? ?
SCN??????? [8].
?????????? ????????, ??????????????
? ?????????????, ????? ????????????? «?????? ??? ???????» ??? «????? ??????». ???
????????????? ????????? ????? ???????????? ?????????????????? ????.
?????????? ? ?? ??????????
???? ??? ???????? ??????????? ? ????????? ? ??????? Fe(III). ?? ???. 1?, ? ?????????
???????? ????????? ????????????: ?????? ?
????? K+, NH4+ (???.1 ?), Cl-, SO42- (???.1 ?), ?
?????? ???? ????????????????? ???????.
4
1
???????????? ??/?
2
3
3
2
1
0
?
0
5
10
15
20
????????????, ?????
25
30
35
14
????????????, ??/?
12
10
1
8
2
6
4
2
0
?
0
5
10
15
20
25
30
35
????????????, ?????
???. 1. ???????? ????????? ???????????? ?????? (III) ? ?????????? ????? K+, NH4+, Cl-, SO42- ? ??????
???? ????????????????? ??????? ?????? ? ???? ?.??????
?) 1 ? Fe(III), 2 ? K+, 3 ? NH4+
?) 1- Cl-, 2 ? SO42# 272 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
???? ???????????, ??? ???????? ??????????? ????? ?????? ????????? ? ???????
?????? 4 ? (? 2,5 ?? 0,3 ??/?). ????????????
??????????? ?????????? ?????????? Cl- (c 1,7
?? 5 ??/?) ? SO42- (? 9,6 ?? 11,4 ??/?) ? ??????
???? ???????. ?? ??? ??????, ????? ????????? ?????????? ??????? ????? ???? ???????
?????????. ????, ? ??????? ???? ???????? ????????????????? ????????, ??????????
?? ????, ? ??????? ??? ???????? ???????. ??
???? ????? ????? ????????? ????????????????? ??????? ? ??????????? ???????? ? ????
???????? ?? ???????????? ??????????. ? ???
??? ?????????? ????????? ???? ???????????????, ?? ??? ???????? ?????????? ??????????? ?? ????? ?????? ????????????. ? ?????? ???????, ??????????? ????? ??????????
Fe(III) ?? ?????? ????? ??????? ??????????
??????????, ???????????? ? ????????????????? ???????, ?????? ???, ????????, ???????? Fe(III) ?? ???? ???????? ? ??????????? ???????? ? ??????????? ?????????? ??
??????? ??????? ??????? ? ???????.
? ????????? ?? 20 ? ?? 24 ????? ???????????? ????????? ???????????? ??????, ???
?? ??? ? ???????????? ???????????? ??????? ? ?????? ????, ???? ???????????????.
??? ???? ~95 % ?? ?????? ?????????? ??????100
??????? ? ???? ?????? ?????????? ? ???? ???????? ? ???? ~ 3 % ? ? ???? ??????????? ??????????. ???????????? ?????????? Fe(III) ?
????????? ? ???? ?????? ????????? 2,8 ?/?? ?????? ????. ?????? ?? 21-? ????? ? ?????? ????
???? ?????????? ?????????? ????????????
Fe. ????? ? ??????? ??????????? ???????????
??????????? ??????????? ?????? ?? ??? ???????. ????????, ???????????? ?????? ? ???
?????????????? ?????? ??????????? ???????, ????????? ???????? ??????? ?? ????????
????? ?????????????? ??????. ???? ??????????, ??? ? ???? ?????? ??????? Fe, ??????????? ? ???????????? ???? ?????????????? ?
???????? ???????? ~45 %, ? ??????? ? ~35 % ?
20 % ? ? ???? ??????????? ??????????. ???????? ?? ??????? ???????? ??????????? ? 7
?? ~9,5, ??? ?????? ???????? ????????, ??????????? ?? ??????????? ???????????????
???????? ? ?????? ?????????.
???? ???? ??????? ????????????? ?????????? ?????? ?? ??????????? ????????????????? ??????? (????, ???????? ????????,
?????? + ?????) ?? ??????, 7, 22 ? 33-? ?????
????? ?????? ????????????. ?????????? ????????? ?? ???. 2.
??? ????? ?? ?????????????? ???????????, ??? ?????? ????? 7 ????? ??????????
%
????
????????
80
??????+?????
60
40
20
0
1
7
?????
23
33
???. 2. ??????????? ????????????? ?????????? ?????? ?? ??????????? ????????????????? ???????
(????, ???????? ????????, ??????) ?? ???????
# 273 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
?????????????? ?????????? ?????? ? ?????
«???? + ??????» (2 % ?? ?????? ??????????
??????? ? ???????). ???, ????????, ???????
? ??? ????? ? ???, ??? ? ???? ?????? ????????????? ??????????? ?????????? ??????????????? ? ???? ????????, ??????? ???????? ?????????? ?? ???????????? ???????,
??????? ??????? ? ???????? ?? ???? ?????
?????????? ? ??????? ???????. ??? ????????? ??????????? ?? ????????, ?.?. ????? 22
????? ?????????? Fe ? ?????? ??????????
13 %, ????? 33 ????? ? 25 %. ? ?????? ???????, ?????????? ??????? ? ???????? ??????????? ??????????? ? ? 88 ?? 46 %. ?????
???? ???? ??????????, ??? ? 21 ?? 33 ?????
??????? ????????????? ?????????? ?????
K+ (? 0,7 ?? 1,3 ??/?) ? NH4+ (? 1,6 ?? 2,9 ??/?)
(???. 1). ??? ??????????????? ? ?????????,
????????? ? ??????????? ????????? ??????? ? ??????????? ?????????? ?????????
????????. ?????????????, ???????? ?????????? ?????????? ?????? ? ?????? ???? ????? ???? ?????????? ????????? ???????
? ?????????? ???????????? ?????????
????????, ?????????? ????? ???????????
??????. ????? ????, ?? ??? ???????? ?????????? ????????? ????????. ?? ???? ?????
??????????? ???? ?????? ? ????????, ? ??
80
?? ????? ????????????? ?????????? Fe(III)
? ?????? ? ?????? ?? ?????? ????????????????? ???????.
??? ???????????? ????????????? ??????
?? ????????? ?????? ???????? ?????? ????
???? ????????? ???????????????? ?????????? ???????????????? ???????? ????????
?? ?????. ?????????? ???????????????? ?????????? ?? ???. 3.
??? ????? ?? ?????????????? ???????????, ? ??????? ????? ??????? ??????????
???????????? ?????????? ????????????????? ??????? ?? ???????? ???????????
????????. ???? ????????, ??? ??????????
????????, ?????????? ? ????? ????????
(??????? III+IV), ????????? ? ???????????
?? ?????????? Fe(III) ? ???????? (????????????) ???? (??????? I). ?? ??? ??????, ???
????? ???? ????????? ?????????. ??????
????????? ?? ???? ???? ? ??????????? ???????? ? ?????????? ????????? ????????????.
????? ???? ???? ?????? ???????????????
? ?????????????? ?? ??????????? ???????? ??????? (??????? II). ??? ??? ?????? ??
??????????? ???????? ????????? ?? ??????????????? ?????????????? ??????????
(?????????, ???????, ??????????), ???????
?? ?????? ?????? ????????? ? ????????,
%
I
II
III+IV
60
40
20
0
1
7
?????
23
33
???. 3. ?????????? ????????????????? ??????????? ???????????????? ???????? ???????? ??????
# 274 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
?? ???????? ???????? ???????????? ? ??????? ??????????????. ?????????? ????? ????????????? ???????-????????????? ????
(??????? I+II) ????? ??????????????? ???
????????? ?????????, ? ????????? ??????, ?
?????? ???????? ? ??????????? ?????????????? ?????? ????????.
??????
1. ? ????????? ??????? «?????? ? ????»
???????????? Fe(III) ?? ???? ???? ? ??????????? ???????? ????? ???? ?????? ?????????? ?????????? ? ??????????? ?????????? ???????, ??????????? ?? ???????????
??????????? ????????. ??? ???? ?????-
????? ????????? ??????? ??????? ??????
?????.
2. ? ??????????? ?? ???????????? ??????????? ???????????? ??????????? ????????????????? Fe(III), ??-??????, ????? ???????????? ????????????????? ??????? (????,
????????, ?????? ?? ??????? ? ??? ????????),
??-??????, ????? ?????????? ??????? ??????????????? ???????? (?????????????
???????-????????????? ???? ????????, ???????? ????????).
3. ?????????? Fe(III), ??????????? ? ????????, ??????? ?? ??? ?????????? ? ????????
? ????????????? ?????, ??????????? ?? ??????????? ????????.
?????? ????????? ??? ????????? ?????????? ????????? ?????? ???? ? 08-05-00137.
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
9.
??????? ?.?. ????????? ?????? ???????? ? ?????????? ???????????? ???????? ?????.
?.: ????????-?????, 2005. 224 ?.
Luoma, S.N. Bioavailability of trace metals to aquatic organisms ? A review. // The Science of the
Total Environment, 1983. V. 28, p. 1-22.
???????????? ?.?., ?????? ?.?., ????????? ?.?. ?????? ????????????? ?????? ????????-241 ??
???????? ?????? ???????? ???? ??????. ??????? ???????? ????, 2003. ?.392, ? 4. ?.560-563.
???????????? ?.?., ????????? ?.?., ???????? ?.?. ???????? ?????????? ?????????? ????????
????? ?? ??????? ?????? ?? ????? ?????? ???????? (Elodea canadensis) ???? ??????. ???????
??????. ?????: ???????????? ?????, ?????????????? ?????, 2005. ? 2. ?. 70-73.
James C.S., Eaton&K. Hardwick J.W. Competition between three submerged macrophytes,
Elodea canadensis Michx, Elodea nuttallii (Planch.), St John Lagarosiphon major (Ridl.) Moss.
Hydrobiologia, 1999. 415. P. 35-40.
Samecka?Cymernam A., Kempers A.J. Biomonitoring of water pollution with Elodea canadensis.
A case study of three small Polish rivers with different levels of pollution. Water, Air, and Soil
Pollution, 2003. 145. P.139?153.
????????? ?.?., ???????? ?.?., ???????????? ?.?. ???????? ??????? ????????? ???????
?? ???????? ??????????-????????? ? ??????? ?????? ????????? ? ???? ???? ??????
???????? ?????????????? ?????? ????????????? ? ?????-?????????????. ???, 2006.
?.61, ? 4. ?.388-392.
???????? ?.?. ??????????? ?? ??????????? ??????????? ???????? ???? ????????
????????. ???.: ???????+, 2004.
Harris D.C. Quantitative Chemical Analysis 6th ed. Rapid Test. Handbook. 2003. P. 453, 461-476,
707-709.
# 275 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????? ?. ?????????, ????? ?. ????????. ???????? ?????????? Fe(III) ??????????? ???????????
The Study of Accumulation Fe(III) to Elodea canadensis
by Analytical Methods: Ion Chromatography, Ion-measurement
and Spectrophotometry
Lidiay G. Bondarevaa and Olga P. Kalyakinab
a
Institute of Biophysics SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
We studied of accumulation of Fe(III) to components of Elodea canadensis by ion chromatography,
ion-measurement and spectrophotometry methods. We determined that concentration Fe(III) was
decreased during first day from 2.5 to 0.3 mg/l. Concentrations of some anions were increased:
Cl- from 1.7 to 5 mg/l, SO42- from 9.6 to 11.4 mg/l. The maximum concentration factor was calculated,
CF = 2.8 g/kg dried wet. We determined that transportation of metal can be between components of
system and between parts of biomass (exchangeable ? adsorption layer ? biomass of plant).
Keywords: accumulation, Fe(III), ion-measurement, ion chromatography, spectrophotometry
# 276 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 277-285
~~~
??? 544.472.3
?????????????? ????????? ????????
? ????????? ???????? ? ??????????????
???????????? ?????????????? ??????????
??????? ?. ??????????a, ??????? ?. ???a,
????? ?. ???????? ?,?*, ???? ?. ??????a,
???????? ?. ????????? ?,?, ?????? ?. ??????????a ,
?????? ?. ??????????
a
???????? ???????? ????? ?.?. ????????? ?????????? ????????? ???,
??. ????????? ???????????, 5, ???????????, 630090 ??????
?
???????? ????? ? ?????????? ?????????? ?? ???,
?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
??????????? ??????? ??????????????? ????????? 35 % ????????? H2O2 ???????? ? ???
????????? ? ????? ????????? ?? ?????????. ??????? ????????? ? ?????? ????????: ???????????
????????, 60-80 ?? ? ?????????? ?????-???????????? ???????. ??????? ????????? ?????????
???????? ???????????? ? ??????? ?????????????? (90 %) ?? ???????? ??? 98 % ?????????
????????? ???????? ? ??????????? ??????????????????? ??????????? ????????????
[CH3(n-C8H17)3N]3{PO4[WO(O2)2]4}.
???????? ?????: ????????? ???????, ????????? ???????? ? ????????? ????????, ????????
????????, ???????????????????????????????? ?????????.
????????
? ????????? ????? ???? ?? ????????????? ??????????? ??? ????????????? ??????? ????????? ????????? ????????????
?????????? ??????? ? ??????????? ??????
?????????? ???????? ? ?????????????? ???????????????? ?????????????????????
????????????? ?? ?????? ??????????????????????????? [1-5]. ???????????? ? ???????? H 2O2 ? H 3PO 4 ? Na 2WO 4 ? H 3PW12O 40 ? H 2O2
*
1
???????????????? ?????????? ?????????,
? ???????? ???????? ? ???????? ????????? ???????? ????? {PO 4[WO(O2)2]4}3- [1,
4]. ?????????? ????????????? ??????????
???????? ? ???????????? ?????????? ???????? (Q +) ? ????????? ? ?????????????
????????? ? ??????????????????????????? ????????? ????????? ??????? ????????? ? ?????????? ???????? ? ???? ??????????????? ??????.
Corresponding author E-mail address: bnk@icct.ru
© Siberian Federal University. All rights reserved
# 277 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
????????????? ???????? ???????????????? ????????????? ?????? ?? ???????????????? ??? ?????????? ? ????????
????????????? ????????????? ?????????
????????? ??????????, ? ?????????, ???????????, ? ?????????? ??????? ? ????????????
????????????? ???????????. ? ????? ???????? ????????? ??????????? ????????? ???????, ??????? ?????????? ? ???????????? ??????????? (?? 30-40 % ???.) ?? ??????? ????
?????? (???????) [6].
? ?????? ?????? ??????? ???????????
?????????? ?????? ?????????? ???????? ?
?????????? ???????? ??? ????????? ???????? ? ??? ????????? ? ?? ?????????????????.
1/10 ?????? ? ?????????? ??????? ????????
? ????. ???????? ?????? ??????-?????????
????? ??????????????? ? ????????? ?? ??????????? ??????? ???????????????? ?????, ?
????? ?????? ?? ???????. ????? ???????????
???????? ???????? 38 % ?? ????? ?????????
????? ??????? (?.?.?.). ??? ???????? ????????
?????????? ??????? ?????????? ? ????????
?????? ??? ??????????, ????????? 0,5 ? ??????????????? ???? ????? ??-? ? ????????
? ??????? 20-30 ??? ? ????? ? ???????? ?????????????, ????? ????? ???????????????
????? ???????? ??????. ????? ?????????????????? ? ??????? ?????? ????????? ????????? ???????? ?????? ????? ? ????????????
????????? 223 ??.
????????????????? ?????
?????????? ?????? ????????? ???????? ????????? ? ?????????????? ???????????
??????????? FLASH TM 1112.
????????????
?????????????????
H7[P(W2O7)6?2H2O («?.?.») ? ????????????
?????????? ???? [Bun4]3Cl (> 98 %) «Fluka
Chemie», [C5H5N(n-C16H33)]3Cl (98 %) ? [Me(nC8H17)3N]3Cl (Aliquat® 336) «Acros». ?????????, ??????????, ?????????????, ???????????, ?????? ? ?????? ????????????
???????????? ????? «?.?.» ??? «?.?.?.», ? ????????? ??????? ????????? ??????????????
??????? ??????????.
????????? ????????. ? ??????? ???????? ???????? 45 ? ????????? ? ???????????? ??????? ???? ??????, 300 ?? ???????
???-????????? (??????????? / ???? = 9 / 1).
?????????? ???? ? ??????? 3 ?. ????????
?????????, ?????????????? ?????? ???????????????, ?????? ?? ??????? ? ????????????????????? ?? ???-?????????. ???? ???????? 6 ? ???????? ? ?. ??. 255-257 °?.
????????? ????????? ????????. ? ??????? ???????? ???????? 10 ? ??????? ????
??????, ???????????? ?? ??????? 3-5 ??, 250
?? «???????» ???????? ??????? ? ????????
? ??????? 6-10 ?. ????? ????? ???????? ??????? ???????? ?? ???????? ?????????? ??
??-??????????????????
????????????
??????????? ???????? ????????? ?? FTIR????? ???????????? Vector 22 (Bruker). ???????? ???????? ?????????? ? ????????? ??????
? ??????????? ???????. ????????? ???????????? ?????????? ????????? ? ??????????????
????????? OPUS/Y (?????? 2.2).
???-?????????????????? ????????????
??????? ???? ??????????? ?? ????????????
Bruker DPX-200 ??? ??????? 200 MHz = (1?),
???????????? ? ?DCl3.
???????? ?? ?????????? ???????? ????????????? ????? ? ??????? ??? ?? ?????????? «Silufol», ?????? ? ????????? : ?????? (20:1).
??????
??????????????
??????????. ? ???????? ????????????? ???????????? ???????????? ?????????? ????
??? ?????(??????????????????????)??????? Q3{PO4[WO(O2)2]4}, ??? Q ? [Bun4]+,
[C5H5N(n-C16H33)]+, [Me(n-C8H17)3N]+, ??????????????? ?? ????????, ???????????
? ?????? [4]. ????????????? ??????????
# 278 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
???????????? ??????? ??-?????????????.
??????? ????????????? [Bun4]3{PO4[WO(O2)2]4},
[ C 5 H 5 N ( n - C 1 6 H 3 3 ) ] 3 { P O 4 [ W O ( O 2 ) 2 ] 4 },
[Me(n-C8H17)3N]3+{PO4[WO(O2)2]4} ? ???? ????????? ? ??????????? ????? ??????????????
?? ??-?????-???????????? (FTIR) «Bomen
MB-102» ? ??????? 400-4000 ??-1. ? ?????????? ?????????? ?????????????? ????????? ??????????? ?????? ?????????? (??):
??? [Bun4]3{PO4[WO(O2)2]4} ??????????????
?? ???? PO43? (1085, 1052, 1038 (??) ???1), ????? W=O (971 ???1), ????? O?O (856, 845 ???1) ?
???????????????? ? ???????????? ????????? W?O?O (590, 521 ???1). ? ??????? ?????
???????????? ? ?????? ?? (722, 736, 651, 577,
550 ???1), ????????? ? ??????????? ???????;
??? [C5H5N(n-C16H33)]3{PO4[WO(O2)2]4} ?????????????? ?? ???? PO43? (1088, 1061, 1038 (??)
???1), ????? W=O (988, 961 ???1), ????? O?O
(856, 844 ???1), ???????????????? ? ???????????? ????????? W?O?O (591, 526 ???1), ?
????? ?? ??????? ??? 722, 650, 571 ? 548 ???1;
??? [Me(n-C8H17)3N]3+{PO4[WO(O2)2]4} ?????????????? ?? ???? PO43? (1082, 1051, 1036
(??) ???1), ????? W=O (970 ???1), ????? O?O
(855, 844 ???1), ???????????????? ? ???????????? ????????? W?O?O (591, 521 ???1),
? ????? ??, ??????????????? ??????.
????????? ????????. ??????? ?????????
????????? ? ?????????? ???????? (????? 15
??), ?????????? ???????? ?????????????
? ???????? ??? ?????????????????. ??????????? ??????? ???????????? ? ???????
???????? ?????????? ? ????????? ± 1,0 є?.
????????????? ??????????? ????? ???????????? ? ??????? ????????? ???????
(? 400 ??/???). ???????? ????????? ? ????????? ???????: ? ?????????????? ?????
???????????? ? 35 % ???????? ????????? ???????? ? ????????? ??????????? ?????????
??????? 0,57 ????? ???????? ? 10 ?? ????????????? ????????????. ??????????? ?????
????????? ?? ???????? ??????????? ? ????????? ???????.
??????? ???????? ?? ??????????? ??????? ???????????? ??????? ??? ?? ????????? «Merck» ? ??????? ???? ????????????
???? ????? ?????? 30 ???, ??????????????
???????????? ????????? ???????????????? ????????????????? (H7[P(Mo2O7)6].2H2O)
(20 % ? ???????) ? ??????????? ???????????
?? 100 °?.
??? ??????? ??????? ??????????????
????????????? ????? ??????????? ?????
???????????? N,O-???(?????????????)????????????????? ? ???????????? ? ?????????????? ????????? [7]. ?????? ???????????
????? ????????? ? ?????????????? ???????????? ????? 500? ?? ?????????? ??????????? ???????? (40 ? Ч 0,25 ??) ? ????????????????????? ??????????. ???????????
???? ? ???????????????? ?????? ??? ????????? ???? SE-30. ???-???????? ? ?????. ??????
????????? ? ????????????????? ????????
???????: ?? ??????????? ? ??????? 1 ??? ???
60 °?, ????? ????????? ?? ????????? 40 °?/???
?? 280 °?, ??????????? 5 ??? ??? ???? ???????????, ????? ????????? ?? ????????? 5 °?/
??? ?? 320 °? ? ??????????? 10 ??? ??? ????
???????????. ?????? ? ?????? ????????????
????????? ? ?????????????? ????????????
??????? ???????????? [8].
?????????
?????????
????????.
? 0,05 ? (0,023 ?????) ???????????? ? 0,9 ??
(11,3 ?????) 35 % ???????? ????????? ???????? ????????? ??????? 0,3 ? (0,57 ?????) ????????? ???????? ? 10 ?? ??????????. ??????????? ????? ??????????? ??? 60 °? ? ???????
4 ?. ?? ????????? ??????? ???????????? ????
????????, ????????? ????? (3Ч5 ??), ??????
Na2SO4, ? ?????????. ??????? ??????????????? ?? ???????. ???????? 0,25 ? (82 %) ????????
????????? ???????? ? ?.??.184-190 °?. ??????
??? 1? (?, ?.?., J, ??): 0,75 ? (3?, ??3), 0,82 ?
# 279 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
(3?, ??3), 0,83 ? (3?, ??3), 0,94 ? (3?, ??3),
1,00 ? (3?, ??3), 1,22 ? (3?, ??3), 0,70-2,00 ?
(24?), 2,01 ? (3?, ????3), 2,55 ?, 2,69 ? (2?,
?30?2, J 9,2), 3,66 ?, 4,20 ? (2?, ?28?2, J 11,2),
4,46 ? (?3?). ?????? ??? 13? (?C, ?.?.): 14,65
(?27), 15,99 (?24), 16,02 (?25), 16,37 (?26), 18,01
(?29), 18,08 (?6), 21,02 (??3??), 21,04 (??3??),
23,60 (?11), 25,81 (?2), 26,72 (?12), 26,98 (?15),
27,65 (?23), 29,71 (?16), 31,48 (?21), 34,09 (?7),
34,30 (?22), 36,52 (?13), 37,00 (?10), 37,72 (?4),
38,36 (?1), 40,86 (?8), 42,59 (?14), 46,26 (?19),
46,62 (?17), 49,94 (?18), 50,08 (?9), 56,92 (?5),
56,92, 59,87 (?20, ?30), 62,43 (?28), 81,09 (?3),
170,84 (????), 171.,29 (????).
?????????? ? ??????????
??????? ???????????? ????? ??????????????? ??????????, ????????????? ? ???? ?
??????????????? ? ??????????? ??????????????? ? ????? ???????????? ?????????????. ??????? ??????? ???? ??????? ?????????
???????? ? ????? ????????? ?????????????.
???? ???????????, ??? ??????????????????
???????????? ???????? ? ???????????? ????
??? ???????????? ???? 70 °? ??????? ????????
?????? ??? ????????????? ?????????????????.
??? ???????????? ???? 70 °? ?? ??????? ??????? ??????? ??????? ??????????? ????????
???? ??? ??????? ???????????? ????????????.
???, ?? 6 ? ????????? ? ???????? ??????????
????????? ????????? ????????? ?? ?????????
30 %. ?????????? ?????????? ????????? ???????? ?? ??????? ? ????????? ????????? ???????. ?????? ?????????? ?? ????? ????????????? ????????????? ? ????????? ???????????
?? 70 °? ??????? ? 80 % ????????? ??? ??? ??
??????? ???????? ? ??????? ???????????? ?
??????????? ????? ????????? ?????????? ????? 10 ? (????. 1).
? ???????? ????????? ???????? ????
???????????? ?????????????? ??????? ??
?????? ????????????? ?????????? ????????:
????????
?????-?-????????????,
N-???????????????????
?
????????-?????????????. ???? ???????????, ??? ???????? ??????????? ????????????? ??????????
???????? ? ??????? ????????? ???????? ? ?????????????? ??? ??????????? 70 °?, ???????? 6
????? ? ???????????? ???????/??????????? =
30 ? H2O2/??????? = 18 ???????? ????????-?????????????. ?????????? ??????????????
??????? ? ?????? ???????? ???????? ? 100 %
????????? ????????, ????? ??? ??? ????????????? N-??????????????????? ??????????? ???????? ?????????? ???? ?? 80 %, ? ??? ?????????? ???????????? ? ?????-?-?????????????
????????? ?? ????????? 50 %.
????? ????, ???? ??????????, ??? ???
?????? ???????????? ???????????? ? ?????????? ???? ??? ??????????? 90 °? ?????????
??????? 1. ??????? ???????????, ??????? ???????????? ? ???????????? ???????????? ?? ?????????
???????? ??? ??? ????????? ? ????????? ????????
?
?/?
????????????
????????? ????????/
???????????
T єC
?, ???
?????????, %
1
CHCl3
30
40
2
10
2
CHCl3
184
40
4
18
3
CHCl3
44
50
6
25
5
C2H4Cl2
30
70
6
80
6
C2H4Cl2
30
70
10
100
??????????? - [C5H5N(CH2)15CH3]3{PO4[WO(O2)2]4},. ????????? H2O2/???????? = 18
# 280 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
?? ????????? 70 %. ?????????? ??????????? H2O2/??????? ? 1,5 ?? 18 ? ???/??????? ?
5Ч10 -3 ?? 3.3Ч10 -2 ????????? ???????? ???????
??????????? ???????? ?? 100 %, ?? ?? ???????????? ?????????? ????????????? ???????.
?? ???? ??????? ? ?????????? ??????????????
????? ?????????? ????????? ?????????, ??
???? ?? ??????? ?? ?????????? ? ??????????? ????? (????. 2).
????????? ?????????? ????????????? ?
????????? ??????? ??????? ???????? ? ???????? ???????? ?? ??????? ???? ???? ???????? ????????? ????????? ??? ?????????????
???????????, ??? ???????? ??????? ????????? ???????????? ???????-?????????? ?????
? ???????? ????????? ???? ??? ???????????
???????? ????????.
????????? ??????? ????????? ????????? ?????????? ???????? ?? ???????? ?????????????? ????????, ?????????????? ??????????? ?? ???? ?????? [9]. ??? ???????,
??? ???????? ??????????????? ? ???????
????????????? ??????? ????????? ? ????????????? ?????????. ? ???? ?? ??? ???????
??????????????? ?????????? ???????? ?? ??????? ???????? ?????????? ???????, ???????? ?? ?????????? ????????????????? ??????? ??? ?????????. ??? ??? ????????? ??????
????????? ???????? ? ?? ????????? ???????
??? ???????? ?????? ? ??????? ?? ????????
?????????? ???????? ? ????????? ????.
? ?????? ?????? ??????????? ????????
????????, ?????????? ??????????????? ??
???? ?????? ????? ????????, ??????????
?? ?????????? ?????? ????????? ????????
?? ???????-???????????? ????????? ???? ?????? ? ??? ???????????? ??? ????????? ???????????? ??????? ? ???????? ??????? [10].
??????????? ??????????? ???????? ????????? ???????? ????????? ?? ??????? ????????? ????????? ???????? ? ??????????
????????????? ?????. ??????????? ?????
????????? ???????? ????????? ?? ?????? «???????» ???????? ???????. ??????? ????????
???????? ????????? ????????? ????????.
?? ????????? ?????? ??????????? ??????? ???????, %: (?) 78,06; (?) 10,2; (?) 11,9.
?????????, %: (?) 77,6; (?) 10,3; (?) 12,2.
?????????? ????????, ???????? ???????????? ????????????? (???), ???????????
?? ???????? ????????, ? ???????????? ?????
??????, ????? ??????????? ???????? ????????????? ????????? ????????.
??-?????? ????????? ????????: 3070,9
(?=?); 2953,56; 2872,73 (?-?); 1739,93
(? = ?); 1458,23; 1391,79; 1368,56 (?-?); 1246,14;
1151,11; 1108,63 (?-?-?) (???. 1).
?????? ??? 1? (?, ?.?., J, ??): 0,78 ? (3?,
??3), 0,82 ? (3?, ??3), 0,90 ? (3?, ??3), 0,96
? (3?, ??3), 1,32 ? (3?, ??3), 1,61 ? (3?, ??3),
0,70-1,95 ? (24?), 1,97 ? (3?, ????3), 2,00 ?
(3?, ????3), 2,38 ? (1?, ?19?), 3,77 ?, 4,18 ?
??????? 2. ??????? ???????????, ???????????? ???????????? ? ????????? ???????? ?? ?????????
???????? ??? ??? ????????? ? ????? ??????????????
?
?/?
1
????????? ????????/
???????????
200
????????? H2O2/
????????
1.5
2
200
3
3
85
4
5
T, єC
?, ?
?????????, %
90
20
35
90
20
70
5
85
10
50
50
6
85
10
80
30
18
70
6
100
??????????? -[CH3(n-C8H17)3N]3{PO4[WO(O2)2]4}
# 281 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
???. 1. ??-?????? ????????? ????????
(2?, ?28?2, J 11,2), 4,39 ? (?3?), 4,52 ?, 4,62 ?
(2?, ?30?2). ?????? ??? 13? (?C, ?.?.): 14,95
(?27), 15,79 (?24), 15,92 (?25), 16,27 (?26), 17,94
(?6), 18,89 (?29), 20,58 (?11), 20,77 (??3??), 21,04
(??3??), 23,46 (?2), 24,92 (?12), 26,83 (?15), 27,71
(?23), 29,35 (?16), 29,52 (?21), 33,91 (?7), 34,32
(?22), 36,82 (?10), 37,32 (?13), 37,55 (?4), 38,16
(?1), 40,66 (?8), 42,45 (?14), 46,08 (?17), 47,47
(?19), 48,54 (?18), 50,05 (?9), 55,15 (?5), 62,50
(?28), 80,61 (?3), 109,69 (?30), 149,80 (?20), 170,63
(????), 171,23 (????).
????????? ????????? ???????? ????????? ? ???????? ?????????? 35 %
??????????
????????
?
???????????
????????(??????????????????????)??????????????-?-???????????? ??? ???????????
60 °?. ???? ???????????, ??? 98 % ?????????
????????? ???????? ??????????? ????? 4 ? ??????? ???????. ??? ???? ? ???????? ????????
??????? ? ?????????????? 90 % ??????????
??????? ????????? ???????? ?? ????? (???. 2)
??????? ??? ??????? ?? ??????????? ?????, ?????????????????? ?? ??????? ? ??????????????? ??????? ???-????????????? (???. 3).
? ??????? ??? 1? ???????? ??????? ??????????? ??????? ???????? ??? ???????
???. 2. ????? ??????????? ???????? ????????? ????????
# 282 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
????? (4,52 ? 4,62 ?.?. ? ??????? ?????????
????????), ? ? ??????? ??? 13? ???????????
??????????????? ??????? ?????????? ?????? ???????? (???????? ??? 109,69 ? 149,80
?.?. ??? ????????? ????????). ????? ?????????????? ??? 2,38 ?.?. ? ??????? ??? 1? ????????? ?????????? ????????????? ??????
??????? ??? ?19 ? ??????? ???????? ?????????
? ????? ??????? ????, ??? ????????????? ????????? ?????? ????????????? ????????. ? ??
?? ?????, ? ??????? ??? 1? ???????? ??????? ????????? ??? 2,55 ?.?. ? 2,69 ?.?. ????????? ??? ??????? (J=9,2 ??), ???????? ?? ?
???? ????????????? ???????? ???????? ???????????? ????????????. ? ??????? ??? 13?
???????? ??????? ????????? ?????????? ?
?????????? ???????, ?? ??????? (56,92 ?.?.
? 59,87 ?.?.) ?????????? ??? ?????? ????????
?????????? ??????.
????? ???????, ?? ????????? ??????????
?????? ????? ??????? ?????????? ? ???, ???
? ????????????? ???????? ??????? ?????????
????????? ???????? ???????? ?? ???? ??????????????? ???????????? ??????? ?????.
? ??????? ????????? ???????? ?????????? ??????? ????????? ???????? ? ?????????????? 90 % ?? ???? ?????????????. ???
???? ????????? 98 % ??????????? ?????? ???
????????????? ??????????? H2O2/????????
?? ????? 10. ?????????? ???????????? ???????????? ??? ????????????? ????????????
?????????? ? ??????????? ????? ?? ????????? ??????? ??????? ????????? ???? 60 %.
??????????
??????? ?????????????? ??????? ????????? ???????? ? ??? ????????? ? ?????????????? 35 % ???????? ????????? ???????? ? ??????-
???. 3. ????????? ???????? ??? 1? ????????? ???????? ? ???????? ????????? ????????
# 283 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
????? ????????????? Q3{PO4[WO(O2)2]4}, ??? Q
? [Bun4]3+, [C5H5N(n-C16H33)]3+, [Me(n-C8H17)3N]3+
? ?????????????? ??????? ????????? ???????? ????????? ????????.
??????????, ??? ??? ????????? ???????? ?????? ??? ????????? ????? ???? ?????????? ?????? ??? ??????? ?????????????
???????????? ? ?????????? ? ??????????? ??????? ???? 70 °?, ?????? ??? ???? ?????????? ??? ???????? ?????????.
???????????, ??? ? ????????????? ???????? ??????? ????????? ????????? ????????
?????????????? ????? ??????????????? ???????????? ??????? ?????, ??? ???? ???????
????????? ????????? ??????????? ??? ????????? H2O2/???????? ? 10. ??? ????????????
????????/??????????? = 1000 ? H2O2/????????
= 10 ??????????? ???????? ????????? ???????? ?????????? ?? 6 ? ??? 60 °? ? ??????????
98 % ? ?????????????? 90 %.
?????? ????????? ??? ?????????? ????????? ????????? ????? ? ???? ? ??????????
??? (?????? ?5.6.3.).
?????? ??????????
1.
2.
3.
4.
Venturello C. and Gambaro M. Selective oxidation of alcohols and aldehydes with hydrogen
peroxide catalyzed by methyltrioctylammonium tetrakis(oxodiperoxotungsto)phosphate(3-)
under two-phase conditions // J. Org. Chem. 1991. V. 56. ?. 5924-5931.
Noyori R., Aoki M. and Sato K. Green oxidation with aqueous hydrogen peroxide // Chem.
Commun. 2003. V.16. ?. 1977-1986.
Ishii Y., Yamawaki K., Ura T., Yamada H., Yoshida T. and Ogawa M. Hydrogen peroxide oxidation
catalyzed by heteropoly acids combined with cetylpyridinium chloride. Epoxidation of olefins
and allylic alcohols, ketonization of alcohols and diols, and oxidative cleavage of 1,2-diols and
olefins // J. Org. Chem. 1988. V. 53, N15. ?. 35873593.
??? ?.?., ????????? ?.?., ?????????? ?.?., ??????? ?.?., ?????????? ?.?., ??????????
?.?., ??????? ?.?., ??????????? ?.?. ?????????????? ????????? ?????????? ??????????
? ??????? ?????????? ???????? ?? ????- ? ???????????? ?????? // ???. ??? ???. ???.
2005. ?8. ?.1-8.
5. ??? ?.?., ?????????? ?.?., ????????? ?.?., ?????????? ?.?., ?????????? ?.?. ?????????
?????????????? ????????? ???????????? ?????????? ?????????? ???????? ? ???????????
????????????????????????? // ??????? ? ??????????????. 2006. ?5. ?. 12-23.
6. ???????? ?.?. ????????????? ???????? ???????: ?????????, ??????, ????????, ??????????
// ????? ?????????. 1994. ?3. ?. 3-28.
7. Johnson C. B. Isolation of cholesterol oxidation products from animal fat using aminopropyl
solid-phase extraction // Journal of Chromatography A. 1996. V. 736. P. 205-210.
8. Kalambet Yu.A., Kozmin Yu.P., Perelroyzen M.P. Computer spectrochromatography: Principles
and practice of multi-channel chromatographic data processing // J. Chromatography. 1991. V.
542. P. 247-261.
9. ???????? ?.?., ???????? ?.?., ???????? ?.?., ??????? ?.?. ?????? ????????? ?????????
????????. ?????? ?? ? 2150473. ?????. 06. 10. 2000.
10. ????????? ?.?., ???????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?. ??????
????????? ????????? ??????????. ?????? ?? ? 2324700. ?????. 20. 05. 2008.
# 284 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
Catalutic Oxidation of Betulin and Betulin Diacetate
with Ecology Friendly Reagents
Tatiana B. Khlebnikovaa, Zinaida P. Paia, Boris N. Kuznetsovb,c,
Yulia V. Mattsata, Svetlana A. Kuznetsovab,c,
Polina V. Berdnikovaa, Galina P. Skvortsovab
a
Boreskov Institute of catalysis
5 pr. Lavrentieva, Novosibirsk, Russia 630090
b
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
c
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
The conditions of betulin and betulin diacetate oxidation with 35 % H2O2 into their epoxides were
studied. In the two-phase water-organic medium the oxidation reactions are carried out at mild
conditions: atmosphreric pressure and temperature 60-80 °C. The reaction of betulin diacetate
oxidation was realized with high yield of epoxide (90 %) and degree of the conversion 98 % in the
presence of soluble catalyst [CH3(n-C8H17)3N]{PO4[WO(O2)2]4}.
Keywords: phase-transfer catalysis, oxidation, betulin, betulin diacetate, hydrogen peroxide,
peroxopolyoxotungstenphospate complexes.
# 285 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ?????????, ???????? ?. ?????????? ???????? ? ?????????? ??????????? ???????????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 286-292
~~~
??? 547.595 + 676.164
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?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
??????????? ??????, ????????? ? ??????????? ???????? ?????????, ??????????
?????????????? ? ???????? ?????????? ???? ???? ??????. ????????? ?????? ?????????????
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?? ???? ??????? ?????????????, ????????
??? ? ???????????? ??????????? ???????????????? ? ?????????? [9, 10]. ?????? ????????? ?????????? ???????????? ????????????
??????? ??????????????? ????????????? ?????? ??????????????? ????????????? ?????
??? ????????? ???????????????. ??? ???????
??????????, ?????????? ?????????? ?????????? [1, 2]. ??? ????????????? ????? ?????????????? ?????? ????????, ???????????? ??
????? ?????????, ??????? ????????? ? ?????
[3-8]. ???, ? ???????? ???????????? ?????????? ??????????? ??????????? ???????????
????????????? ????? «?????????» ?? ??????
???????????? ???????. ?????? ???????? ???????? ??????? ??????????? ?????????? ?
???????? ????? ??????????? ? ????????????-
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????????? ????????? ?? ??????? ???????? ?????????? ???? ???? ?????? ? ????????? ????,
????????????? ??? ????????????? ? ???????
????????????? [11-13].
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????????? ?? ???? ???? ??????, ?? ???????????? ???????? ????????????? ??????????
??? ??????? ???? ????????? ? ????????? ??
*
1
Corresponding author E-mail address: shchipko@krsk.info
© Siberian Federal University. All rights reserved
# 286 #
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???????? ?????? ??? ????????? ???????? ???-1 ??????? ??? ???? ?????? ????????
(Betula pendula Roth.) ?????????? ??????? (%
?? ????? ????????? ?????? ????): ???????????? 48,8-49,1; ?????? 33,1-34,2; ??????????????? ???????? 13,1-13,7; ???? 2,4-3,4. ??? ????????? ???????? ???-2 ????????????? ???????
??????? ???????????????? ?????????? ????
?????????? ?????????????? (??????, ??????????, ???????????, ????). ?????? ??????? ?????
? ?????????? ?????????, ? ????? ???????????????? ?????????? ???? ????????????? ?????????????? ????????? ?? ???????????? ?
????? ????????? ????????? [14].
???????? ??? - 1 ? ??? - 2 ???????? ?????????? ???????????????? ????? 2 %-???
????????? NaOH ??? ??????????? 60 °?, ??????????? 5, ????????????????? 1 ? ??? ?????????????.
???????? ?????????? ????????? ????????? ?? ?? ??????????? ????????? ????????
? ???????, ????????????? ??????????????
??????????? ??? ???????????? ???????????????: ??????????? ?????, ???????????
?????????????????? ??????????, ? ????????
? ??? ?????? ?????????????????? ?????????? ???????? ?????????? [15, 16]. ????????????? ????????? ??????????? ??????????
????????? ? ????????? ???? ???????? ??????,
??????????? ? ???? 6217-74.
????????? ????? ??? ??????????? ????????? V??? ?????????? ?? ?????????? ???????? ? ????????? ?? ???????: V??? = (m1 - m)
/(m??), ??? m ? ????? ??????? ???????, ?; m1 ?
????? ??????? ???????, ???????????? ?????????, ?; ? ? ????????? ????????, ?/??3.
1
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??????? ?? ??????? «Specord-75 JR? ? ??????? 400-4000 ??-1. ?????????????? ?????????? ??????? ?????????????? ? ???????? ?
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??????????.
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??????????? ??????????? ?????????????
????? «?????????», ????????? ??????????
????????? ????? ?????????????? ? ????????
?? ???? ???? ?????? ??????? [10, 12, 17].
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?????????? ???????? ?? ???? ???? ?????? ???????????? ????? ??????????????? ????????? ??????-??????????? ?????
? ?????????? ?????? ?? ????? 200-250 ???.
?????????? ?? ?????? ??????? ??????????
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? ???????? ????????? ?????????? (% ?? ?????
????????? ?????? ????????): ????????????
? 21,6-26,3; ?????? ? 27,9- 49,6; ??????????????? ???????? ? 1,1-3,8; ???? ? 1,6-2,1. ???????? ???-1 ? ???-2, ?????????? ?? ??????????
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??????? ? 49,6 ? 27,9 % ? ?????????? ??????????????? ??????? ? 3,8 ? 1,1 % ??????????????. ???? ???? ??????????? ???, ??? ??? ???????????????? ?????????? ???? ? ??? ?????
????????? ?????????? ?????????? ???????
? ?? 20,2 % ? ??????????????? ??????? ? ??
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?? ????? ????????. ???????? ?? ???? ???????????, ??????????? ? ??????, ????????????
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# 288 #
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? ????. 2 ????????? ???????? ?????????????? ???????????, ???????????? ?????????? ???????, ? ???????? ????????? ??
???? ????????? ????.
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# 289 #
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?? ???? ???? ?????? (???)
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2,3 ± 0,2
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29,2 ± 1,4
38,3 ± 1,2
76,3 ± 5,4
3,9 ±0,1
1,4 ± 0,1
4,5 ± 0,3
17,9 ± 1,3
48,9 ± 1,8
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4,5 ± 0,2
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27,3 ± 1,2
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59,1 ± 3,3
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2
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? ???????? ??????? ??? ??????????, ??????????????, ??????????? ?? ?????????? (????.2).
???? ????????????? ?????? ???????????????? ?????????????? ???? ???????????? ????????????? ????????? ??????????? ???????
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??? ???????? ????????????? ??????? ?????????? ? ????????? ?????? - ?? 134,9 ??/?.
?? ????????? ????????? ?????? ????????
???????? ????????? ???????? ??????????,
?? ???????? ?? ??????? ????????????????,
?????????? ? ?????????? [9]. ?? ???? ??????
???????? ????????? ????? (11,4 - 12,3 ??/?)
???????? ?? ???? ???? ?????? ?????????????? ??? ??????????? ?????? ????????.
?????? ???????????? ????? ??????????????
? ?????? ???????????? ?????????? ? ???????????? ????? ???????? ?????????????? ?
?????????? ??????? ?????? ?????????? ?????
? ??????? ?????????????, ???????????? ???
??????????? ???????????????? ??????????
???????? ? ???????? [9, 19].
????????? ???????????? ????????????? ????????? ???????? ???????? ?? ????????????????? ???? ???? ?????? ??? ??????
?????????-???????? ????????? ? ???????????? ?????. ???????????, ??? ??????????? ???????? ?? ???? ????????????
??????????? ????????????? ??? ??????
???????? ????????? ? ?? ????????? ????????? ???????. ?????????? ?????????? ????????? ????????????? ???????? ?? ???? ????
# 290 #
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??????????
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???????? ? ???????? ?? ???????? ?????????.
??? ???? ??????????? ?????????? ????????? ???????? ?? ???? ????????????? ????????????? ?? ????????? ? ???????? ?????,
?????? ??? ??????? ?? ???????????? ??????
????????????? ? 1,5 -2,9 ????, ????????, ??
???? ?????????? ?????? ???????.
????????????? ?????? ???????????????
?????????? ???? ????????????? ?????????????? ???????? ? ???????? ?????????? ???-
???? ? ?????????? ??????????????? ???????
? ???????? ???-2 ?? ????????? ? ?????????
???-1, ??? ???????? ??? ?????? ???????????,
?? ???? ?????? ?? ??????????? ? ??????????? ?????????????? ??????????? ?????????
?????????.
????????, ??? ????????????? ?????????? ????????? ?? ???? ???? ?????? ?? ????????, ??????????????? ??????????????
???????????, ? ????? ?????????? ?????????? ??????????????? ??????? (1,1-3,8 %) ?
???? (1,6-2,1 %) ????????????? ???????????,
????????????? ? ???????????????.
?? ?????? ??????????? ???????, ????????? ? ??????????? ????????? ???????? ????????? ?? ???? ????????????? ????????????
???????? ?????????????? ???? «?????????».
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
9.
??????? ?.?., ??????????? ?.?. ??????????? ?????? ???????????? ? ???????. ?????,
1983. ? 182 ?.
???? ?. ??., ????? ?.?., ????? ?. ???????? ? ?? ??????????? ?????????? / ??? ???. ?.
?????????. ? ????, 1989. ? 398 ?.
??????? ?.?. ??????-?????????? ???????? ? ?????????? ??????????????? ?? ??????
????????????? ???????? ?????: ???????. ???. ? ????. ???. ????. ????, 1991. ? 20 ?.
???????? ?.?., ?????? ?.?., ???????? ?.?. ??????? ??????? ?????? ? ???????????
???????????? ?????????? ?? ????????? ????????? ? ????????????? ????????? // ?????????????????????? ??????. ? 2000.-?. 34. ? ? 5. ? ?. 44-47.
???????? ?.?., ???????? ?.?., ???????? ?.?, ????????????????? ?????????? ???????
???????????? ?????????? ?? ?????????? ??????? // ??????-???????????????? ??????. ?
2000. ? ?. 34. ? ? 12. ? ?. 38-40.
?????? ?.?., ??????????? ?.?., ??????? ?., ??????? ?.?., ????? ?.?., ?????? ?.?.
??????? ??????? ? ????????? ??????????? ?? ?????????????? ? ??????????? //
????????????? ? ????????????????? ?????. ? 2004. ? ?. 40. ? ? 3. ? ?. 113-139.
??? ?.?., ??????????? ?.?., ???????????? ?.?. ????????????? ?? ?????? ????????
???????????? ????? ? ??? ???????????????? ??????????? ?????????????? ?????????????
// ??????-???????????????? ??????. ? 2007. ? ?. 41. ? ? 1. ? ?. 21-26.
????? ?.?., ???????? ?.?., ??????? ?.?., ????????? ?.?., ????????? ?.?. ??????? ?.?.
??????? ?????????-?????????? ??????? ?????????????? ????? ?? ?? ???????????????
????????????? // ??????-???????????????? ??????. ? 2007. ? ?. 41. ? ? 6. ? ?. 44-48.
??????? ?.?., ???? ?.?., ?????? ?.?., ??????? ?.?. ????????????? /??? ???. ?.?.
????????. ? ?.: ????? ??????????? ??????????, 1991. ? 328 ?.
# 291 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ?????????, ???????? ?. ?????????? ???????? ? ?????????? ??????????? ???????????
10. ?????? ?.?., ???????? ?.?., ?????? ?.?. ??????????? ????????? ?? ??????? ????????????
???????????? // ????? ? ????????? ??????????? ????????. ? 1994. ? ?. 2. ? ? 2-3. ? ?. 559-581.
11. ????????? ?.?., ????? ?.?., ???????? ?.?., ?????????? ?.?., ????????? ?.?., ?????????
?.?. ????????? ? ???????? ??????????????? ?? ???? ????????? ???? // ????? ?????????????
?????. ? 2004. ? ? 2. ? ?. 25-29.
12. ????????? ?.?., ????? ?.?., ????????? ?.?., ???????? ?.?. ????????? ???????????????
?? ??????? ?????? ?????? // ????? ????????????? ?????.-2005. ? ? 1. ? ?. 65-70.
13. ????????? ?.?., ????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?., ????? ?.?.
????????????? ? ?????? ??? ?????????. ?????? RU 2311954, 2006.
14. ?????????? ?.?., ????????? ?.?., ???????? ?.?. ???????????? ?????? ?? ?????
????????? ? ?????????. ?.: ????????, 1991. ? 319 ?.
15. ??????????????? ?????????? ????. ???. 2. ????? ?????? ???????. ?????????????
???????????? ?????. ?.: ????????, 1990. ? 679 ?.
16. ?????????? ?.?. ?????? ????????????? ??????????? ??????????????? ? ?? ?????????????
???? // ??????-???????????????? ??????. ? 2003. ? ?. 37. ? ? 5. ? ?. 28-32.
17. ????????? ?.?. ??????? ???? ?? ??????? ???????? ? ????????? ??????? ??????????,
??????????? ?? ????? ????????????? ???? (?? ??????? ???? ???? ?????? ? ?????? ????):
???????. ???. ? ????. ????. ????. ? ??????????, 2007. ? 19 ?.
18. ???? ?.?., ????????? ?.?. ???????????? ???????? ? ???????????? ????. ?.: ????????,
1984. ? 298 ?.
19. ?????????? ?.?. ????????????? ???? ?????????????? ? ????????? ???????? ? ????????.
?.: ?????, 1977. ? 184 ?.
Properties and Application of the Sorption Materials
from Outer Birch-Bark
Evgeniya V. Veprikova, Svetlana A. Kuznetsova,
Galina P. Skvortsova, Maxim L. Shchipko
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Composition, structure and sorption properties of the sorbents, obtaining by outer birch-bark
extraction and alkaline treatment have been studied. Estimations of their sorption activity with the use
of marker substances for enterosorbents and contents of water-soluble residual substances and ash in
sorbents have been made. It was found that the properties of the sorbents from outer birch-bark are
corresponding to properties of the industrial enterosorbents ?Polifepan? type.
Keywords: outer birch - bark, extraction and alkaline treatments, enterosorbent, structure,
properties.
# 292 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 293-300
~~~
??? 543:585.2
???????-????-?????????????????? ???????? ???????????
??????? ??????????? ????????? ???? ?????
???? ?. ??????????, ???????? ?. ???????????,?,
?????? ?. ?????????, ????? ?. ?????????,?*
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ??????
?
???????? ????????? ?? ???
?????????????, ??????????, 660036 ?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
??????? ???????-????-????????????? ???????? ???????? ? ?????????? ??????? ???????????
????????? ???? ????? ?????????? (Pinus sibirica Du Tour). ???????????, ??? ?????????
???????????? ??????????? ??????? ????????? ???????? ?????????? (thunbergol) (30,1 %),
?-?????????? (16,5 %) ? ?????????? ????? (10 %), ? ?????? ??????? ? ?????????????? ???????
(40,2 %), ????????????? ??????? (12,1 %) ? ???????? ???? ?????????????? (??????????????)
??????? (7,6 %).
???????? ?????: ???? ?????, ?????????? ????????, ?????? ??????? ??????????? ?????????,
??????????? ??????? ??????????? ?????????.
????????
???????? ??????????? ??????? ????????? ??????? ???? ??????? ????? ????????
????????? ???????????? ????? ?????. ???????? ?????? ?????????? ?????? ???????
????? ? ??????? ????????? ???? ????? [1,
2], ???, ????? ? ???????????. ???????? ?????? ????? ?????????? ????????? ?????? [3],
? ??????? ??????? ?????????? ????????????? ?? ????? ????????, ????????????????
???????????? ????????, ?? ????? ????????
?????? ???????? ?????????????? ???????, ?
?? ??????????? ????? ?????? ? ?? ????????? ????.
*
1
?????????? ?????? ????????? ???????
???? ????? ?????????? ?????? ?? ??? ????????. ? ?????? [4], ? ?????????????? ????????????? ?? ?????????? ? ???????????
???????? ??????? ??????? ??? ?? ???????
????-5, ???????? ?????? ? ??????? ????????
????????? ???????????? ??????? ????? ??????????.
??? ??????????????????? ???????? ????????? ???? ????? ?? ???????????
????????, ? ??????????? ???????? ?????????? ??????? ??????? ????????????? ?? ??????, ??- ? ??-?????????????
?????????? ???? ??????????????? ??????
Corresponding author E-mail address: inm@icct.ru
© Siberian Federal University. All rights reserved
# 293 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
(?-?????????, ????????, ?????????, ?????????????? ? ???????????) ? ??? ?????????: 4,4?-?????????????????? ? 3,5,4???????????????????? (???????????) [5,6].
????? ?????? ???????? ???????? ??????????? ??????? ??????????? ????????? ????
????? ??????? ???????-????-?????????????.
????????????????? ?????
? ?????? ? ???????? ????? ????????????
???? ????? ?????????? (Pinus sibirica Du Tour),
?????????? ?? ????????? ??????? ?. ??????,
???????????? ?? ??????? 1,0 - 2,0 ??. ??????
???????????? ???? ???????? ? ????. 1.
????????? ?????????. ??????????
????????-????? ???? ????? ????????? ? ???????? ????????, ???????????? ? ??????, ?????
?????????? ? 20 ?. ?? 110 ? ???? ????? ?????
???????? ???????????? ???????? 6,5 ? ????????? ? ???? ?????-??????? ?????? ????? ??
????????? ???????. ????? ????????? 5,9 %.
????????? ?????????. ?????????? ??????????? ????????? ?? ?????? ? ???????????
???????????? ????????? ????????? ???????. ???????? (6,5 ?) ?????????? ? 100 ??
0,5 ? ?????????? ???????? ?????? ????? ? ????????? ? ????? ? ???????? ?????????????
?? ??????? ???? ? ??????? 1 ?. ?? ?????????
?????????? ??????????? ????? ?????????
????? ? ?????? ????. ?????????? ????? ?????????????? ?????????? ?????? ??????
? ??????????? ???????. ??????? ???????
?????????? ? ?????? ?? Na2SO4. ???? ????????, ??????? ?????? ?? ??????????? ????.
????? ??????????? ??????? ???????? 1,7 ?
(26,1 %). ?????? ??????? ??????????????
???????????? ??????? ???????? ?? ??????????? ????? (?? 4), ?????????? ????? ?????????????? ?????? ??????, ???????? ??????????, ?????? ??? Na2SO4, ???? ????????,
??????? ?????? ?? ??????????? ????. ?????
?????? ??????? ???????? 4,2 ? (64,6 %).
???????-????-?????????????????? ?????? ?????????? ?? ??????? ????????????
GCD Plus (Hewlett-Packard, USA) ? ????????????? ????-???????? (HP MSD). ???????????? ??????????? ??????? HP-5S ?????? 30
?, ?????????? ????????? ? 0,25 ??. ???????
???????????????????: ??? ???????? ? ?????;
???????? ?????? 1 ??/???; ??????????? ????? ??????? 220 ??; ????????? ??????????? 50
?, ????????? ??????? ??????????? ?? 320
? ?? ????????? 8 ??/???; ??????????? ??????????? ????? 230 ??; ??????????? ?????????
????? 175 ??; ????? ???????????? ????? ???
70 eV; ???????? ???? ?? 45 ?? 450 m/z. ???????????? ?????? ??????? ?? ????????? ?????? ??????????? ? ?????? ????-????????
? ???????????????? ??????? ??????????
????-????????????.
?
?
?????????? ? ??????????
????????, ??? ????????? ????????
??????? ????? ???????? ???????????? ????? ??????? ????? ?????????? ??????????,
??????, ?????, ?????????? ? ???????????? ?????? ??????, ???????? ??????. ????????????? ?????? ??????? ??????????? ??
??????? 1. ?????????? ?????? ???? ????? ??????????
??????????
??????, % ???. ?? ?????
????????? ????? ????
?????????
??????
?????????????
????????
27,7
32,3
16,7
# 294 #
????????????
??????????????????
???????????????????
?????????
18,7
26,2
2,3
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
????????????? ????? ??????????? ??????????????. ????????????? ?????? ???????????-????????????? ????????? ???????
?????????? ????????? ??????? ?? ?????????????? ?????????? ? ????????????????
?? ? ?????????? ??????? ?????????. ????????????? ?????????????? ???????????
??????????? ?????????? ????? ??????????
????? ??????? ?? ?????? ? ???????????
???????.
?????????? ???????? ???? ????? ?????????? ????? ???????? ???????????? ??? ???????? ?? ??????????? ? ?????? ???????.
??? ???????? ?????????? ???????-??????????????????????? ????????????, ??????
??????? ??????????? ????????? ????????
???????? ? ?????? ??????? ??????? ?16-?26
? ?? ???????? ?????. ????????? ?? ???
???????? ?????????????? ??????? (40,2 %),
????????????? ??????? (12,1 %) ? ????????
???? ?????????????? (??????????????) ??????? (7,6 %). ?? ???. 1 ???????? ????????????? ?????? ??????? ??????????? ?????????, ?
?? ???. 2 ? ?? ????-??????. ? ????. 2 ???????
???????? ?????? ???????, ?????????????
?????????? ??????? ? ?????? ??????? ????????? 0,5 % ? ??????? ??????? ???????????????? ? ??????????? ????????? (? ???????????? ????? 85 %).
?????????????? ??????? ????????? ?
?????? ?????????? ????????????? ? ???????? ???????? ??????????? ?????????????
???. 1. ????????????? ?????? ??????? ??????????? ????????? ???? ?????
???. 2. ????-?????? ????????? ?????????? ?????? ??????? ??????????? ????????? ???? ????? ?
?????????????? ???????
# 295 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
??????? 2. ?????? ?????? ??????? ??????????? ????????? ???? ?????
????? ???????????,
???
?+
?????????????
??????????, %
????????????? (??????????????) ???????
?15?31????
19,72
256
12,1
???????? ???? ?????????????
(??????????????) ??????? ?15?31??2C2H5
19,92
284
4,2
????????????????? ??????? ?16?33COOH
20,90
270
1,6
???????? ???? ?????????????? (????????????)
??????? ?16?33COOC2H5
21,24
298
0,9
???????????????? (?????????) ???????
C17H29COOH
23,00
280
6,9
???????? ???? ????????? ???????
C17H33CO2?2?5
23,12
310
4,9
????????????? (???????????) ???????
C17H35COOH
23,30
284
0,6
???????? ???? ??????????? (?????????????)
??????? C17H35CO2?2?5
23,55
312
0,9
???????? ???? ?????????????
(?????????????) ??????? C18H37COOC2H5
24,79
326
0,7
???????? ???? ?????????? (???????????)
??????? ?19?39CO2?2?5
26,94
340
5,4
?????????????? ???????
28,52
316
40,2
???????? ???? ??????????? (?????????)
??????? C21H43CO2?2?5
30,14
368
5,4
???????? ???? ??????????????
(??????????????) ??????? C23H47CO2?2?5
33,03
396
7,6
???????? ???? ?????????????? (???????????)
??????? C25H51COO?2?5
35,68
424
1,9
?????????
??????? ???? ? ?????? [3] ?????, ??? ?????
???????? ???????? ???????????? ???????
?????? ???????? ????????? ???????????? ??????? ????? ?????????? [4].
????????????? ????????? ??????? ?
?????????????? ??????? ? ?????????????????? ???????????? ?????????? [7]. ???????? ?????? ? ?????????? ?????????? ????????? ???????? ??????????? (??????????
? ?????????), ?????????? ?????????????
????????????? ???????????, ? ??? ????? ?
????????????????? ????????? [8]. ????????
??????????? ?????????????? ???????, ?????????? ???????????????? ? ????????????????? ????????? [9].
??????????? ????? ??????????? ????????? ???????? ????????? ??????????? ? ????????????? ??????. ????????? ???????????? ??????????? ????? ??????????? ?????????
???? ????? ???????? ?????????? (thunbergol)
(30,1 %), ?-?????????? (16,5 %) ? ??????????
????? (10 %). ?? ???. 3 ???????? ????????????? ??????????? ??????? ??????????? ?????????, ? ?? ???. 4 ? ?? ????-??????. ? ????. 3 ????????? ?????????? ??????????? ???????,
??????? ???????????????? ? ????????????
????? 85 %, ????? ?? ???????????, ???????????? ????? ? ????????????? ??????????.
????????????? ??????????? ??????????? ????? ??????????? ????????? ????????
# 296 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
??????? 3. ?????? ??????????? ??????? ??????????? ????????? ???? ?????
????? ???????????,
???
?+
?????????????
??????????, %
???????
3,58
154
0,4
?-???????
12,99
204
2,2
?????????
?-?????????
13,81
222
1,6
3,7,11-????????-1,3,6,10-?????????????????????
18,87
272
9,6
?????????? (thunbergol)
21,27
290
30,1
1-??????????? ?19?39??
28,51
284
5,0
1-????????? (?????????? ?????) ?20?41??
31,62
298
10,0
?-??????????
40,03
414
16,5
?????????-3,5-????-7-??
41,02
410
1,9
C???????-4-??-3-??
41,5
412
5,0
???. 3. ????????????? ??????????? ??????? ??????????? ????????? ???? ?????
???. 4. ????-?????? ????????? ?????????? ??????????? ??????? ??????????? ????????? ???? ????? ?
??????????? (thunbergol)
# 297 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
??????????????? ???????????? ????? ??????????, ?????????? ???????????????????
????, ??? ????????????? ?????????? ?????????? ????? 30 %. ??????? ??? ???? ??????? ?
???? ????? ??????? (Douglas fir). ??? ????????
?????????? ?? ?????????? ???????????? ?????
???????????? Pinus cembra [10], ? ???????????
?????????? ??? ???????? thunbergol. ?????????? ? ???????? ??????????? ???????????
?????? ????? ?????????? [11], ?????? ? ????
? ??????? ??????? ?? ??????????? [4]. ?? ??????????? ???????? ???????????, ?????????? ??????? ??????????????? ???????????
[12]. ?-?????????, ???????????? ? ??????????
????????? ???? ?????, ??? ????? ?????? ? ???????????? ??????? [4] ? ?????? [13] ????? ??????????. ??? ?????????? ????? ???? ???????
? ??????? ?????? ??????? ????????.
????? ?????????? ????????, ???????????? ? ??????????? ????? ??????????? ????????? ???? ?????, ????????? 23,4 %. ????????? ?? ??? ???????? ?-?????????? (16,5 %),
????????-4-??-3-?? (5,0 %) ? ????????-3,5????-7-?? (1,9 %). ?-?????????? ?????????? ?
?????????? 5 % ? ??????????? ??????? ?????????????????? ????????? ???? ???????????
Larix Decidua [14]. ??????????? ??????????
?-?????????? ???????? ???????? ??????????? ??????? ???????? ??????????? ?????-
????? ???????? ????????? ???????????? ??????? ????? [4]. ?-?????????? ?????????? ?
???????? ???????????????????????? ????????
? ??? ??????? ? ?????????? ????????? ??????????? ???????? (???????? ?????????? ?).
C???????-4-??-3-?? ??? ????????? ? ??????? ??????????? ? ???????? ?????????? ?????? ?????????? ??????? (Hedysarum theinum
Krasnob.) [15].
? ??????????? ????? ??????????? ????????? ???? ????? ?????????? ?????????????? ?????????? ???????????? ????????????
- ??????????? ????? (0,33 %). ???????????
???????? ???, ??? ?? ?????? ? ?????? ?????
???? ????? ??????????, ??????, ???? ? ????.
?????????? ??? ?????????? ? ??????????? ??
???? ?????????. ????????? ? ???? ????????? ?????? ????? Abies broxteata, ? ???????
???? ????? ???????????? ????????? 59 %.
????? ???????, ? ?????????????? ?????? ???????-????-????????????? ???????? ???????? ? ?????????? ??????? ?????? ?
??????????? ??????? ??????????? ?????????
???? ????? ??????????. ????????, ??? ????????? ???????????? ????????? ???????? ???????????? ???????? ?????????? ? ?????????????? ???????, ??????????, ?-??????????,
??????? ????? ????? ?????????? ? ????????
? ???????????????? ??????????????.
?????? ??????????
1.
2.
3.
4.
?????????? ?.?., ????????? ?.?., ?????????? ?.?., ???????? ?.?. ??????????? ???????????
???? ????? // ????? ????????????? ?????. ? 2000. ? ? 4. ? ?. 21-28.
???????? ?.?., ?????????? ?.?., ???????? ?.?., ????????? ?.?., ??????? ?.?., ??????
?.?. ?????????????? ??????????? ?????????????? ??????? ???? // ????? ? ?????????
??????????? ????????. ? 1997. ? ? 5. ? ?. 179-185.
????????? ?.?., ?????? ?.?., ???????? ?.?., ????????? ?.?. ?????????????? ??????? ?
?? ????????? ???? ? ?????? Pinus sibirica R. Mayr // ???. ???. ???. ????. ???? ????. ???.
???. ????. ? 1967. ? ? 2. ? ?. 126-129.
?????? ?.?., ?????? ?.?., ????????? ?.?., ???????? ?.?, ??????? ?.?. ?????????
?????????? ?????? ? ???????? ?????????? ????????? ???????????? ??????? ?????
?????????? // ????????? ???. ????. ? 1991. ? ???. 2. ? ?. 94-97.
# 298 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
5.
6.
7.
8.
9.
???????????? ?.?. ????????? ??????? ???? Pinus sibirica. ???????? ??????? ?????
??????. ? ??????????, 1972.
???????????? ?.?., ??????? ?.?., ????????? ?.?., ???????? ?.?. ???????? ??????? ?
????????? ????????? ??????????? ???? ?????. ???????????? ? ??????? ????? ?????????.??????????, 1973.
?????????? ?.?., ?????? ?.?., ????????? ?.?. ?????????????? ??????? ? ??
???????????????? ? ????? ?????? ????????????? ???????????? ??????? // ????. ??. ?
2000. ? ??? 374, ? 2. ? ?. 268-270.
????????? ?.?., ??????? ?.?., ?????????? ?.?., ????? ?.?. ????????????? ?????????????
?????? ??????????? ? ?????????? // ????? ? ???????????? ?????????????. ????????????
?????????. ? 2002. ? ? 7. ? ?. 9-20.
?????????? ?. ?., ??????? ?. ?., ?????? ?. ?., ???????? ?. ?. ???????????? ??????????
?????????????? ??????? ? ?? ???????????????? // ????????????????? ? ???????????
????????????. ? 2002. ? ? 2. ? ?. 9-11.
10. ??????? ?.?. ????? ????? ????????? ??????????. ? ???????????: ?????. ?????????
???????????? ????? ???, 2000. ? 664 ?.
11. ???????? ?.?., ????????? ?.?., ????????? ?.?. ????????? ?????? ?????? ????? ??????????
// ????? ??????. ??????. ? 1984. ? ?. 677-678.
12. ??????? ?.?. ?????????? ? N-??????????????? ??????? ? ??????? ?????????????
??????????????? ????????????: ???????. ???. ????. ???. ????. ? ???. ? 2007.
13. ??? ?.?., ?????????? ?.?., ????????? ?.?., ????????? ?.?. ?-????????? ? ???????
????????? Pinaceae // ????? ??????. ??????. ? 1985. ? ? 4. ? ?. 575-576.
14. Torbjцrn N., Bjцrn W. Neutral constituents of Larix Decidua bark // Phytochemistry. ? 1974. ? V.
13. ? P. 1290-1292.
15. ?????????? ?.?., ?????????? ?.?., ??????????? ?.?., ??????????? ?.?., ????????? ?.?.,
???????????? ?.?. ???????? ??????????? ??????? ?????? ?????????? ??????? ? ???????
???????-????-????????????? // ????????? ??????. ????. «????? ?????????? ? ????? ?
?????????? ?????????? ????????????? ?????». ? ???????. ? 2005. ? ?. 452-455.
# 299 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
Chromato-Mass-Spectrometric Investigation
of Chemical Composition of Pinus Sibirica Bark Hexan Extract
Anna I. Butylkinaa, Vladimir A. Levdanskiia, b,
Galina S. Kalachevac, Boris N. Kuznetsova, b
a
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
b
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
c
Institute of Physics, SB RAS,
Akademgorodok, Krasnoyarsk, 660036 Russia
Using chromato-mass-spectrometry the information on chemical composition of pinus sibirica bark
hexan extract was received. It was established, that the basic components of a neutral fraction of an
extract are isocembrol (thunbergol) (30,1 %), ?-sitosterol (16,5 %) and arachidyl alcohol (10 %), and
acid fraction ? lambertianic acid (40,2 %), palmitic acid (12,1 %) and ethyl ether of lignoceric acid
(7,6 %).
Keywords: pinus sibirica bark, hexan extract, acid fraction of hexan extract, neutral fraction of hexan
extract.
# 300 #
. 10. 2000.
10. ????????? ?.?., ???????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?. ??????
????????? ????????? ??????????. ?????? ?? ? 2324700. ?????. 20. 05. 2008.
# 284 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ??????????, ??????? ?. ???? ?????????????? ????????? ???????? ? ????????? ?????????
Catalutic Oxidation of Betulin and Betulin Diacetate
with Ecology Friendly Reagents
Tatiana B. Khlebnikovaa, Zinaida P. Paia, Boris N. Kuznetsovb,c,
Yulia V. Mattsata, Svetlana A. Kuznetsovab,c,
Polina V. Berdnikovaa, Galina P. Skvortsovab
a
Boreskov Institute of catalysis
5 pr. Lavrentieva, Novosibirsk, Russia 630090
b
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
c
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
The conditions of betulin and betulin diacetate oxidation with 35 % H2O2 into their epoxides were
studied. In the two-phase water-organic medium the oxidation reactions are carried out at mild
conditions: atmosphreric pressure and temperature 60-80 °C. The reaction of betulin diacetate
oxidation was realized with high yield of epoxide (90 %) and degree of the conversion 98 % in the
presence of soluble catalyst [CH3(n-C8H17)3N]{PO4[WO(O2)2]4}.
Keywords: phase-transfer catalysis, oxidation, betulin, betulin diacetate, hydrogen peroxide,
peroxopolyoxotungstenphospate complexes.
# 285 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ?????????, ???????? ?. ?????????? ???????? ? ?????????? ??????????? ???????????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 286-292
~~~
??? 547.595 + 676.164
???????? ? ?????????? ??????????? ??????????
?? ???? ???? ??????
??????? ?. ??????????, ???????? ?. ??????????,?,
?????? ?. ??????????, ?????? ?. ??????*
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
??????????? ??????, ????????? ? ??????????? ???????? ?????????, ??????????
?????????????? ? ???????? ?????????? ???? ???? ??????. ????????? ?????? ?????????????
?????????? ? ?????????????? ??????? ? ????????, ??????????????? ??? ??????????????? ?
?????????? ?????????? ??????????????? ??????? ? ???? ? ?????????. ???????????, ???
???????? ????????? ?? ???? ????????????? ????????? ???????????? ???????????????.
???????? ?????: ??? ???? ??????, ?????????????? ? ???????? ?????????, ?????????????,
?????????, ????????.
????????
??????????? ?????????????? ?????????
? ????????? ????????? ? ?????????? ????????????. ????? ????????? ??????? ???????????? ?????? ????? ???????? ?????????????
?? ???? ??????? ?????????????, ????????
??? ? ???????????? ??????????? ???????????????? ? ?????????? [9, 10]. ?????? ????????? ?????????? ???????????? ????????????
??????? ??????????????? ????????????? ?????? ??????????????? ????????????? ?????
??? ????????? ???????????????. ??? ???????
??????????, ?????????? ?????????? ?????????? [1, 2]. ??? ????????????? ????? ?????????????? ?????? ????????, ???????????? ??
????? ?????????, ??????? ????????? ? ?????
[3-8]. ???, ? ???????? ???????????? ?????????? ??????????? ??????????? ???????????
????????????? ????? «?????????» ?? ??????
???????????? ???????. ?????? ???????? ???????? ??????? ??????????? ?????????? ?
???????? ????? ??????????? ? ????????????-
??????? ?????????? ??????? ??????????? ??????????? ???? ?????? ??? ?????????? ??????
????????? ????????? ?? ??????? ???????? ?????????? ???? ???? ?????? ? ????????? ????,
????????????? ??? ????????????? ? ???????
????????????? [11-13].
????? ?????? ???????? ???????? ???????
????????? ?? ???? ???? ??????, ?? ???????????? ???????? ????????????? ??????????
??? ??????? ???? ????????? ? ????????? ??
*
1
Corresponding author E-mail address: shchipko@krsk.info
© Siberian Federal University. All rights reserved
# 286 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ?????????, ???????? ?. ?????????? ???????? ? ?????????? ??????????? ???????????
?????????? ????????????? ??????????????
«?????????».
????????????????? ?????
???????? ?????? ??? ????????? ???????? ???-1 ??????? ??? ???? ?????? ????????
(Betula pendula Roth.) ?????????? ??????? (%
?? ????? ????????? ?????? ????): ???????????? 48,8-49,1; ?????? 33,1-34,2; ??????????????? ???????? 13,1-13,7; ???? 2,4-3,4. ??? ????????? ???????? ???-2 ????????????? ???????
??????? ???????????????? ?????????? ????
?????????? ?????????????? (??????, ??????????, ???????????, ????). ?????? ??????? ?????
? ?????????? ?????????, ? ????? ???????????????? ?????????? ???? ????????????? ?????????????? ????????? ?? ???????????? ?
????? ????????? ????????? [14].
???????? ??? - 1 ? ??? - 2 ???????? ?????????? ???????????????? ????? 2 %-???
????????? NaOH ??? ??????????? 60 °?, ??????????? 5, ????????????????? 1 ? ??? ?????????????.
???????? ?????????? ????????? ????????? ?? ?? ??????????? ????????? ????????
? ???????, ????????????? ??????????????
??????????? ??? ???????????? ???????????????: ??????????? ?????, ???????????
?????????????????? ??????????, ? ????????
? ??? ?????? ?????????????????? ?????????? ???????? ?????????? [15, 16]. ????????????? ????????? ??????????? ??????????
????????? ? ????????? ???? ???????? ??????,
??????????? ? ???? 6217-74.
????????? ????? ??? ??????????? ????????? V??? ?????????? ?? ?????????? ???????? ? ????????? ?? ???????: V??? = (m1 - m)
/(m??), ??? m ? ????? ??????? ???????, ?; m1 ?
????? ??????? ???????, ???????????? ?????????, ?; ? ? ????????? ????????, ?/??3.
1
??-???????1 ??????????? ??????????
??????? ?? ??????? «Specord-75 JR? ? ??????? 400-4000 ??-1. ?????????????? ?????????? ??????? ?????????????? ? ???????? ?
????????? ?? ????. ?? ???? ?????? ?????????? ??????????? ??????? ? ????????? ????
??????????.
? ???????? ??????? ????????? ??? ??????
??????????? ??????????? ?????????????
????? «?????????», ????????? ??????????
????????? ????? ?????????????? ? ????????
?? ???? ???? ?????? ??????? [10, 12, 17].
?????????? ???????????
?????? ? ???????? ????????? ????????? ?? ????
?????????? ???????? ?? ???? ???? ?????? ???????????? ????? ??????????????? ????????? ??????-??????????? ?????
? ?????????? ?????? ?? ????? 200-250 ???.
?????????? ?? ?????? ??????? ??????????
6,8±0,2. ?????????? ???????? ???????????
? ???????? ????????? ?????????? (% ?? ?????
????????? ?????? ????????): ????????????
? 21,6-26,3; ?????? ? 27,9- 49,6; ??????????????? ???????? ? 1,1-3,8; ???? ? 1,6-2,1. ???????? ???-1 ? ???-2, ?????????? ?? ??????????
????????? ????????? ? ???? ? ???????? ??????? ??? ??????????, ?????????? ???????????
??????? ? 49,6 ? 27,9 % ? ?????????? ??????????????? ??????? ? 3,8 ? 1,1 % ??????????????. ???? ???? ??????????? ???, ??? ??? ???????????????? ?????????? ???? ? ??? ?????
????????? ?????????? ?????????? ???????
? ?? 20,2 % ? ??????????????? ??????? ? ??
1,5 [11]. ?? ?????????? ????????????? ???
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????????? ?????? ?????????????? ????????? ? ??????? ????, ?????, ?????????????
????????? ????????? ?.?. ???????? (???? ?? ???)
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??? ??????? ??????? ??? ??????????) ?????
???????????? ??????? ?????????? 59-29 %
?? ????? ????????. ???????? ?? ???? ???????????, ??????????? ? ??????, ????????????
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??????????????? ??????????????? ?????????, ????????????? ????????????? ?????
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?????? ???????? ?????????? ?????? ???.
????????? ????????????? ??????????? ??????? ? ?????????? ???????? ????????? ???????? ???-1 ? ???-2, ?????????? ?? ?????????
???? ? ???, ??????????????, ??????????, ???
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?????? ? ???????? ?????? ?????? ??? ???
???? ???????? ??????????? ?????????. ???
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???????? ????????? ????????? ? ????????
???????? ??????????.
??????? ? ??????? ??????????? ???? ?
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?????????? ??????????? ??????? ? ????????????? ??????? ? ?????? ?????? ????????. ????????? ? ?????? ?? ???????????
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?? ???? ???? ?????? ? ???????? ??????? ???
?????????? (???)
???????
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,%
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? ?????????? ?????? ?????????????? ?????
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?? ????????? ?????? ????????? [12].
?????? ??-????????????? (???. 1) ??????????, ??? ?????????? ???????? ?? ????
???? ?????? ???????? ??????? ???????
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????????????????? ????????????. ? ?????????? ???????? ???-1 ???????????? ?????? ??????????, ??????????? ??? ?????????
?????????????, ????????????? ? ?????????,
?????????????, ???????????? ?????????????? ????? (???. 1, ?????? 2).
????????? ??-???????? ??????? ???????? ???-1, ??????????? ?? ????, ? ???????
??????????, ??????????? ?? ????????????
???????, ??????????, ??? ?????? ?????????????? ????? ??? ???? ???? ????????? ??
?????? ??????, ???? ? ??????? ??? ????????,
????????? ? ????????????? ??????? ????????? ?????. ? ??????? ?? ??????????, ?
??-???????? ??????? ???????? ?? ???? ?????????? ?????????????? ?????? ??????????
??? 1735 ??-1, 1620 ??-1 ? 883 ??-1, ????????????? ?????? ?????????? ??? 1712 ??-1 ?????????, ? ?????? ?????????? ??? 1057 ??-1
??????????? ???????????.
# 288 #
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???. 1. ??-??????? ?????????? (1) ? ???????? ???-1 (2)
?????????? ?????? ???????? ???-1 (Cdaf
64,0; Hdaf 6,8; Sdaf??? 0,03) ???? ?????????? ??
?????????? ???????? ? ???????? ?? ??????????, ????????????? ?? ?????????? ?????????? ????????? ????? ?? ??? (Cdaf 68,9; Hdaf
6,1; Sdaf??? 0,07), ?? ???????? ? ??? ???? ?????? ????.
??????????? ???????? ???????? ?????????? ?? ????
????????????, ????????????? ??????????? ?????????? ???????? ?????????? ??
???? ? ???????? ???????????????, ????????:
????????? ???????????? ?????? ? ?? ????
20 ??/?; ??????????? ????????? ??????? ????????????? ???????, ???????? ????????;
??????????? ?????????? ?????????? ?????????? ??????????????? ??????? ? ?? ?????
5 % ? ???? ? ?? ????? 3 % ?? ????? ????????. ??????????? ??????????? ???????????
? ????????? ????????? ????????????? ???
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????????????? ??????? ???????????????,
?? ????????, ??????????? ???????? ???????????? ??????????? ????????????? ?
?????? ?????????????? ??????? ????????
??????? [18].
? ????. 2 ????????? ???????? ?????????????? ???????????, ???????????? ?????????? ???????, ? ???????? ????????? ??
???? ????????? ????.
????????? ??????????? ?????? ??????????, ??? ?? ???????? ??????????????? ?????????? ?????????????? ?? ???????? ???????????? ????????. ???????? ?????????
???????????? ?????? ???????????? ? ???????? ???????? 38-65 ??/?, ?????????? ? ?????????? ??? ?????????? [10]. ?????????????
???????? ?? ???? ????????? ???? ?? ?????????? ? ????????? ????????? ?????????????
???????? ??????????. ?????? ??????????
?????????? ?? ??????? ??????? ??????? ???????? ? ???????? ???????? ??? ?????? ????????? ??????????????? ? 5-100 ??/? [9].
?????????? ?????????? ??????????????? ??????? ? ???? ? ???????? ????????
????? ?? ????????, ?????????????? ???????????? ???? ?????? ??????????????. ?????????????? ?????????? ???? ???????????
???????????????? ?????????????? ??????????? [15]. ??????????? ???????????? ????????, ??? ?? ?????????? ?????????? ??????????????? ??????? ? ????????? ? ??????????
????????? ??????? ?? ???? ????????? ????-
# 289 #
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?? ???? ???? ?????? (???)
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?.?????????, ?.80.1211.3
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?? 001047/03-2002
?????????, ??«???????»,
?.?.-?????????, ?.80.1211.3
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1,5 ± 0,1
2,6 ± 0,1
43,2 ± 1,7
57,1 ±1,5
78,7 ± 6,5
3,8 ± 0,1
2,3 ± 0,2
6,9 ±0,3
29,2 ± 1,4
38,3 ± 1,2
76,3 ± 5,4
3,9 ±0,1
1,4 ± 0,1
4,5 ± 0,3
17,9 ± 1,3
48,9 ± 1,8
77,2 ± 5,9
4,5 ± 0,2
1,6 ± 0,1
3,8 ±0,2
27,3 ± 1,2
58,9 ± 2,5
59,1 ± 3,3
5,2 ± 0,3
2,1 ± 0,2
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27,9 ± 1,5
58,7 ± 2,1
50,6 ±2,8
W ? ?????????? ?????, A ? ????, ?? ? ??????????????? ?????????, A I ? ????????? ????, ? ?? ? ????????????
2
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? ???????? ??????? ??? ??????????, ??????????????, ??????????? ?? ?????????? (????.2).
???? ????????????? ?????? ???????????????? ?????????????? ???? ???????????? ????????????? ????????? ??????????? ???????
????? ??????????????? ?????????, ???? ?????????? ??? ????????, ?????????? ??? ???????????????? ???????????????, ?????????????
??????????? ????????????? ???????????
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???????????? ?????? ??????????????? ?????????? ???? ?? ???????? ???????????.
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?????????? ?? ????????? ????????? ????????, ??? ????????????? ??????? ???????????
??????????? ????????? ?? ???????? ??????????? ???????. ???????? ?? ???? ????????
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????????? ???????? ??. ??? ???? ??????????-
??? ???????? ????????????? ??????? ?????????? ? ????????? ?????? - ?? 134,9 ??/?.
?? ????????? ????????? ?????? ????????
???????? ????????? ???????? ??????????,
?? ???????? ?? ??????? ????????????????,
?????????? ? ?????????? [9]. ?? ???? ??????
???????? ????????? ????? (11,4 - 12,3 ??/?)
???????? ?? ???? ???? ?????? ?????????????? ??? ??????????? ?????? ????????.
?????? ???????????? ????? ??????????????
? ?????? ???????????? ?????????? ? ???????????? ????? ???????? ?????????????? ?
?????????? ??????? ?????? ?????????? ?????
? ??????? ?????????????, ???????????? ???
??????????? ???????????????? ??????????
???????? ? ???????? [9, 19].
????????? ???????????? ????????????? ????????? ???????? ???????? ?? ????????????????? ???? ???? ?????? ??? ??????
?????????-???????? ????????? ? ???????????? ?????. ???????????, ??? ??????????? ???????? ?? ???? ????????????
??????????? ????????????? ??? ??????
???????? ????????? ? ?? ????????? ????????? ???????. ?????????? ?????????? ????????? ????????????? ???????? ?? ???? ????
# 290 #
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??????? ?. ?????????, ???????? ?. ?????????? ???????? ? ?????????? ??????????? ???????????
?????? ??? ?????????? ? ??????????? ? ???????? ???????????????.
??????????
???????????, ??? ???????? ????????? ???? ???? ?????? ? ???????? ??????? ???
?????????? ????????????? ??????????????
???????? ? ???????? ?? ???????? ?????????.
??? ???? ??????????? ?????????? ????????? ???????? ?? ???? ????????????? ????????????? ?? ????????? ? ???????? ?????,
?????? ??? ??????? ?? ???????????? ??????
????????????? ? 1,5 -2,9 ????, ????????, ??
???? ?????????? ?????? ???????.
????????????? ?????? ???????????????
?????????? ???? ????????????? ?????????????? ???????? ? ???????? ?????????? ???-
???? ? ?????????? ??????????????? ???????
? ???????? ???-2 ?? ????????? ? ?????????
???-1, ??? ???????? ??? ?????? ???????????,
?? ???? ?????? ?? ??????????? ? ??????????? ?????????????? ??????????? ?????????
?????????.
????????, ??? ????????????? ?????????? ????????? ?? ???? ???? ?????? ?? ????????, ??????????????? ??????????????
???????????, ? ????? ?????????? ?????????? ??????????????? ??????? (1,1-3,8 %) ?
???? (1,6-2,1 %) ????????????? ???????????,
????????????? ? ???????????????.
?? ?????? ??????????? ???????, ????????? ? ??????????? ????????? ???????? ????????? ?? ???? ????????????? ????????????
???????? ?????????????? ???? «?????????».
?????? ??????????
1.
2.
3.
4.
5.
6.
7.
8.
9.
??????? ?.?., ??????????? ?.?. ??????????? ?????? ???????????? ? ???????. ?????,
1983. ? 182 ?.
???? ?. ??., ????? ?.?., ????? ?. ???????? ? ?? ??????????? ?????????? / ??? ???. ?.
?????????. ? ????, 1989. ? 398 ?.
??????? ?.?. ??????-?????????? ???????? ? ?????????? ??????????????? ?? ??????
????????????? ???????? ?????: ???????. ???. ? ????. ???. ????. ????, 1991. ? 20 ?.
???????? ?.?., ?????? ?.?., ???????? ?.?. ??????? ??????? ?????? ? ???????????
???????????? ?????????? ?? ????????? ????????? ? ????????????? ????????? // ?????????????????????? ??????. ? 2000.-?. 34. ? ? 5. ? ?. 44-47.
???????? ?.?., ???????? ?.?., ???????? ?.?, ????????????????? ?????????? ???????
???????????? ?????????? ?? ?????????? ??????? // ??????-???????????????? ??????. ?
2000. ? ?. 34. ? ? 12. ? ?. 38-40.
?????? ?.?., ??????????? ?.?., ??????? ?., ??????? ?.?., ????? ?.?., ?????? ?.?.
??????? ??????? ? ????????? ??????????? ?? ?????????????? ? ??????????? //
????????????? ? ????????????????? ?????. ? 2004. ? ?. 40. ? ? 3. ? ?. 113-139.
??? ?.?., ??????????? ?.?., ???????????? ?.?. ????????????? ?? ?????? ????????
???????????? ????? ? ??? ???????????????? ??????????? ?????????????? ?????????????
// ??????-???????????????? ??????. ? 2007. ? ?. 41. ? ? 1. ? ?. 21-26.
????? ?.?., ???????? ?.?., ??????? ?.?., ????????? ?.?., ????????? ?.?. ??????? ?.?.
??????? ?????????-?????????? ??????? ?????????????? ????? ?? ?? ???????????????
????????????? // ??????-???????????????? ??????. ? 2007. ? ?. 41. ? ? 6. ? ?. 44-48.
??????? ?.?., ???? ?.?., ?????? ?.?., ??????? ?.?. ????????????? /??? ???. ?.?.
????????. ? ?.: ????? ??????????? ??????????, 1991. ? 328 ?.
# 291 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? ?. ?????????, ???????? ?. ?????????? ???????? ? ?????????? ??????????? ???????????
10. ?????? ?.?., ???????? ?.?., ?????? ?.?. ??????????? ????????? ?? ??????? ????????????
???????????? // ????? ? ????????? ??????????? ????????. ? 1994. ? ?. 2. ? ? 2-3. ? ?. 559-581.
11. ????????? ?.?., ????? ?.?., ???????? ?.?., ?????????? ?.?., ????????? ?.?., ?????????
?.?. ????????? ? ???????? ??????????????? ?? ???? ????????? ???? // ????? ?????????????
?????. ? 2004. ? ? 2. ? ?. 25-29.
12. ????????? ?.?., ????? ?.?., ????????? ?.?., ???????? ?.?. ????????? ???????????????
?? ??????? ?????? ?????? // ????? ????????????? ?????.-2005. ? ? 1. ? ?. 65-70.
13. ????????? ?.?., ????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?., ????? ?.?.
????????????? ? ?????? ??? ?????????. ?????? RU 2311954, 2006.
14. ?????????? ?.?., ????????? ?.?., ???????? ?.?. ???????????? ?????? ?? ?????
????????? ? ?????????. ?.: ????????, 1991. ? 319 ?.
15. ??????????????? ?????????? ????. ???. 2. ????? ?????? ???????. ?????????????
???????????? ?????. ?.: ????????, 1990. ? 679 ?.
16. ?????????? ?.?. ?????? ????????????? ??????????? ??????????????? ? ?? ?????????????
???? // ??????-???????????????? ??????. ? 2003. ? ?. 37. ? ? 5. ? ?. 28-32.
17. ????????? ?.?. ??????? ???? ?? ??????? ???????? ? ????????? ??????? ??????????,
??????????? ?? ????? ????????????? ???? (?? ??????? ???? ???? ?????? ? ?????? ????):
???????. ???. ? ????. ????. ????. ? ??????????, 2007. ? 19 ?.
18. ???? ?.?., ????????? ?.?. ???????????? ???????? ? ???????????? ????. ?.: ????????,
1984. ? 298 ?.
19. ?????????? ?.?. ????????????? ???? ?????????????? ? ????????? ???????? ? ????????.
?.: ?????, 1977. ? 184 ?.
Properties and Application of the Sorption Materials
from Outer Birch-Bark
Evgeniya V. Veprikova, Svetlana A. Kuznetsova,
Galina P. Skvortsova, Maxim L. Shchipko
Institute of Chemistry and Chemical Technology SB RAS,
42 K. Marx st., Krasnoyarsk, 660049 Russia
Siberian Federal University,
79 Svobodny, Krasnoyarsk, 660041 Russia
Composition, structure and sorption properties of the sorbents, obtaining by outer birch-bark
extraction and alkaline treatment have been studied. Estimations of their sorption activity with the use
of marker substances for enterosorbents and contents of water-soluble residual substances and ash in
sorbents have been made. It was found that the properties of the sorbents from outer birch-bark are
corresponding to properties of the industrial enterosorbents ?Polifepan? type.
Keywords: outer birch - bark, extraction and alkaline treatments, enterosorbent, structure,
properties.
# 292 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
Journal of Siberian Federal University. Chemistry 3 (2008 1) 293-300
~~~
??? 543:585.2
???????-????-?????????????????? ???????? ???????????
??????? ??????????? ????????? ???? ?????
???? ?. ??????????, ???????? ?. ???????????,?,
?????? ?. ?????????, ????? ?. ?????????,?*
?
???????? ????? ? ?????????? ?????????? ?? ???,
??. ?. ??????, 42, ??????????, 660049 ??????
?
????????? ??????????? ???????????,
??. ?????????, 79, ??????????, 660041 ??????
?
???????? ????????? ?? ???
?????????????, ??????????, 660036 ?????? 1
Received 4.08.2008, received in revised form 22.09.2008, accepted 29.09.2008
??????? ???????-????-????????????? ???????? ???????? ? ?????????? ??????? ???????????
????????? ???? ????? ?????????? (Pinus sibirica Du Tour). ???????????, ??? ?????????
???????????? ??????????? ??????? ????????? ???????? ?????????? (thunbergol) (30,1 %),
?-?????????? (16,5 %) ? ?????????? ????? (10 %), ? ?????? ??????? ? ?????????????? ???????
(40,2 %), ????????????? ??????? (12,1 %) ? ???????? ???? ?????????????? (??????????????)
??????? (7,6 %).
???????? ?????: ???? ?????, ?????????? ????????, ?????? ??????? ??????????? ?????????,
??????????? ??????? ??????????? ?????????.
????????
???????? ??????????? ??????? ????????? ??????? ???? ??????? ????? ????????
????????? ???????????? ????? ?????. ???????? ?????? ?????????? ?????? ???????
????? ? ??????? ????????? ???? ????? [1,
2], ???, ????? ? ???????????. ???????? ?????? ????? ?????????? ????????? ?????? [3],
? ??????? ??????? ?????????? ????????????? ?? ????? ????????, ????????????????
???????????? ????????, ?? ????? ????????
?????? ???????? ?????????????? ???????, ?
?? ??????????? ????? ?????? ? ?? ????????? ????.
*
1
?????????? ?????? ????????? ???????
???? ????? ?????????? ?????? ?? ??? ????????. ? ?????? [4], ? ?????????????? ????????????? ?? ?????????? ? ???????????
???????? ??????? ??????? ??? ?? ???????
????-5, ???????? ?????? ? ??????? ????????
????????? ???????????? ??????? ????? ??????????.
??? ??????????????????? ???????? ????????? ???? ????? ?? ???????????
????????, ? ??????????? ???????? ?????????? ??????? ??????? ????????????? ?? ??????, ??- ? ??-?????????????
?????????? ???? ??????????????? ??????
Corresponding author E-mail address: inm@icct.ru
© Siberian Federal University. All rights reserved
# 293 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
(?-?????????, ????????, ?????????, ?????????????? ? ???????????) ? ??? ?????????: 4,4?-?????????????????? ? 3,5,4???????????????????? (???????????) [5,6].
????? ?????? ???????? ???????? ??????????? ??????? ??????????? ????????? ????
????? ??????? ???????-????-?????????????.
????????????????? ?????
? ?????? ? ???????? ????? ????????????
???? ????? ?????????? (Pinus sibirica Du Tour),
?????????? ?? ????????? ??????? ?. ??????,
???????????? ?? ??????? 1,0 - 2,0 ??. ??????
???????????? ???? ???????? ? ????. 1.
????????? ?????????. ??????????
????????-????? ???? ????? ????????? ? ???????? ????????, ???????????? ? ??????, ?????
?????????? ? 20 ?. ?? 110 ? ???? ????? ?????
???????? ???????????? ???????? 6,5 ? ????????? ? ???? ?????-??????? ?????? ????? ??
????????? ???????. ????? ????????? 5,9 %.
????????? ?????????. ?????????? ??????????? ????????? ?? ?????? ? ???????????
???????????? ????????? ????????? ???????. ???????? (6,5 ?) ?????????? ? 100 ??
0,5 ? ?????????? ???????? ?????? ????? ? ????????? ? ????? ? ???????? ?????????????
?? ??????? ???? ? ??????? 1 ?. ?? ?????????
?????????? ??????????? ????? ?????????
????? ? ?????? ????. ?????????? ????? ?????????????? ?????????? ?????? ??????
? ??????????? ???????. ??????? ???????
?????????? ? ?????? ?? Na2SO4. ???? ????????, ??????? ?????? ?? ??????????? ????.
????? ??????????? ??????? ???????? 1,7 ?
(26,1 %). ?????? ??????? ??????????????
???????????? ??????? ???????? ?? ??????????? ????? (?? 4), ?????????? ????? ?????????????? ?????? ??????, ???????? ??????????, ?????? ??? Na2SO4, ???? ????????,
??????? ?????? ?? ??????????? ????. ?????
?????? ??????? ???????? 4,2 ? (64,6 %).
???????-????-?????????????????? ?????? ?????????? ?? ??????? ????????????
GCD Plus (Hewlett-Packard, USA) ? ????????????? ????-???????? (HP MSD). ???????????? ??????????? ??????? HP-5S ?????? 30
?, ?????????? ????????? ? 0,25 ??. ???????
???????????????????: ??? ???????? ? ?????;
???????? ?????? 1 ??/???; ??????????? ????? ??????? 220 ??; ????????? ??????????? 50
?, ????????? ??????? ??????????? ?? 320
? ?? ????????? 8 ??/???; ??????????? ??????????? ????? 230 ??; ??????????? ?????????
????? 175 ??; ????? ???????????? ????? ???
70 eV; ???????? ???? ?? 45 ?? 450 m/z. ???????????? ?????? ??????? ?? ????????? ?????? ??????????? ? ?????? ????-????????
? ???????????????? ??????? ??????????
????-????????????.
?
?
?????????? ? ??????????
????????, ??? ????????? ????????
??????? ????? ???????? ???????????? ????? ??????? ????? ?????????? ??????????,
??????, ?????, ?????????? ? ???????????? ?????? ??????, ???????? ??????. ????????????? ?????? ??????? ??????????? ??
??????? 1. ?????????? ?????? ???? ????? ??????????
??????????
??????, % ???. ?? ?????
????????? ????? ????
?????????
??????
?????????????
????????
27,7
32,3
16,7
# 294 #
????????????
??????????????????
???????????????????
?????????
18,7
26,2
2,3
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
????????????? ????? ??????????? ??????????????. ????????????? ?????? ???????????-????????????? ????????? ???????
?????????? ????????? ??????? ?? ?????????????? ?????????? ? ????????????????
?? ? ?????????? ??????? ?????????. ????????????? ?????????????? ???????????
??????????? ?????????? ????? ??????????
????? ??????? ?? ?????? ? ???????????
???????.
?????????? ???????? ???? ????? ?????????? ????? ???????? ???????????? ??? ???????? ?? ??????????? ? ?????? ???????.
??? ???????? ?????????? ???????-??????????????????????? ????????????, ??????
??????? ??????????? ????????? ????????
???????? ? ?????? ??????? ??????? ?16-?26
? ?? ???????? ?????. ????????? ?? ???
???????? ?????????????? ??????? (40,2 %),
????????????? ??????? (12,1 %) ? ????????
???? ?????????????? (??????????????) ??????? (7,6 %). ?? ???. 1 ???????? ????????????? ?????? ??????? ??????????? ?????????, ?
?? ???. 2 ? ?? ????-??????. ? ????. 2 ???????
???????? ?????? ???????, ?????????????
?????????? ??????? ? ?????? ??????? ????????? 0,5 % ? ??????? ??????? ???????????????? ? ??????????? ????????? (? ???????????? ????? 85 %).
?????????????? ??????? ????????? ?
?????? ?????????? ????????????? ? ???????? ???????? ??????????? ?????????????
???. 1. ????????????? ?????? ??????? ??????????? ????????? ???? ?????
???. 2. ????-?????? ????????? ?????????? ?????? ??????? ??????????? ????????? ???? ????? ?
?????????????? ???????
# 295 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
??????? 2. ?????? ?????? ??????? ??????????? ????????? ???? ?????
????? ???????????,
???
?+
?????????????
??????????, %
????????????? (??????????????) ???????
?15?31????
19,72
256
12,1
???????? ???? ?????????????
(??????????????) ??????? ?15?31??2C2H5
19,92
284
4,2
????????????????? ??????? ?16?33COOH
20,90
270
1,6
???????? ???? ?????????????? (????????????)
??????? ?16?33COOC2H5
21,24
298
0,9
???????????????? (?????????) ???????
C17H29COOH
23,00
280
6,9
???????? ???? ????????? ???????
C17H33CO2?2?5
23,12
310
4,9
????????????? (???????????) ???????
C17H35COOH
23,30
284
0,6
???????? ???? ??????????? (?????????????)
??????? C17H35CO2?2?5
23,55
312
0,9
???????? ???? ?????????????
(?????????????) ??????? C18H37COOC2H5
24,79
326
0,7
???????? ???? ?????????? (???????????)
??????? ?19?39CO2?2?5
26,94
340
5,4
?????????????? ???????
28,52
316
40,2
???????? ???? ??????????? (?????????)
??????? C21H43CO2?2?5
30,14
368
5,4
???????? ???? ??????????????
(??????????????) ??????? C23H47CO2?2?5
33,03
396
7,6
???????? ???? ?????????????? (???????????)
??????? C25H51COO?2?5
35,68
424
1,9
?????????
??????? ???? ? ?????? [3] ?????, ??? ?????
???????? ???????? ???????????? ???????
?????? ???????? ????????? ???????????? ??????? ????? ?????????? [4].
????????????? ????????? ??????? ?
?????????????? ??????? ? ?????????????????? ???????????? ?????????? [7]. ???????? ?????? ? ?????????? ?????????? ????????? ???????? ??????????? (??????????
? ?????????), ?????????? ?????????????
????????????? ???????????, ? ??? ????? ?
????????????????? ????????? [8]. ????????
??????????? ?????????????? ???????, ?????????? ???????????????? ? ????????????????? ????????? [9].
??????????? ????? ??????????? ????????? ???????? ????????? ??????????? ? ????????????? ??????. ????????? ???????????? ??????????? ????? ??????????? ?????????
???? ????? ???????? ?????????? (thunbergol)
(30,1 %), ?-?????????? (16,5 %) ? ??????????
????? (10 %). ?? ???. 3 ???????? ????????????? ??????????? ??????? ??????????? ?????????, ? ?? ???. 4 ? ?? ????-??????. ? ????. 3 ????????? ?????????? ??????????? ???????,
??????? ???????????????? ? ????????????
????? 85 %, ????? ?? ???????????, ???????????? ????? ? ????????????? ??????????.
????????????? ??????????? ??????????? ????? ??????????? ????????? ????????
# 296 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
??????? 3. ?????? ??????????? ??????? ??????????? ????????? ???? ?????
????? ???????????,
???
?+
?????????????
??????????, %
???????
3,58
154
0,4
?-???????
12,99
204
2,2
?????????
?-?????????
13,81
222
1,6
3,7,11-????????-1,3,6,10-?????????????????????
18,87
272
9,6
?????????? (thunbergol)
21,27
290
30,1
1-??????????? ?19?39??
28,51
284
5,0
1-????????? (?????????? ?????) ?20?41??
31,62
298
10,0
?-??????????
40,03
414
16,5
?????????-3,5-????-7-??
41,02
410
1,9
C???????-4-??-3-??
41,5
412
5,0
???. 3. ????????????? ??????????? ??????? ??????????? ????????? ???? ?????
???. 4. ????-?????? ????????? ?????????? ??????????? ??????? ??????????? ????????? ???? ????? ?
??????????? (thunbergol)
# 297 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
??????????????? ???????????? ????? ??????????, ?????????? ???????????????????
????, ??? ????????????? ?????????? ?????????? ????? 30 %. ??????? ??? ???? ??????? ?
???? ????? ??????? (Douglas fir). ??? ????????
?????????? ?? ?????????? ???????????? ?????
???????????? Pinus cembra [10], ? ???????????
?????????? ??? ???????? thunbergol. ?????????? ? ???????? ??????????? ???????????
?????? ????? ?????????? [11], ?????? ? ????
? ??????? ??????? ?? ??????????? [4]. ?? ??????????? ???????? ???????????, ?????????? ??????? ??????????????? ???????????
[12]. ?-?????????, ???????????? ? ??????????
????????? ???? ?????, ??? ????? ?????? ? ???????????? ??????? [4] ? ?????? [13] ????? ??????????. ??? ?????????? ????? ???? ???????
? ??????? ?????? ??????? ????????.
????? ?????????? ????????, ???????????? ? ??????????? ????? ??????????? ????????? ???? ?????, ????????? 23,4 %. ????????? ?? ??? ???????? ?-?????????? (16,5 %),
????????-4-??-3-?? (5,0 %) ? ????????-3,5????-7-?? (1,9 %). ?-?????????? ?????????? ?
?????????? 5 % ? ??????????? ??????? ?????????????????? ????????? ???? ???????????
Larix Decidua [14]. ??????????? ??????????
?-?????????? ???????? ???????? ??????????? ??????? ???????? ??????????? ?????-
????? ???????? ????????? ???????????? ??????? ????? [4]. ?-?????????? ?????????? ?
???????? ???????????????????????? ????????
? ??? ??????? ? ?????????? ????????? ??????????? ???????? (???????? ?????????? ?).
C???????-4-??-3-?? ??? ????????? ? ??????? ??????????? ? ???????? ?????????? ?????? ?????????? ??????? (Hedysarum theinum
Krasnob.) [15].
? ??????????? ????? ??????????? ????????? ???? ????? ?????????? ?????????????? ?????????? ???????????? ????????????
- ??????????? ????? (0,33 %). ???????????
???????? ???, ??? ?? ?????? ? ?????? ?????
???? ????? ??????????, ??????, ???? ? ????.
?????????? ??? ?????????? ? ??????????? ??
???? ?????????. ????????? ? ???? ????????? ?????? ????? Abies broxteata, ? ???????
???? ????? ???????????? ????????? 59 %.
????? ???????, ? ?????????????? ?????? ???????-????-????????????? ???????? ???????? ? ?????????? ??????? ?????? ?
??????????? ??????? ??????????? ?????????
???? ????? ??????????. ????????, ??? ????????? ???????????? ????????? ???????? ???????????? ???????? ?????????? ? ?????????????? ???????, ??????????, ?-??????????,
??????? ????? ????? ?????????? ? ????????
? ???????????????? ??????????????.
?????? ??????????
1.
2.
3.
4.
?????????? ?.?., ????????? ?.?., ?????????? ?.?., ???????? ?.?. ??????????? ???????????
???? ????? // ????? ????????????? ?????. ? 2000. ? ? 4. ? ?. 21-28.
???????? ?.?., ?????????? ?.?., ???????? ?.?., ????????? ?.?., ??????? ?.?., ??????
?.?. ?????????????? ??????????? ?????????????? ??????? ???? // ????? ? ?????????
??????????? ????????. ? 1997. ? ? 5. ? ?. 179-185.
????????? ?.?., ?????? ?.?., ???????? ?.?., ????????? ?.?. ?????????????? ??????? ?
?? ????????? ???? ? ?????? Pinus sibirica R. Mayr // ???. ???. ???. ????. ???? ????. ???.
???. ????. ? 1967. ? ? 2. ? ?. 126-129.
?????? ?.?., ?????? ?.?., ????????? ?.?., ???????? ?.?, ??????? ?.?. ?????????
?????????? ?????? ? ???????? ?????????? ????????? ???????????? ??????? ?????
?????????? // ????????? ???. ????. ? 1991. ? ???. 2. ? ?. 94-97.
# 298 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???? ?. ?????????, ???????? ?. ??????????,.. ???????-????-?????????????????? ???????? ????????????
5.
6.
7.
8.
9.
???????????? ?.?. ????????? ??????? ???? Pinus sibirica. ???????? ??????? ?????
??????. ? ??????????, 1972.
???????????? ?.?., ??????? ?.?., ????????? ?.?., ???????? ?.?. ???????? ??????? ?
????????? ????????? ??????????? ???? ?????. ???????????? ? ??????? ????? ?????????.??????????, 1973.
?????????? ?.?., ?????? ?.?., ????????? ?.?. ?????????????? ??????? ? ??
???????????????? ? ????? ?????? ????????????? ???????????? ??????? // ????. ??. ?
2000. ? ??? 374, ? 2. ? ?. 268-270.
????????? ?.?., ??????? ?.?., ?????????? ?.?., ????? ?.?. ????????????? ?????????????
?????? ??????????? ? ?????????? // ????? ? ???????????? ?????????????. ????????????
?????????. ? 2002. ? ? 7. ? ?. 9-20.
?????????? ?. ?., ??????? ?. ?., ?????? ?. ?., ???????? ?. ?. ???????????? ??????????
?????????????? ??????? ? ?? ???????????????? // ????????????????? ? ???????????
????????????. ? 2002. ? ? 2. ? ?. 9-11.
10. ??????? ?.?. ????? ????? ????????? ??????????. ? ???????????: ?????. ?????????
???????????? ????? ???, 2000. ? 664 ?.
11. ???????? ?.?., ????????? ?.?., ????????? ?.?. ????????? ?????? ?????? ????? ??????????
// ????? ??????. ??????. ? 1984. ? ?. 677-678.
12. ??????? ?.?. ?????????? ? N-??????????????? ??????? ? ??????? ?????????????
??????????????? ????????????: ???????. ???. ????. ???. ????. ? ???. ? 2007.
13. ??? ?.?., ?????????? ?.?., ????????? ?.?., ????????? ?.?. ?-????????? ? ???????
????????? Pinaceae // ????? ??????. ??????. ? 1985. ? ? 4. ? ?. 575-576.
14. Torbjцrn N., Bjцrn W. Neutral constituents of La
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