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223.Журнал Сибирского федерального университета. Сер. Химия №4 2014

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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Журнал Сибирского федерального университета
2014
Journal of Siberian Federal University
7 (4)
Химия
Chemistry
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Editorial Advisory Board
Chairman:
Eugene A. Vaganov
Members:
Josef J. Gitelzon
Vasily F. Shabanov
Andrey G. Degermendzhy
Valery L. Mironov
Gennady L. Pashkov
Vladimir V. Shaidurov
Vladimir V. Zuev
Editorial Board:
Editor-in-Chief
Mikhail I. Gladyshev
Founding Editor
Vladimir I. Kolmakov
Managing Editor
Olga F. Alexandrova
Executive Editor for Chemistry
Boris N. Kuznetsov
CONTENTS
Marina V. Ananyeva and Alexander V. Kalenskii
The Size Effects and Before-Threshold Mode of Solid-State
Chain Reaction
? 470 ?
Rodion V. Okunev,
Boris R. Grigoryan and Adelina I. Sharipova
Determination of Free Proteinogenic Amino Acids in Soil
Solutions by HPLC with Phenyl Isothiocyanate Derivatization
? 480 ?
Alina M. Shushenacheva and Aleksander A. Efremov
Chemical Composition of the Essential Oil from Fruits of Heracleum dissectum L. Growing in Krasnoyarsk Krai
? 487 ?
Valery Е. Tarabanko,
Marina A. Smirnova and Yulia V. Chelbina
Obtaining of Hollow Fibers of Titanium Dioxide by Interaction
of Titanium Tetrachloride with Cotton Cellulose
? 494 ?
Liubov T. Denisova, Liliya A. Irtyugo,
Vladimir P. Shereb and Viktor M. Denisov
High Temperature Heat Capacity of Bismuth-gallium Sillenite
? 504 ?
Svetlana L. Didukh and Vladimir N. Losev
Application of Zirconium Oxide and Titanium Oxide Sequentially
Modified with Polyhexamethylene Guanidine and 4,7-diphenyl1,10-phenantrolinedisulfonic Acid for Preconcentration and
Determination of Iron(II) in Natural and Mineral Waters
? 510 ?
???????? ?.?. ??????. ????????? ?.?. ???????
???????????? ??????? ?.?. ?????????
????????? ? ?????? 30.12.2014 ?. ?????? 84?108/16. ???. ???. ?. 11,7.
??.-???. ?. 11,2. ?????? ???. ?????? ????????. ????? 1000 ???. ????? 65.
?????????? ? ?? ??? ???. 660041, ??????????, ??. ?????????, 82a.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Editorial board for Chemistry:
Boris Kuznetsov ? Series Editor,
Professor, Siberian Federal University
Nicolai Chesnokov ? Associate Editor,
Professor, Siberian Federal University
Vladimir Agabekov ? Professor, Institute
of Chemistry of New Materials NAS,
Belarus
Lyubov Altunina ? Professor, Institute
of Petroleum Chemistry, Russian
Academy of Sciences, Siberian Branch
Natalia Bazarnova ? Professor, Altai State
University
Vasili Babkin ? Professor, AE Favorsky
Irkutsk Institute of Chemistry, Russian
Academy of Sciences, Siberian Branch
Vicente Cebolla ? Dr, Instituto de
Carboquimica, CSIC, Spain
Alain Celzard ? Professor, Universite de
Lorreine Institut Universitaire de Frans
Viktor Denisov ? Professor, Siberian
Federal University
Zinfer Ismagilov ? Professor, Boreskov
Institute of Catalysis, Russian Academy
of Sciences, Siberian Branch
Sergey Kachin ? Professor, Siberian
Federal University
Sergey Kirik ? Professor, Siberian Federal
University
Vladimir Likholobov ? Corresponding
Member, RAS, Institute of
Hydrocarbons Processing, Russian
Academy of Sciences, Siberian Branch
Yury Mikhlin ? Professor, Siberian
Federal University
Konstantin Neyman ? ICREA Professor,
Departament de Quimica Fisica
Universitat de Barcelona, Spain
Gennady Pashkov ? Corresponding
Member, RAS, Professor, Siberian
Federal University
Anatoly Rubailo ? Professor, Siberian
Federal University
Tatyana Ryazanova ? Professor, Siberian
State Technological University
Vladimir Sobyanin ? Professor,
Novosibirsk State University
Valery Tarabanko ? Professor, Institute of
Chemistry and Chemical Technology,
Russian Academy of Sciences, Siberian
Branch
Tatiana Shendrik ? Professor, Litvinenko
Institute of Physical Organic Chemistry
and Coal Chemistry, Ukraine
Olesya V. Popova, Viktoriya V. Sursyakova,
Galina V. Burmakina and Anatoliy I. Rubaylo
Application of Capillary Electrophoresis for Determination of
Stability constants of Complexes of Iron (III) with Sulfosalicylic
Acid with a 1:1 and 1:2 Stoichiometries
? 519 ?
Luiza F. Sayfulina,
Evgeniy A. Buluchevskiy and Alexander V. Lavrenov
Direct Synthesis of Propylene from Ethylene over PdO-Re2O7/
So42-/Zro2 Catalyst
? 527?
Irina L. Simakova, Аndrey А. Morozov,
Valery Е. Tarabanko and Mikhail Yu. Chernyak
5-Butoxymethylfurfural Catalytic Hydrogenation over Palladium
Catalysts
? 537 ?
Natalia Yu. Vasilyeva, Alexander V. Levdansky,
Anton A. Karacharov, Elena V. Mazurova,
Galina N. Bondarenko, Vladimir A. Levdansky,
Alexander S. Kazachenko and Boris N. Kuznetsov
Study of Structure of Product?s Obtained by Sulfation of
Arabinogalactan from Larch Wood with Chlorosulfonic Acid in
Pyridine
? 547 ?
Еvgeniya V. Veprikova,
Galina P. Skvortsova, Svetlana А. Kuznetsova,
Nikolai V. Chesnokov and Boris N. Kuznetsov
Study of Phosphates Sorption on the Porous Supports from
Birch Bark
? 556 ?
Andrey A. Morozov, Mikhail Y. Chernyak,
Valery E. Tarabanko and Alexander A. Kondrasenko
Preparative 5-Hydroxymethylfurfural Oxydation by Concentrated
Nitric Acid
? 567 ?
Alexander N. Zaloga, Sergey V. Burakov,
Eugeniy S. Semenkin and Igor S. Yakimov
Multipopulation Genetic Algorithm for Simulation of the Crystal
Structure from X-Ray Diffraction Data
? 573 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
????????????? ? ??????????? ???
?? ? ??77-28-726 ?? 29.06.2007 ?.
????? ???????? ? «???????? ??????? ????????????? ??????? ???????? ? ???????, ? ??????? ??????
???? ???????????? ???????? ??????? ?????????? ??????????? ??
????????? ?????? ??????? ??????? ?
????????? ????» (???????? 2010 ?.)
Anna O. Eremina, Valentina V. Golovina,
Nikolay V. Chesnokov and Anatoly A. Sobolev
Adsorption of the Volatile Aliphatic Acids from Aqueous
Solutions by Active Carbons
? 582 ?
Olga S. Shchipitsyna and Alexander A. Efremov
Features of the Essential oil Accumulation in the Angelica
Decurrens (Ledeb.) B. Fedtsch. Roots in Comparison with
Angelica Аrchangelica L.
? 590 ?
Nikolay V. Gromov,
Artem B. Ayupov, Cyril Aymonier,
Vladimir Е. Agabekov and Oxana P. Taran
Development of Solid Acid Catalysts Based on Sibunit
Carbon Material for Cellulose Transformation into
5-hydroxymethilfurfural
? 597 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
СОДЕРЖАНИЕ
М.В. Ананьева, А.В. Каленский
p=???!?/? , ?%C%!%?%"/? .--?*2/ 2"?!?%-=??/. ??C?/. !?=*?,L
? 470 ?
Р.В. Окунев, Б.Р. Григорьян, А.И. Шарипова
nC!??????,? ?"%K%??/. C!%2?,?%????/. =?,?%*,??%2 C%?"???%?% !=?2"%!= ??2%?%? b}fu ?
C!??*%?%?%??%L ??!,"=2,?=?,?L -??,?,?%2,%?,=?=2%?
? 480 ?
А.М. Шушеначева, А.А. Ефремов
j%?C%???2?/L ?%?2=" .-,!?%?% ?=??= *%!??L K%!??",*= !=???????%?%, C!%,?!=?2=????% " j!=??% !?*%?
*!=?
? 487 ?
В.Е. Тарабанько, М.А. Смирнова, Ю.В. Челбина
o%?3???,? C%?/. "%?%*%? ?,%*?,?= 2,2=?= "?=,?%??L?2",?? 2?2!=.?%!,?= 2,2=?= ? .?%C*%"%L
??????%?%L
? 494 ?
Л.Т. Денисова, Л.А. Иртюго, В.П. Жереб, В.М. Денисов
b/?%*%2??C?!=23!?= 2?C?%??*%?2? ",??32-?=??,?"%?% ?,????,2=
? 504 ?
С.Л. Дидух, В.Н. Лосев
o!,?????,? %*?,?%" ?,!*%?, , 2,2=?=, ?%?,-,?,!%"=??/. C%?,??*?=??2,????3=?,?,?%? , 4,7-?,-??,?1,10--??=?2!%?,??,?3??-%*,??%2%L, ?? *%????2!,!%"=?, , %C!??????, ?????=(II) " C!,!%??/. ,
?,??!=???/. "%?=.
? 510 ?
О.В. Попова, В.В. Сурсякова, Г.В. Бурмакина, А.И. Рубайло
o!,?????,? ??2%?= *=C,?? !?%?% .??*2!%-%!??= ?? %C!??????, *%??2=?2 3?2%L?,"%?2, *%?C??*?%"
?????= (III) ? ?3??-%?=?,?,?%"%L *,??%2%L " ?%%2?%???,, 1:1 , 1:2
? 519 ?
Л.Ф. Сайфулина, Е.А. Булучевский, А.В. Лавренов
n??%?2=?,L?%? C%?3???,? C!%C,???= ,? .2,???= ?= *=2=?,?=2%!? PdO-Re2O7/So42-/Zro2
? 527 ?
И.Л. Симакова, А.А. Морозов, В.Е. Тарабанько, М.Ю. Черняк
j=2=?,2,???*%? ?,?!,!%"=?,? 5-K32%*?,??2,?-3!-3!%?= ?= C=??=?,?"/. *=2=?,?=2%!=.
? 537 ?
Н.Ю. Васильева, А.В. Левданский,
А.А. Карачаров, Е.В. Мазурова, Г.Н. Бондаренко,
В.А. Левданский, А.С. Казаченко, Б.Н. Кузнецов
h?3???,? ?2!%??, C!%?3*2%" ?3??-=2,!%"=?, =!=K,?%?=?=*2=?= ,? ?!?"??,?/ ?,?2"???,?/
.?%!?3??-%?%"%L *,??%2%L " C,!,?,??
? 547 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Е.В. Веприкова, Г.П. Скворцова,
С.А.Кузнецова, Н.В. Чесноков, Б.Н. Кузнецов
h?3???,? ?%!K?,, -%?-=2%" ?= C%!,?2/. C%??%?*=. ,? *%!/ K?!??/
? 556 ?
А.А. Морозов, М.Ю. Черняк, В.Е. Тарабанько, А.А. Кондрасенко
o!?C=!=2,"?%? %*,????,? 5-?,?!%*?,??2,?-3!-3!%?= =?%2?%L *,??%2%L
? 567 ?
А.Н. Залога, C.В. Бураков, Е.С. Семенкин, И.С. Якимов
l3??2,C%C3? ?,%??/L ????2,???*,L =??%!,2? ?%???,!%"=?,
!??2???%?,-!=*?,%??/. ?=??/.
*!,?2=??,???*%L
?2!3*23!/
,?
? 573 ?
А.О. Еремина, В.В. Головина, Н.В. Чесноков, А.А. Соболев
`??%!K?, ??23?,. =?,-=2,???*,. *,??%2 ,? "%??/. !=?2"%!%" ?= =*2,"?/. 3?? .
? 582 ?
О.С. Щипицына, А.А. Ефремов
n?%K???%?2, ?=*%C???, .-,!?%?% ?=??= " *%!? . Angelica decurrens (Ledeb.) B. Fedtsch. " ?!="???,,
? Angelica =rchangelica L.
? 590 ?
Н.В. Громов, А.Б.Аюпов, С. Амони, В.Е. Агабеков, О.П. Таран
p=?!=K%2*= 2"?!?/. *,??%2?/. *=2=?,?=2%!%" ?= %??%"? 3???!%??%?% ?=2?!,=?= q,K3?,2 ?? C%?3???,
5-?,?!%*?,??2,?-3!-3!%?= ,? ??????%?/
? 597 ?
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 470-479
~~~
??? 544.431.7
The Size Effects and Before-Threshold Mode
of Solid-State Chain Reaction
Marina V. Ananyeva and Alexander V. Kalenskii*
Kemerovo State University
6 Krasnaya, Kemerovo, 650043, Russia
Received 12.07.2014, received in revised form 18.08.2014, accepted 00.09.2014
In this work size effects and before-threshold mode of the solid state reaction in silver azide crystals
were experimentally and theoretically researched. It was shown that if the crystal?s size decreases the
critical initiation energy density considerably increases. This is because of the bigger speed of the
electron-carriers? recombination on the crystal surfaces in comparison with the same value for the
bulk. Before-threshold mode of the solid state branched chain reaction can be observed if the energy
of the initiation is smaller than the critical value; and the carriers? diffusion length is comparable with
the sample sizes or with the area there the initiating irradiation absorbed. The results of the research
are necessary to work out the details of optical detonator.
Keywords: explosive decomposition, solid-state chain reaction, size effects, before-threshold mode,
kinetics, laser initiation.
????????? ? ??????????? ???????
???????????? ?????? ???????
?.?. ????????, ?.?. ?????????
??????????? ??????????????? ???????????
??????, 650043, ????????, ???????, 6
? ?????? ???????????????? ? ???????????? ??????????? ????????? ? ??????????? ??????
????????????? ???????????? ?????? ??????? ?????????? ?????????? ????? ???????. ????????,
??? ? ??????????? ??????? ????????? ????????? ????????? ??????? ???????? ??????????
?????????? ?? ???????? ??????????? ?????????????. ??????? ?????????? ?????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: kriger@kemsu.ru
# 470 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Marina V. Ananyeva and Alexander V. Kalenskii. The Size Effects and Before-Threshold Mode of Solid-State Chain?
???????? ??????? ? ?????????? ????????? ?????? ???? ?? ??????????? ?? ????????? ?
???????. ??????????? ??????? ????????????? ???????????? ?????? ??????? ???????????
? ??? ???????, ????? ???????????? ????? ????????? ???? ??????????? ? ????????? ???????
??? ? ???????? ?????????? ????????? ?????????, ? ??????? ????????????? ???????? ??????
??????????????? ??????????? ????????.
???????? ?????: ???????? ??????????, ???????????? ?????? ???????, ????????? ???????,
??????????? ???????, ????????, ?????????? ?????????????.
1. Introduction
One of the most important problems of the physical chemistry is the processes? mechanism
identification in order to regulate their speed in case of different external actions. The importance of
the presented research is determined by the necessity of working out the optical detonators based on the
secondary explosives [1-3]. There are two main points of view using to explain the explosive process
? thermal model [1-5] and chain model [6-8]. In terms of the thermal model it is supposed that the
material decomposes according to the one-step reaction, which kinetic constant obeys the Arrhenius
law [9-11]. At the same time it is supposed that the preexponential factor and the activation energy do
not depend on the temperature. In terms of the chain model the self-accelerating decomposition relates
to the multiplication of the electron and ion defects of lattice [12-13]. Using the chain model several
regularities of the silver azide (SA) crystals? explosive decomposition initiated by the excimer laser
were explained [14-17].
In spite of the fact that the chain model was experimentally and theoretically approved to be true
for the SA [17], the common conception in the order of the elementary stages of the process are still
absent in literature. The main difficulties of identification of the chain reaction?s elementary stages
(generation and evolution) occur because it was widely experimentally investigated only the selfaccelerating mode of the explosive decomposition process. To work out the experimentally approved
solid-state chain reaction it is necessary to investigate the kinetics of the before-threshold mode of
the decomposition process and the regularities of the transition from the damped mode to the selfaccelerating mode Aim of this work is to experimentally and theoretically investigate size effects and
before-threshold mode of the solid-state branched chain reaction in the silver azide crystals.
2. Experimental section
The depiction of experimental set-up, which was used to research the regularities of the silver
azide explosive decomposition, one can find in [18]. Silver azide macrocrystals with dimensions
1*1*0.3 mm3 were used as experimental samples. The crystals had no visible imperfections. The main
impurities? concentration was not exceed 1017 cm-3.As a source of pulse influence, which initiates
explosive decomposition, a Nd: Yag laser (? = 1060 nm) was used. The initiation wavelength is in
the area of the impurity absorption, this allowed to initiate the reaction homogeneous throughout the
sample [19]. Maximum energy density of the laser was 20 J. Pulse duration was 30 ns.
It was experimentally shown that before-threshold mode, in which the initiated chain reaction
decayed without reaching the self-accelerating mode, is observed in microcrystals initiated by the
# 471 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Marina V. Ananyeva and Alexander V. Kalenskii. The Size Effects and Before-Threshold Mode of Solid-State Chain?
pulses which energy density is smaller than the critical value Hc(r). The dependence of the critical
energy density on the crystal size for the silver azide crystal is shown on Fig. 1. The crystal size range
for which the before-threshold mode might be observed is also shown on Fig. 1.
3. Model of the branched chain reaction
In the work [19] a new reason of increase of critical energy density (?c) of azide heavy metals
explosion initiated by pulse radiation was proposed. This reason is the result of the branched chain
reaction and is the feature of all chain reactions. According to the model it is bound up with the
increased rate of electron-hole (e-h) pairs (breaking chain stage) on crystal surface in comparison with
the bulk recombination. It results in increase of ?c if the sample size is comparable with the free path of
electron excitations ? chain carriers. The proposed model is a solid-state analogue of the dependence of
explosion initiation critical parameters on vessel dimensions of gas-phase reaction [20-21].
Let us consider the effect of laser 20ns pulse radiation on silver azide microcrystal. Taking into
account the influence of surface on the reaction propagation the kinetics of the process will be described
by the system of integro-differential equations [20-23]:
­dp / dt G (t ) 2k2 p 2 kr p 3k1EA D'p,
°
2
°dA / dt k2 p k1 A,
°
®
dp
D
sp,
°dN 2 / dt 3k1 A,
dx x 0, x l
°
°ЇEE ( L p 1,5[N 2 ] 2 A) / L;
(1)
Fig. 1. Dependence of the initiation critical energy density of the silver azide crystals (relative units) on the crystal
size. Points are experimental data, line is calculation. Hc ? critical energy density necessary to initiated explosive
decomposition of the microcrystal, H0 ? critical energy density of big crystals, r ? crystal?s size
# 472 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Marina V. Ananyeva and Alexander V. Kalenskii. The Size Effects and Before-Threshold Mode of Solid-State Chain?
where p, A, N2 are concentrations of holes, N6 complexes and molecular nitrogen in the bulk of the
crystal; k2, k1, k r are constants of generation, N6 ? complex destruction and e-h pair recombination
rates in the bulk of the crystal; D is the diffusion constant of holes; s=5*105cm/s is the rate of surface
recombination in silver azide crystals; sp is a boundary condition taking into account the recombination
rate of charge carriers on the surface; ? is the coefficient taking into account anion expenditure during
the reaction; L is Loshmidt number.
The dependence of initiation energy critical density on the size of the crystal under short pulses
might be presented as:
Hc
Є kr*
є E
2 � (kr* ) 2
« k2 »�
k
k
�
2
1
¬
ј D
(2)
2
where kr* kr S D 2 is the effective constant of the recombination rate, which includes the
r
inhibitory influence of the surface; ? is the average energy of one e-h generation; ? is the effective
absorption coefficient.
In work [19] it is shown that increase of Hc will reveal itself in the most effective way if the size
of the crystal is in following range
r1
§ 6D2 ·
SЁ
ё
© k1k2 L №
1
4
d r d r2
2
S2 D
kr
(3)
With the reaction constants estimated in [23] these values are r1 = 1?m, r2 = 20?m.
If the crystal size is r> (2-3) r2 ? 50?m the critical initiation energy density practically coincides
with the bulk density Hc =Ho. If r ? 1?m Hc increases in more than 103 times that practically corresponds
to the total ionization of anionic sublattice. Finally, the branched-chain reaction is not realized and
microcrystals are decomposed without explosion.
The results are presented in Fig. 1. From these results it follows that according to [23] Hc increases
in more than 30 times if the crystal size decreases from 35 to 3?m, and tends to ?? if the crystal
size increases. After the action of pulse radiation the large crystals (r > 50?m) either explode over
exceeding initiation threshold or show no visible changes (including flash of light emission). The
microcrystals with sizes r ? 1?m cannot be initiated up to the energy density ? ? 10 J/cm2. Under these
? microcrystals are practically decomposed entirely under pulse duration, but the stage of exponential
increase of the reagents? concentration is absent.
On Fig. 1 the experimental and calculated using equation (2) dependences of the explosion
initiation critical energy density on the sizes of silver azide microcrystals are shown. The comparison
with the experiment has allowed to determine the parameters k r= 1,6 * 106 s?1 and k1= 6,2 * 107 s?1 for
silver azide microcrystals which do not much differ from the values obtained in [22] while studying
other experimental explosive characteristics in silver azide.
Thus, the experimental results confirm the viewpoint [23] that the breaking chain stage is the
recombination of electron excitations. High rate of this stage on the surface of the crystal is one of
the main reasons for ?? increase if the sample sizes are comparable with the free path of electron
excitations.
# 473 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Marina V. Ananyeva and Alexander V. Kalenskii. The Size Effects and Before-Threshold Mode of Solid-State Chain?
The obtained results also allow to estimate the mobility (diffusion constant) of electron excitations
directly during explosive decomposition. The calculations were carried out with the diffusion constant
of holes D = 0.25 cm2/s which corresponds to their experimental mobility ? ? 10 cm2/ V s.
The close coincidence calculated at D=0.25cm2/s and experimental values ?? (r) indicate firstly
that the mobility (diffusion constant) of electron excitations during explosion decomposition slightly
differs from the values determined with use of Hall effect, and secondly that the temperature rise is not
the first cause of silver azide explosive decomposition.
4. Before-threshold behavior of silver azide chain
explosive decomposition
The model described above allows to predict theoretically and to detect experimentally a new
before-threshold mode of the chain reaction. This mode is observed in case of irradiation of the
microcrystals with sizes r2< r<r2 by pulses with the energy density ??<?(r)<?? (r).
The before-threshold mode take place because the reaction after being initiated in the bulk of
the crystal goes out on the crystal surface owing to the diffusion of electron excitations where the
recombination process is very intensive. By increasing pulse energy density it is possible to fulfill the
condition ?(r) ? ?? (r) and the reaction process transforms from damping mode to self-acceleration
mode resulting in the explosion of the sample. In «MATLAB» environment the software package
was developed for mathematical modeling the kinetics of solid-state chain reactions in silver azide.
The package allows to solve numerically the system of 1500?2000 integro-differential equations. The
obtained solution allows to visualize the image of the reaction propagation at any moment of time and
at any point of the crystal. Fig. 2 and 3 present the results of the reagent space distribution calculated
for silver azide microcrystyals with sizes 5?m at different points of time. The initial rate of e-h pair
generation is taken the same for the whole bulk of the sample. Fast decrease of holes? concentration
owing to N6 complex generation is realized directly after the ending of the pulse. In subsurface areas
faster decrease of holes? concentration is realized owing to the high recombination rate on the crystal
surface. The following growth of reagents? concentrations, especially in the central part of the crystal,
is because of the multiplication of electron excitations during chain reaction (Fig. 2). The maximum
concentration is achieved in 326 ns, and then the decrease of the reagent concentrations is realized
owing to the sample burnout (Fig. 3).
On Fig. 4 the oscillogram of before-threshold illumination of the silver azide monocrystals is
presented. When the initiating energy density was smaller than Hc(r) the zonal photomultiplier in the
spectral areas 800 ч 900 nm and 500 ч 550 nm registered a glow peak. This illumination is a result
of the physic-chemical process in the initiated part of the sample. This glow might be the result of the
reaction or the laser-induced breakdown.
Before-threshold glow one can observe for microcrystals which sizes are r ? 10 mcm. The
lowest value of the initiation energy density (Hp) for which the pre-threshold glow is observed for
the microcrystals is about 60-65 mJ/cm2. For 10?m crystals the values of Hp and Hc are almost equal
and the before-threshold glow might be observed only in narrow area Hp < H0 < H?. The lowest value
of the initiation energy density, for which the before-threshold glow might be observed, almost does
not depend on the microcrystal size. Hp value is about doubled critical initiation energy density of the
macrocrystals (Hp ? 2 H?c). Although to prove experimentally that Hp is put and therefore depends on
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Fig. 2. ?alculated distribution of reagents? concentration along microcrystal in 8, 60, 120, 180, 240, 270 and 326
ns time. Cp ? concentration of the holes, main reagents of the solid ?state chain reaction, axis r symbolizes the
different places in the crystal
Fig. 3. The calculated kinetics of distribution of reagents concentration in microcrystal along crystal in 326, 440,
550, 660, 770, 880 and 1000 nc. Cp ? concentration of the holes, main reagents of the solid ?state chain reaction,
axis r symbolizes the different places in the crystal
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Fig. 4. Oscillogram of glow of silver azide microcrystal in case H < Hc: 1 ? impulse, 2 and 3 ? signals of the
photomultipliers registered luminescence in the spectral areas 800 ч 900 nm and 500 ч 550 nm correspondingly.
I ? intensity of the signal, registered by the photomultiplier (relative units); t ? time
Fig. 5. Dependences of the peak value in the spectral areas 800 ч 900 nm and 500 ч 550 nm correspondingly for 5
m? silver azide microcrystals on the initiation energy density. In part A crystal show no visible changes, in part
B one can observe before-threshold mode of the solid-state reaction, C ? explosive decomposition. Ho ? energy
density of the laser impulse
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Marina V. Ananyeva and Alexander V. Kalenskii. The Size Effects and Before-Threshold Mode of Solid-State Chain?
the critical initiation energy density of the macrocrystals it is necessary to make additional experiments
and examine the dependence of Hp on the impulse duration and intensity and the spectrum of the
preliminary irradiation.
The threshold of the laser-induced breakdown for a bulk of AgN3 microcrystal is well known [18]
(Hb ~ 500 mJ/cm2) and exceeds in more than 8 times the value of the lowest energy density for which
the before-threshold glow is observed (Hp ? 8 Hb). This allows to conclude that optical breakdown could
not explain the fact of before-threshold glow in this experiment. The reason of the glow, registered
by the zone photomultiplier while the initiation energy density is lower than Hc, is physic-chemical
processes in individual microcrystals of silver azide. In this case there are two possible way of energy
liberation ? recombination of electrons and holes and decay of complex N6 till N2. We can suppose that
the reaction is generated and then attenuates because the chain carriers? concentration decreases. The
decrease occurs because of the recombination processes and the decomposition reaction.
The kinetic curves of before-threshold glow in spectral areas 800 ч 900 nm and 500 ч 550 nm are
similar to each other and after being standardized on maximum almost coincide. Main parameters of
the curves (constants of exponential growth and slop, peak values) also coincide. Small difference in
the glow curves in these spectral areas is observed in the part of slope below the half of the amplitude.
The difference is the slower decay of the signal in the area 800 ч 900 nm.
If the initiating energy density is bigger than its critical value H? the kinetics of glow changes ? it
has two peaks. First peak of kinetics is similar to that of the before-threshold kinetics, for example has
the same constant of exponential growth.
On Fig. 5 one can see the dependence of the kinetic curve maximum on the initiating energy
density for the silver azide microcrystals with sizes 5?m. Each point is the averaging of 5 tests. The
signal observed if the initiating energy density is equal to doubled critical energy density of the
macrocrystals. On the figure the critical energy density of silver azide macrocrystals and microcrystals
of examined sample party are marked with vertical lines. Regularities of the glow in case of initiating
energy density growth till the critical value remain the same. The glow peak in both spectral areas
depends linearly on the initiating energy density. In case of macrocristals initiation with the energy
which is smaller than 60 ?J/cm2, they show no visible changes. The intermediate area of energies (area
B) is the area there the before-threshold mode in AgN3 crystals.
The second peak on the kinetic curve in case of silver azide microcrystals initiation with energy
bigger than Hc is observed in 100-300 ns. Its intensity is not equal to the intensity of the first peak.
While the energy of the impulse growths the peak value almost does not change. The interval between
the first and the second peak becomes smaller if the impulse energy growths. For impulse energy
which is near to the critical value Hc the signal between two peaks might fall till zero.
5. Resume
In this work size effects and before-threshold behavior of the solid state reaction in silver azide
crystals were experimentally and theoretically researched. It was shown that if the crystal?s size
decreases the critical initiation energy density considerably increases. This is because of the bigger
speed of the electron-carriers recombination on the crystal surfaces in comparison with the same
value for the bulk. Before-threshold effects of the solid state brainched chain reaction can be observed
if the energy of the initiation is smaller than the critical value; and the carriers? diffusion length is
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Marina V. Ananyeva and Alexander V. Kalenskii. The Size Effects and Before-Threshold Mode of Solid-State Chain?
comparable with the sample sizes or with the area there the initiating irradiation absorbed. The results
are necessary to work out the details of optical detonator. The authors thank Ministry of Education and
Science of the Russian Federation (state order ? 2014/64) and Russian Foundation for Basic Research
for the financial support (grant ?14-03-00534 ?), prof. Kriger V. and prof. Tsipilev V. for help in
experimental part of the work and useful discussion.
References
1. Aduev B.P., Nurmukhametov D.R., Furega R.I., Zvekov A.A., Kalenskii A.V. Vzryvchatoye
razlozheniye TENa s nanodobavkami alyuminiya pri vozdeystvii impulsnogo lazernogo izlucheniya
razlichnoy dliny volny. Khimicheskaya fizika, 2013, 32(8), 39?42.
2. Zykov I.Y. Accounting of the absorbance of nano-inclusions heated by laser impulse.
International scientific periodical ?Modern fundamental and applied researches?, 2012, 3 (6), 42?48.
3. Ananyeva M.V., Zvekov A.A., Zykov I. Yu., Kalensky A.V., Nikitin A.P. Promising compounds
for the cap of optical detonator. Perspektivnye materialy, 2014, 7, 5?12.
4. Kalenskii A.V., Zvekov A.A., Ananyeva M.V., Zykov I.Yu., Kriger V.G., Aduev B.P. Influence
of the laser irradiation wavelength on the energetic materials? initiation critical energy. Fizika goreniya
i vzryva, 2014, 50(3), 98?104.
5. Kriger, V.G., Kalenskii A.V., Zvekov A.A., Zykov I.Yu., Aduev B.P. Vliyaniye effektivnosti
pogloshcheniya lazernogo izlucheniya na temperaturu razogreva vklyucheniya v prozrachnykh
sredakh. Fizika goreniya i vzryva, 2012, 48(6), 54?58.
6. Kriger V.G., Kalenskii A.V., Zvekov A.A., Zykov I.Yu., Borovikova A.P., Grishaeva E.A.
Opredeleniye shiriny fronta volny reaktsii vzryvnogo razlozheniya azida serebra. Fizika goreniya i
vzryva, 2012, 48(4), 129?136.
7. Kriger V.G., Kalenskii A.V., Zvekov A.A. Relaksatsiya elektronno-vozbuzhdennykh produktov
tverdofaznoy reaktsii v kristallicheskoy reshetke. Khimicheskaya fizika, 2012, 31(1), 18?22.
8. Kalenskii, A.V., Anan?eva M.V., Kriger V.G., Zvekov A.A. Koeffizient zahvata elektronnyh
nositeley zaryada na ekranirovannom ottalkivaushyem centre. Khimicheskaya fizika, 2014, 33(4), 11?16.
9. Ananyeva M.V., Kalenskii A.V., Grishaeva E.A., Zykov I.Yu., Nikitin A.P. Kinetic regularities
of the explosive decomposition of PETN containing nanosized inclusions of aluminium, cobalt, and
nickel. Bulletin of Kemerovo State University, 2014, ?1-1 (57), 194?200.
10. Aduev B. P., Nurmukhametov D. R., Belokurov G. M., Zvekov A. A., Kalenskii A. V., Nikitin
A. P., and Liskov I. Yu. Integrating Sphere Study of the Optical Properties of Aluminum Nanoparticles
in Tetranitropentaerytrite. Zhurnal Tekhnicheskoi Fiziki, 2014, 84(9), 126?131.
11. Kriger V.G., Kalenskii A.V., Zvekov A.A., Zykov I.Yu., Nikitin A.P. Protsessy teploperenosa
pri lazernom razogreve vklyucheny v inertnoy matritse. Teplofizika i aeromekhanika, 2013, 20(3),
375?382.
12. Zhuravlev Yu. N., Lisitzin V. M. Izuchenie reakzionnoi sposobnosti azida serebra po dannim
zonnych raschetov v ramkach teorii funkzionala plotnosti. Khimicheskaya fizika, 2014, 33(3), 3?12.
13. Kriger V.G., Kalenskii A.V., Zvekov A.A., Anan?eva M.V. Determination of Spatial Characteristics
of the Chain Reaction Wave in Silver Azide. Khimicheskaya fizika, 2014, 33(8), 22?29.
14. Kalenskii A.V., Kriger V.G., Zvekov A.A., Grishaeva E.A., Zykov I.Yu., Nikitin A.P. The
Microcenter Heat Explosion Model Modernization. Izvestia Vuzov Fizika, 2012, 8(11/3), 62?66.
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15. Kriger V.G., Kalensky A.V., Zvekov A.A., Ananyeva M.V., Borovikova A.P. Diffuzionnaya
model razvetvlennoy tsepnoy reaktsii vzryvnogo razlozheniya azidov tyazhelykh metallov.
Khimicheskaya fizika, 2009, 28(8), 67?71.
16. Kriger V.G., Kalenskii A.V., Zvekov A.A. Opredeleniye nachala mekhanicheskogo
razrusheniya kristallov azida serebra, initsiirovannykh lazernym impulsom. Fizika goreniya i vzryva,
2010, 46(1), 69?72.
17. Ananyeva M.V., Kriger V.G., Kalensii A.V., Zvekov A.A. Comparative analysis of energetic
materials explosion chain and thermal mechanisms. Izvestia Vuzov Fizika, 2012, 55(11/3), 13?17.
18. Kriger V.G., Kalenskii A.V., Zvekov A.A., Tsipilev V.P. Explosive decomposition of silver
azide single crystals for various diameters of the irradiated area. Fizika goreniya i vzryva, 2009, 45(6),
105?107.
19. Kalenskii A.V., Kriger V.G., Tzipilev V.P., Ananyeva M.V. Dependence of the critical initiation
energy of the silver azide monocrystal on the diameter of the irradiation area. Polzunovskii vestnik,
2006, 2?1, 75?77.
20. Kriger V.G., Kalenskii A.V., Zakharov Yu.A., Tzipilev V.P. Mechanisms of the Solid state
chain reaction. Materialovedenie, 2006, 9, 14?21.
21. Grishaeva E.A., Kalenskii A.V., Ananyeva M.V., Zvekov A.A. Non-isothermal model of
branched chain explosive decomposition reaction in energetic materials. Fundamental?nye problemy
sovremennogo materialovedenia, 2013, 10(1), 44?49.
22. Kriger V.G., Kalensky A.V. Initiation of heavy metal azides by pylse radiation. Khimicheskaya
fizika, 1995, 14(4), 152?160.
23. Kriger V.G., Kalensky A.V. The effect of crystal size on initiation of decomposition of heavy
metal azides by pulse radiation. Khimicheskaya fizika, 1996, 15(3), 40?46.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 480-486
~~~
??? 630*114.28
Determination of Free Proteinogenic Amino Acids
in Soil Solutions by HPLC
with Phenyl Isothiocyanate Derivatization
Rodion V. Okunev*,
Boris R. Grigoryan and Adelina I. Sharipova
Kazan (Volga region) Federal University
18 Kremlyovskaya Str., Kazan, 420008, Russia
Received 18.09.2014, received in revised form 06.10.2014, accepted 12.11.2014
A high-performance liquid chromatography method for the determination of seventeen free
proteinogenic amino acids (FPAA) in soil solutions is described. Sample preparation involves obtaining
soil solution and pre-column derivatization of free amino acids using phenyl isothiocyanate. Phenyl
thiocarbamyl derivatives are separated on a reversed-phase column by using linear gradient elution
with 140 mM sodium acetate buffer solution (pH 6.0) contained 0.05% triethylamine as mobile phase A
and acetonitrile-water (60:40,v/v) as mobile phase B. The described method showed adequate linearity,
recovery values, limits of detection, and suitable for the determination of FPAA in soil solutions.
Keywords: amino acid derivatization, soil solution, free amino acids, amino acids in soil, phenyl
isothiocyanate, HPLC.
??????????? ????????? ?????????????? ???????????
?????????? ???????? ??????? ????
? ?????????????? ?????????????? ???????????????????
?.?. ??????, ?.?. ?????????, ?.?. ????????
????????? (???????????) ??????????? ???????????
??????, 420008, ??????, ??. ???????????, 18
?????? ?????? ??????????? ?????????? ????????? ?????????????? ??????????? ??????????
???????? ??????? ????????????????? ?????????? ?????????????. ???????????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: tutinkaz@yandex.ru
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Rodion V. Okunev, Boris R. Grigoryan? Determination of Free Proteinogenic Amino Acids in Soil Solutions by HPLC?
???????? ? ???? ????????? ?????????? ???????? ? ?????????????? ????????????? ?????????
??????????? ???????????????????. ?????????????????? ?????????? ???????????
??????????? ????????? ?? ????????????? ??????? ? ???????? ????????? ??? ?????????????
???????, ????????? ?? ??????, ??????????????? ??????????? 0,5 ??/? ????????????
? 0,14 ? ??????? ?????? (pH 6,0) ? ????? ???????????-???? (60:40). ????????? ??????
????? ?????????????????? ????????????? ?????????????? ? ???????? ??? ???????????
???????????? ????????? ?????????????? ??????????? ? ????????? ????????.
???????? ?????: ????????????? ????????? ???????????, ????????? ???????, ?????????
????????????.
Introduction
Concentrations of free proteinogenic amino acids (FPAA) in soil solutions are important factors
to determine [1, 2]. For this purpose the HPLC method is used, which is a powerful tool in the analysis
of many components in soil solution (organic acids, sugars, amino acids, etc.) [1, 3-6].
However, the determination of free amino acids (FAA) can be complicated by the influence of the
complex sample matrixes of the sample [7, 8]. The soil solution is also a complex system and has a large
number of organic and mineral components [9, 10], which can affect the results of the quantification.
Besides, in order to effectively detect amino acids with ultraviolet or fluorescence detectors, they are
usually requires a chemical modification (derivatization) step [11]. Phenyl isothiocyanate (PITC) is one
of the most widely used reagents for the derivatization of FAA in biological fluids (blood plasma, root
exudates et al.) [7, 12, 13]. It reacts with primary and secondary amino acids and gives the consistent
phenyl thiocarbamyl (PTC) derivatives that can be detected by the UV-detector on wavelength of 254
nm [14].
In this paper, we describe a method for qualitative and quantitative determination of FPAA in soil
solutions by HPLC with pre-column PITC derivatization.
Experimental
Chemicals
L-Amino acids, phenyl isothiocyanate (PICT) and triethylamine purchased from Sigma (St.
Louis, MO, USA). HPLC-grade acetonitrile and methanol were from Component Reactive (Moscow,
Russian). Reagent-grade sodium acetate, sodium phosphate, glacial acetic acid and hydrochloric
acid were from Ecopharm (Kazan, Russian). Water was obtained using a Milli-Q water system from
Millipore (Bedford, MA, USA).
Soil Sampling, Soil Solution Obtaining and Preparation of Standards
Soil samples were obtained from A horizons of Haplic Luvisol (classified according to WRB soil
classification system) [15] in the Tytushsky region of the Republic of Tatarstan, Russian (55°68ґ N,
49°13ґ E). Air dried and sieved finer than 1 mm samples (20 g) were placed into a plastic tube (11 cm
diameter and 7 cm high) and saturated with 6 mL of Milli-Q water. After 72 hour of incubation at room
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Rodion V. Okunev, Boris R. Grigoryan? Determination of Free Proteinogenic Amino Acids in Soil Solutions by HPLC?
temperature soil solutions were obtained by vacuum through a filter paper. Extracted solutions were
filtered by a 0.22-?m pore membrane.
A stock solution containing a mixture of 18 amino acid standards was prepared in 0.1 M HCl at
an individual concentration of 2.5 mmol L?1. Calibration solutions at different concentrations (1.5, 7.5,
15, 30, 120, 300, 600 ?mol L?1) were prepared by serially diluting appropriate amounts of the stock
solution with 0.1 M HCl.
Derivatization
The pre-column derivatization procedure used was a modified version of the reported Refs.[11,14].
A standard solution (20 ?L) or 400 ?L of soil solution was dried under vacuum at 65°C in small plastic
tube (10 Ч 50 mm). The dry residue was neutralized by adding 30 ?L of a 2:2:1 mixture of methanoltriethylamine-water (v/v), mixing well and drying under vacuum. Derivatization was performed by
adding 30 ?L of a mixture of 7.5:1:1:0.5 methanol- triethylamine-water-PITC (v/v). The tubes were
mixed well and allowed to stand at room temperature for 20 min. After derivatization, the tubes were
vacuum-dried at 45°C. Prior to injection, the residue was resuspended with 300 ?L of 5 mM sodium
phosphate buffer (pH 7.4) contained 5% acetonitrile and filtered through 0.22-?m pore membrane.
Instrumentation and Chromatographic Conditions
The HPLC analysis was carried out on a Flexar HPLC system (Perkin Elmer, USA) which consisted
of a Flexar Binary LC Pump and a Flexar UV/Vis detector. Separation of amino acid derivatives was
performed on a Brownlee Analytical C18 column, 150 mm Ч 4.6 mm, 5 ?m (Perkin Elmer, USA).
PTC derivatives of amino acids are separated on a reversed-phase column by using linear gradient
elution with 140 mM sodium acetate buffer solution (adjusted to pH 6.0 with glacial acetic acid)
contained 0.05% triethylamine as mobile phase A and acetonitrile-water (60:40,v/v) as mobile phase
B. The gradient elution program is shown in Table I. Wavelength of UV/Vis-detector was 254 nm, and
the injection volume was 20 ?L.
Results and discussion
The overall time required for the analysis of one sample of soil solution is 72 min, of which 35 min
is spent on the derivatization step and 37 min - on the chromatographic separation. A typical calibration
standard chromatogram containing 7.5 ?mol L?1 of each amino acid (each peak corresponds to 10 pmol
Table 1. Gradient elution program for the separation of PTC derivatives of amino acids
Time (min)
% Eluent A
% Eluent B
0
90
10
14.0
70
30
24.0
52
48
30.0
0
100
34.0
0
100
37.0
90
10
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Table 2. Precision of measurement, recoveries and detection limits obtained for each amino acid (n=6)
Amino acid
Asp ac
Glu ac
Asn
Ser
Gln
His
Arg
Thr
Ala
Pro
Tyr
Val
I-leu
Leu
Phe
Trp
Lis
a
Precision of
measurement CV a (%)
0.47
0.63
1.05
1.94
1.11
0.98
0.45
0.55
0.99
1.23
1.11
1.15
0.86
0.90
1.54
1.90
1.87
Detection limit
(pmol amino acid injected to column)
0.33
0.42
0.25
0.33
0.32
0.46
0.48
0.35
0.48
0.43
0.39
0.25
0.38
0.35
0.40
0.22
0.32
Recovery (%)
76.0
90.3
110.1
101.7
94.9
97.7
99.5
97.2
107.9
102.1
107.1
109.7
105.7
102.2
106.7
107.3
93.1
Coefficient of variation (calculated from the ratios of peak area)
Table 3. Concentrations of free proteinogenic amino acids in soil solution
Amino acid
Concentrationsa (?mol L?1, n = 6)
Asp ac
Glu ac
Asn
Ser
Gln
His
Arg
Thr
Ala
Pro
Tyr
Val
I-leu
Leu
Phe
Trp
Lys
TPFAAc
3,10±0.06
8.15±0.37
0,71±0.17
8.61±3.63
BQLb
4.03±0.090
8.78±0.05
10.68±0.09
15.21±0.29
6.02±0.63
24.75±0.74
11.56±0.16
3.20±0.34
4.27±0.09
2.25±0.14
0.66±0.14
0.51±0.018
112,46±7.09
The concentrations are presented as mean ± standard deviation
below the limit of quantification
c
Total proteinogenic free amino acids
a
b
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Rodion V. Okunev, Boris R. Grigoryan? Determination of Free Proteinogenic Amino Acids in Soil Solutions by HPLC?
of amino acid) appears in Fig. 1a. The column gradient elution program described in [11] has been
optimized for the separation of amino acids on the Brownlee Analytical C18 column (150 mm Ч 4.6 mm,
5 ?m) and provided in Table 1.
The validation of analytical procedure was performed according to EURACHEM [16]. Linearity
of the peak areas for different concentrations, ranging from 2 - 800 picomoles of individual amino
acids (calibration solutions containing 1.5 - 600 ?mol L?1 of each amino acid) were determined.
Correlation coefficients for these data exceeded 0.987. Recoveries of amino acids from soil solutions
were evaluated by measuring the concentration of each amino acid in soil solution spiked with three
Fig. 1. Chromatograms of (a) PTC derivatives of amino acids in a standard solution containing 7.5 ?mol L?1 of
each amino acid; (b) soil solution. Peak identification (1) aspartic acid (Asp ac), (2) glutamic acid (Glu ac), (3)
asparagine (Asn), (4) serine (Ser), (5) glutamine (Gln), (6) histidine (His), (7) arginine (Arg), (8) threonine (Thr),
(9) alanine (Ala), (10) proline (Pro), (11) tyrosine (Tyr), (12) valine (Val), (13) isoleucine (I-leu), (14) leucine (Leu),
(15) phenylalanine (Phe), (16) tryptophan (Trp), (17) lysine (Lys)
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Rodion V. Okunev, Boris R. Grigoryan? Determination of Free Proteinogenic Amino Acids in Soil Solutions by HPLC?
different levels (7.5, 30, 300 ?mol L?1) of standard solution. The recoveries were ranged from 90.3% to
109.7% for most of amino acids (Table 2). For aspartic acid it was around 76%. In order to receive much
higher recoveries of aspartic acid, suggested to use a nitrogen stream rather than heating under vacuum
to drive off the excess derivatization reagent [11]. The high recoveries of most amino acids shows, that
matrices of obtained soil solutions did not have a significant effect on the derivatization step, but it is
possible, the PITC method can be affected by high concentrations of salts in solutions [8], obtained, for
example, from saline soils. The detection limit values for free amino acids were low, between 0.22 and
0.48 pmol of amino acid injected to column (14.6-32 nmol L?1 of soil solution). The average recoveries
(n=6), the detection limits (signal-to-noise ratio=3) and the precision of measurements (for 30 ?mol
L?1 of standard solution) of 17 amino acids are shown in Table 2. Intraday (n=6) and interday (n=3)
precision values not exceeded 9%. (n =6).
In soil solutions except proteinogenic amino acids there are a lot of other organic components
(aminosugars, nonproteinogenic amino acids), which can react with PITC [7, 17], giving the derivatives
that can be detected by the UV-detector and appearing on the chromatogram as peaks. Thus, despite
a large number of unknown peaks the column gradient elution program allowed to determine all 17
amino acids in educated soil solutions (Fig.1b). However, the content of glutamine has been below the
determination limit. The total free proteinogenic amino acid (TFPAA) concentrations in soil solutions
was 112.4±7.09 ?mol L?1, which is consistent with the studies [1, 18]. The major amino acids were
tyrosine and alanine (22.0 and 13.5% respectively from TFPAA).
Conclusion
The method described in this paper was suitable for determining free proteinogenic amino acids
in soil solutions. It includes soil solution obtaining, pre-column derivatization of free amino acids
with PITC, and determination PTC derivatives of amino acid with HPLC. Matrices of educated soil
solutions did not have a significant effect on the quantitative determination results.
Acknowledgments
The work is performed according to the Russian Government Program of Competitive Growth of
Kazan Federal University.
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dissolved organic matter in a rhizosphere soil solution of a humus-rich andosol using size exclusion
chromatography with inductively coupled plasma-mass spectrometry. Soil Sci. Plant Nutr. 2009.
Vol. 55. P. 349?357.
11. Gonzalez-Castro M.J., Lopez-Hernandez J., Simal-Lozano J., Oruna-Concha M.J.
Determination of amino acids in green beans by derivatization with phenylisothiocianate and highperformance liquid chromatography with ultraviolet detection. J. Chromatogr. Sci. 1997. Vol. 35. P.
181?185.
12. Marco S., Hjalmar P.P., Letty A.W., Carel A.W., Ben J.J.L. Amino acid synthesis is necessary
for tomato root colonization by pseudomonas fluorescens strain WCS365. Mol. Plant Microbe In. 1997.
Vol. 10. P. 102?106.
13. Hariharan M., Naga S., Van Noord T. Systematic approach to the development of plasma amino
acid analysis by high-performance liquid chromatography with ultraviolet detection with precolumn
derivatization using phenyl isothiocyanate. J. Chromatogr. 1993. Vol. 621. P. 15?22.
14. Fierabracci V., Masiello P., Novelli M., Bergamini E. Application of amino acid analysis
by high-performance liquid chromatography with phenyl isothiocyanate derivatization to the rapid
determination of free amino acids in biological samples. J. Chromatogr. 1991. Vol. 570. P. 285?91.
15. IUSS Working Group WRB. World Reference Base for Soil Resources. World Soil Resources
Report; FAO, Rome, 2006; No. 103.
16. EURACHEM Working Group. Analytical Methods: A Laboratory Guide to Method Validation
and Related Topics; United Kingdom, 1998.
17. Anumula K.R., Taylor P.B. Quantitative determination of phenyl isothiocyanate-derivatized
amino sugars and amino sugar alcohols by high-performance liquid chromatography. Anal. Biochem.
1991. Vol. 197. P. 113?120.
18. Raab T.K., Lipson D.A., Monson R.K. Soil amino acid utilization among species of the
cyperaceae: plant and soil processes. Ecology 1999. Vol. 80. P. 2408?2419.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 487-493
~~~
??? 547.913:582.099
Chemical Composition of the Essential Oil
from Fruits of Heracleum dissectum L.
Growing in Krasnoyarsk Krai
Alina M. Shushenacheva and Aleksandr A. Efremov*
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
Received 06.10.2014, received in revised form 21.10.2014, accepted 16.12.2014
The constituents of the essential oil from fruits of Heracleum dissectum L. obtained by steam
distillation were determined by GS-MS method. It was found that the essential oil from fruits of
Heracleum dissectum L. growing in Krasnoyarsk region of Russia contains more than 47 compounds;
44 compounds representing 98.6 % of the oil were identified. The major constituents of the oil
were vinylcyclohexane (4.52 %), octyl acetate (58.5 %), 2-methyloctyl propanoate (10.81 %)
and ?-alanine (9,47 %). Five fractions of the essential oil were obtained. It was found that compositions
of all five fractions are different.
Keywords: essential oil, GS, GS-MS, Heracleum, composition.
???????????? ?????? ???????? ?????
?????? ????????? ????????????,
??????????????? ? ???????????? ????
?.?. ??????????, ?.?. ???????
????????? ??????????? ???????????
??????, 660041, ??????????, ??. ?????????, 79
??????? ???????-????-????????????? ?????????? ?????????? ???????? ????? ??????
????????? ????????????, ??????????? ??????? ????????? ? ?????. ??????????, ??? ? ???????
????? ?? ?????? ????????? ????????????, ??????????????? ? ???????????? ????, ??????????
????? 47 ???????????, 44 ?? ???????, ?????????????? ????? 98,6 % ?? ???????? ?????, ????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: chuchic1@yandex.ru
# 487 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alina M. Shushenacheva and Aleksandr A. Efremov. Chemical Composition of the Essential Oil from Fruits?
????????????????. ????????? ???????????? ???????? ????? ???????? ????????????????
(4,52 %), ??????????? (58,5 %), 2-?????????? ????????? (10,81 %) ? ????-?????? (9,47 %).
????? ???? ???????? ???? ????????? ??????? ???????? ?????. ???????????, ??? ??? ????
??????? ???????? ????? ????? ????????? ??????.
???????? ?????: ??????? ?????, ??, ??-??, ????????, ???????????? ??????.
Introduction
The genus Heracleum includes approximately 70 species and most of them can be found in
Russia. Heracleum species growing in Siberia, such as Heracleum dissectum Ledeb are edible
plants. Heracleum dissectum L. grows in broken forests, in forest glades and in the meadows of
Siberia, Central Asia and Far East. It is spread in all areas of forest zone and the neighbouring
forest-steppe and steppe zones. In the north of Krasnoyarsk Region of Russia areal reaches 70 0 of
north latitude. In the west, areal border within forest zone lies along Irtysh and Ob rivers (1-3).
Fruits of Heracleum species contain 1-10 % of essential oil. The essential oil from fruits of
Heracleum dissectum L. contains ?-pinene, ?-pinene, octanol, octyl acetate, octyl butyrate, octanal,
hexyl butyrate; coumarines: umbelliferone, sphondin, xanthotoxin, izopimpinellin, bergapten,
angelicin, isobergapten, pimpinellin, imperatorin, ostol, scopoletin, biakangelicin, heraclesol,
marmezin, fellopterin (4-9).
Composition of the essential oils depends on the habitat of plants and maturity of fruits (10-12).
A literature survey showed that composition of the essential oil of Heracleum dissectum, growing in
Siberia haven?t been investigated. Therefore the objective of this study was to identify the individual
components of the essential oil of Heracleum dissectum from Central Siberia (Krasnoyarsk region of
Russia) and to compare the data with literature.
Experimental
Isolation of the essential oil
Mature fruits of Heracleum dissectum L. were collected in July-August 2011 in Krasnoyarsk
Region of Russia. The essential oil of air-dried fruits of Heracleum dissectum L. was extracted by
steam distillation using Clevenger-type apparatus for 53 hours.
Analysis of the essential oil
The essential oil was analyzed with Agilent Technologies 7890 GC system coupled with Agilent
Technologies 5975 C quadrupole mass spectrometer as detector equipped with 30 m capillary column
(ID=0.25 mm) coated with 5 % diphenyl-95 % dimethylsiloxane. Chromatographic conditions:
isothermal mode at 50 ?C for 2 min, then temperature programmed mode from 50 to 280?C at 4?C/
min and isothermal mode at 280?C for 20 min. Evaporator temperature 280 ?C, ionization chamber
temperature - 230 ? C, ionization energy - 70 eV. The oil components were identified by comparison of
their linear retention indices and full mass spectra with the library of mass spectrometric data Wiley
275 and literature (13-15).
# 488 #
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Alina M. Shushenacheva and Aleksandr A. Efremov. Chemical Composition of the Essential Oil from Fruits?
Results and discussion
It was found that the essential oil from fruits of Heracleum dissectum L. quantitatively distils
within 53 hours. The essential oil is a light-blue liquid with a specific strong odour.
It was shown by GC and GC-MS method that the essential oil from fruits of Heracleum
dissectum L. growing in Krasnoyarsk region contains more than 47 compounds, 43 of which were
identified (in an amount exceeding 0.1 % of the whole oil). In the fi rst fraction of the essential oil
29 constituents were identified, in the second fraction - 31, in the third? 33, in the fourth - 30, in
the fifth? 33 constituents.
The data on distillation dynamics of the essential oil from fruits of Heracleum dissectum L. are
shown in Fig. 1. As it can be seen from Table 1, refraction indices of all five fractions are different and
refraction indices increase from the first to the fifth fraction (except for the second).
The composition of the essential oil from fruits of Heracleum dissectum L. is shown in
Table 2.
As it can be seen from Table 2, the essential oil from fruits of Heracleum dissectum L. contains
three compounds with concentration more than 5 %, five compounds with concentration from 1 to
Fig. 1. Yield of the essential oil during extraction
Table 1. Distillation dynamics and refraction indices of the essential oil from fruits of Heracleum dissectum L.
Fraction
Time of distillation (h)
Yield (% by weight)
Refraction index
1
4.83
27.39
1.4246
2
14.67
42.62
1.4244
3
5.50
9.13
1.4269
4
18.00
16.90
1.4280
5
10.00
3.96
1.4317
whole
53.00
100.00
1.4254
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Table 2. Composition of the essential oil from fruits of Heracleum dissectum L.
?
RT
RI
Compound
% Composition
1 fr.
2 fr.
3 fr.
4 fr.
5 fr.
whole
1
7.96
1003
octanal
2.14
0.45
0.25
-
-
1.31
2
8.08
1008
isobutyl 3-methylbutanoate
0.42
0.24
0.21
-
-
0.46
3
8.73
1026
limonene
0.51
-
-
-
-
0.24
4
8.97
1034
benzyl alcohol
1.56
2.75
1.33
1.48
1.33
1.51
5
9.97
1063
(Z)-5-octene-1-ol
0.30
0.10
-
-
-
0.10
6
10.25
1072
n-octanol
-
2.57
2.06
1.84
1.73
1. 80
7
10.53
1080
Isobutyl 3-methyl-2-butenoate
0.32
0.17
-
-
-
0.21
8
11.38
1105
2-methyl-3-methylbutyl butanoate
0.14
0.38
0.35
0.27
0.16
0.20
9
11.44
1107
Isopentyl 3-methylbutanoate
0.33
-
-
-
-
0.25
10
11.53
1109
3-methyl-2-methylbutyl butanoate
0.29
0.21
0.16
-
-
0.10
11
12.94
1150
n-hexyl isobutanoate
0.47
0.31
0.26
0.20
0.12
0.32
12
14.19
1186
pentyl 3-methyl-2-butenoate
0.25
0.18
-
-
-
0.10
13
14.49
1194
hexyl butanoate
0.77
0.81
0.83
0.57
0.56
0.75
14
14.72
1201
vinylcyclohexane
5.02
3.71
2.85
2.19
1.12
4.52
15
14.96
1208
decanal
0.59
0.53
0.40
0.33
0.23
0.55
16
15.45
1222
octyl acetate
17
16.03
1240
2-methylhexyl butanoate
64.73 57.08 46.73 39.36 25.80 58.50
0.33
0.38
0.39
0.37
0.32
0.37
18
16.20
1244
3-methylhexyl butanoate
0.71
0.73
0.68
0.62
0.51
0.76
19
17.59
1285
(-)-bornyl acetate
-
-
-
-
0.13
0.10
20
18.82
1322
3-methylhexyl 2-butenoate
0.25
0.22
0.26
0.23
0.16
0.22
21
19.63
1347
octyl-2-methyl propanoate
0.69
0.83
0.94
0.92
0.89
0.77
22
20.63
1377
1-ethenylhexyl butanoate
0.49
0.62
0.83
1.12
1.24
1.03
23
21.14
1393
2-methyloctyl propanoate
12.91 18.87 14.21
4.25
-
10.18
24
21.22
1395
1,5-cyclodecadiene
0.29
0.33
0.62
0.27
0.50
0.60
25
21.33
1399
2,6-dimethyl bicyclooctane
-
0.15
0.38
0.15
0.17
0.17
26
21.65
1408
tetradecanal
-
-
0.22
0.25
0.29
0.15
27
21.73
1411
decyl acetate
0.33
0.41
0.55
0.69
0.68
0.40
28
21.88
1416
trans-caryophyllene
0.27
0.13
0.14
0.16
0.24
0.22
29
22.19
1426
cyclodecene
0.16
0.15
0.22
0.24
0.28
0.17
30
22.45
1435
n-octyl-2-methyl butanoate
0.31
0.32
0.50
0.55
0.60
0.21
31
22.60
1440
3-methyloctyl butanoate
0.66
0.64
0.92
0.99
1.06
0.36
32
23.80
1477
germacrene D
0.36
-
-
-
-
0.16
33
25.12
1521
?-cadinene
-
0.26
0.46
0.54
0.78
0.38
34
25.90
1548
octyl hexanoate
0.33
0.24
0.49
0.67
0.88
0.25
35
26.40
1565
(?)-nerolidol
-
-
0.18
0.24
0.36
0.21
36
26.58
1570
4-ethyl-3-ethylydene cyclohexene
-
-
0.20
0.28
0.41
0.23
37
26.98
1585
?-alanine
-
4.80
5.09
13.77
19.61
9.47
38
27.14
1590
decyl butanoate
-
-
0.38
0.53
0.82
0.40
39
28.54
1639
?-cadinol
-
-
-
-
0.23
0.10
40
28.90
1652
?-cadinol
-
-
-
-
0.33
0.10
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alina M. Shushenacheva and Aleksandr A. Efremov. Chemical Composition of the Essential Oil from Fruits?
41
29.73
1681
cis-azarone
-
-
0.61
0.81
1.47
0.62
42
30.92
1725
chamazulene
-
-
0.28
0.42
0.80
0.34
43
32.31
1778
octyl octanoate
-
0.33
0.34
0.89
3.31
1.55
44
36.92
1954
dibutyl phthalate
-
-
0.31
0.31
0.82
0.21
Total
98.54
RI ? experimental linear retention indices calculated against a C8?C20 n-alkanes mixture
5 % and 36 compounds with concentration from 0.1 to 1 %. Mainly constituents are esters, alcohols
and aldehydes. Sesquiterpenes and terpenes content is low (less than 3 %). The major constituents of
the oil are vinylcyclohexane (4,52 %), octyl acetate (58,5 %), 2-methyloctyl propanoate (10,18 %) and
?-alanine (9,47 %). It was found that the essential oil from fruits of Heracleum dissectum L. growing
in Krasnoyarsk Region of Russia contains chamazulene (0,34 %).
As it is seen, first fractions of the essential oil contain highly volatile components and during the
distillation process the content of semi-volatile compounds grows up slowing down the distillation
process. So, in the first fraction one of the major constituents is octanal, whis was not found in the
fourth and fifth fractions.
It was made a comparison of the essential oil from fruits of Heracleum dissectum L. growing in
Krasnoyarsk region of Russia with the essential oils from plants growing in other places obtained by
steam distillation (5,6,16).
As it is seen from Table 3, the composition of the essential oil from fruits of Heracleum dissectum
L. depends on the habitat. The main constituent of the essential oils from fruits of plants growing
in Krasnoyarsk and Leningrad regions of Russia and Mongolia (Mongolia2) is octyacetate, but its
content is different. The largest amount of octylacetate is contained in the essential oil from fruits of
Heracleum dissectum L. growing in Krasnoyarsk region.
It is known that the essential oils from plants of Heracleum dissectum L. growing in natural
environment does not contain terpenes [5], but they were found in small amounts in the essential oil
from fruits of plant growing in Krasnoyarsk region.
There is a difference in composition of the essential oils from fruits of Heracleum dissectum L.
gathered in different years in Mongolia. The essential oil from fruits gathered in 1980 (Mongolia1)
does not contain octylacetate, but it is the main constituent of the essential oil from fruits gathered
later (Mongolia2). The area of growth Heracleum dissectum L. includes Central Asia, so Heracleum
dissectum grows in natural environment. Despite this the main constituents of one of the essential oils
from fruits of Heracleum dissectum L. growing in Mongolia (Mongolia1) are terpenes.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alina M. Shushenacheva and Aleksandr A. Efremov. Chemical Composition of the Essential Oil from Fruits?
Table 3. Some constituents of the essential oils from fruits of Heracleum dissectum L. growing in different
places
Component
Leningrad
Region, Russia*
Mongolia1
Krasnoyarsk
Region, Russia
Mongolia2
? ? pinene
1.1
22.17
-
0.48
myrcene
-
10.91
-
9.49
? ? pinene
2.4
1.31
-
-
octanal
9.2
-
1.31
-
limonene
-
2.82
0.24
2.81
benzyl alcohol
-
-
1.51
-
n-octanol
6.2
-
1. 80
4.82
hexyl butanoate
2.1
-
0.75
-
vinylcyclohexane
-
-
4.52
-
octylacetate
45.1
-
58.50
46.92
octylbutyrate
22.7
-
-
11.21
(-)-bornyl acetate
-
1.58
0.10
-
2-methyloctyl propanoate
-
trans-caryophyllene
-
10.18
-
0.17
0.22
-
germacrene D
-
0.43
0.16
?-cadinene
-
0.15
0.38
-
1.72
0.21
-
(?)-nerolidol
?-alanine
-
-
9.47
-
chamazulene
-
-
0.34
-
1- V.P. Papageorgiou, G. Ochir, O. Motl, N. Argyriadou and H. Dunkel, Composition of the essential oil from
Heracleum dissectum. J. Nat. Prod., 48, 851-853 (1985).
2-S. Shatar, Sh. Altantsetseg, J. Irekhbayar, D. Suran, L.D. Radnayeva, S.V. Jigjitjapova, Chemical composition
of essential oil from fruits of Heracleum dissectum Ledeb. of Mongolian flora (Khimicheskii sostav efirnogo
masla plodov Heracleum dissectum Ledeb. flory Mongolii). Bulleten VSNC SO RAMN, 2 (66), 316-317 (2009).
* - introduced plant
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Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 494-503
~~~
??? 546.824-31
Obtaining of Hollow Fibers
of Titanium Dioxide by Interaction
of Titanium Tetrachloride with Cotton Cellulose
Valery ?. Tarabanko*,
Marina A. Smirnova and Yulia V. Chelbina
Institute of Chemistry and Chemical Technology SB of RAS
50/24 Akademgorodok, Krasnoyarsk, 660036, Russia
Received 22.10.2014, received in revised form 07.12.2014, accepted 20.12.2014
The interaction of TiCl4 and cotton cellulose has been studied. Titanium oxichlorides grains are
precipitated on the cellulose surface at room temperature, and solid film of titanium oxichlorides is
formed on the cotton fiber surface at 100 °?. Heating of such fibers in air up to 600 °? produces titania
hollow fibers. The acid pretreatment of cellulose before titanium oxichlorides precipitation allows the
long solid hollow fibers of titania to be obtained. The obtained mesoporous material is characterized
by surface area of 36 m2/g and average pore width of 12 nm.
Keywords: cellulose, cotton, titanium chloride, titania, hollow fiber.
????????? ????? ??????? ???????? ??????
??????????????? ???????????? ??????
? ????????? ??????????
?.?. ??????????, ?.?. ????????, ?.?. ???????
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50/24
?????? ??????? ?????????????? ???????????? ?????? ? ?????????? ????????????????
?????????? ???????. ??? ????????? ??????????? ??????????? ?????? ?????????? ??
??????????? ????????? ? ????? ??????, ? ??? 100 ?? ????????? ??????? ?????????????????
???????? ??????. ????????, ??? ????????? TiCl4 ?????????????? ??????????????? ?????????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: veta@icct.ru
# 494 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
? ??????????? ?? ??????? ????????? ???????? ??????? ????? ??????? ???????? ??????
????????? ????? 10 ??? ? ???????? ?????? 1?2 ???. ?????????? ???????? ???????????????
???????? ???????????? 36 ?2/? ? ??????? ????????? ??? 12 ??.
???????? ?????: ?????????, ??????, ?????? ??????, ??????? ??????, ????? ???????.
????????
?????????? ?????? ?????????????? ??????????? ?????????? ?? ??????????? ????????? ? ????? ? ??????? ??????????? ??????? [1].
??????? ?????????? ????? ????????? ????????? ??????? ?????????? ??????????? ? ?????? ?????????? ??????, ??????? ????-????-?????? [2]. ????? ??????????? ??????? ?????????
????? ??????? ?????????? ?? ????????? ???????? ????????? ???????? ? ???????? ?????????? ?????? ? ????????? ?? ?????????????. ?????? ?????????? ???????? ????????? ?????
??????? ???????? ??????, ?????????? ???????????????? ????????? ?? ?????? ????? ????-???????????, ??????? ? [3]. ????????? ????????? ??????????????????????????? ??? ?????????
??????? TiO2 ?????????? ? ??????? ?????????? ????? [4]. ????? ??????? ?????? ????????? ??????? ?????????? ? ?????????????? ??????? ???????? ???????????? ??????, ? ???????? ????????? ???????? ?????????? ???????????? ??????? ???????? ?????????? ??????, ???????????? ?? ??????????? ??????? [5].
????? ?????????????? ?????? ????????? ?????????? ?????? ?? ??????????? ?????????
?? ???? ?? ??????????? ??????????????. ? ????? ?? ?????? ?????, ??????????? ?????????
??????? ???????????? ?????? ?? ??????????? ???????? ???????????? ????????? [6], ????????????? ??????????? ????????? ? ???-???-?????????? ?????? Cl3Ti-O. ????????, ??? ?????????? ??????? ????????????? ??????????????? ? TiCl4, ??????? ?????????? ?? ?????????????
Ti : ????????? ????? = 1 : 1,5?2. ??????? ??????? ?????? ??????????? ?????????? ???????????? ???????? ???????? ?? ?????, ????????? ? ?????? ? ??????????? ?? ?????????, ????????
1?2 ?????? ?????? ?? ????? ????????? [6].
? ???????? ????? ?? ??????? ??????????????? ????????? ?????????? ???????? ?????????, ?????????? ? ?????????? ??????? ?????? ?? ??????? ??? ?????????? [7]. ??? ????? ? ??????????????? ?????? ????? ???????????? ????? ???????? ???????? ??????? ??????????????
????????? ? ????????? ??????, ????????? ??????, ???????? ? ??. [8]. ? ?????? [9] ?????????????? ??????????? ??????????????? ?????? ????????? ??? ?????????????? ?????????
? ?????????? ???????????? ?????? ? ??? ??????????????????, ?? ??????????? ?? ?????????
????????????? ????? ?? ???????????. ??? ????????? ???????????? ??????? ?????????? ????????? TiCl4 ?????????? ??????????? ????????????????????? [10]. ??????? ????? ??????????
????????????? ?????? ??? ????????? TiBr4 ? ???????????? ???????????????? ??????????????? [10]. ?????????? ????????? ????????? ? ? ????????? ?????? ?????? ? ???????? ?????????? ?????? (???????? ???????? ??????, ????? ? ??????) [8, 10, 11]. ???????????? ????????
?????????? ???? ????????? ???????????? ???????????? ?????? ?????? ????? ????????????
???????? ????????? ?????? ??????????? [11], ???????? ?? ????????? ??????????? ??????????? ???????????????? ? ??????????? ???????? ?????????????. ??????????? ?????? ??????
# 495 #
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Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
?????? ???????? ?? ?????? ?????????????, ?? ???????????? ? ???????? ???????? ??????????
????????? ??????????? ??????????? ??????????? ?????.
???? ????????? ?????? ??????????? ? ?????? ???????, ??????????? ???????? ???????
????? ??????? ???????? ?????? ? ??????????? ?????????? ???????, ???????????? ?????? ???
????????????? ? ?????????????? ?????????.
????????????????? ?????
? ?????? ???????????? ???????? ??????????????? ????????? ???? ? ??????????? ??????
???????????? «???».
????????? ???? ??????? ? ??????? ??????? ?????? (IV), ??????????? ? ???????? ??????
??? ????????? ??????????? ??? ????????? ?? ??????? ???? ??? 100 °?. ????? ??????? ?????????? ? ?????????? ??? ???????. ????? ????????? ????????? ????? ?????????? ???????? ?
????????? ???? ?? ????????? ??????????? ?? 600 °? ? ??????? 4 ?.
????????? ???????? ??????????? ?? ????????? ??????????? ?????????? Hitachi ??-1000.
??????????? ?????????????? ???????? ???????? ?? ??????? Micromeritics ASAP 2020 (???
??? ?? ???) ?? ??????? ????? ??? 77 ?.
??? ???????? ??????? ??????????? ??????????? ?????? ?????????? ? ?????????? ???????? (????????, ???????, ????????) ????????? ? ???????? ??????? ??????, ??????????? ?
???????? ?????? ??????????? ????? ??? ????????? ??????????? ??? ????????? ?? ????????
????. ??-??????? ?????????? ?? ??-?????-???????????? Tensor 27 (Bruker, ????????).
?????????? ? ??????????
??????? ??????????? ?? ?????????????? ???????????? ?????? ? ??????????. ???
????????? ????????? TiCl4 ??? 20 °? ?? ??????????? ??????? ?????????? ??????? ????????
????? 600?700 ?? (???. 1). ?????????? ??????????? ??????? ?????????? ????????????? ?????? ?????? (IV) ???????????? ? ????. 1. ??????? ??????????? Cl : Ti ????????? ? ?????????
(0,25?0,57) : 1, ?????? ? ???????? ??? ????????? ??????, ??? ?? ???????????. ????? ?????? ?
????? ?????????????? ????????, ???????????? ? ???? ???????? ?????????: ??????, ???????
? ??. ????????? Ti : Fe ?? ??????????? ?????? ??????????? ???? ?? ????????? ? ???? ?????????? ?? ??????????? ???????, ?.?. ?????????? ?????? ???????????? ?????? ??????? ??????????? ?? ??????????? ???????. ???? ?? ??????? ????????? Ti : Fe (????? 2 : 1) ?? ???????????
???????, ???????? ?????? ???????????? ?????? ?? ??????????? ????????? ??? ?? ?????????
??? 20 ?? ??????????? ?? ??????????.
????????? ????????? TiCl4 ??? 100 °? ? ??????? 1 ? ???????? ? ???????????? ????????????????? ????? ? ?????? ???????? ????? 1000 ?? ?? ??????????? ??????? (???. 1). ????????
?????? ??????????? ??????? (????. 2) ????? ? ??????? ????? ??????? ??????? ???????????
Cl : Ti = (0,5 ? 0,8) : 1.
?????????? ????????? ????? ???????? (????. 3).
?????????? ?????????? ??????????, ??? ??? 20 °? ????? ?????????? ?? ??????????? ??????????? ??????? ? ???????? ? ???? ?????? (???. 1). ????????? ?????????? ?????? ? ??????
?? ??????????? ????????? ?????? ?? 5 ??? ?????? ?? ????????? ? ??????? ? ????????. ???
??????????, ??? ?? ??????? ????? ??????????? ????????? ????? ????? ?? ?????????? ? ???# 496 #
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???. 1. ??? ??????????? ???????? ????????? ?????????, ???????????? TiCl4 ??? 20 ?? (?????) ? ???
100 ?? (??????)
??????? 1. ?????????? ????????? (??????? %) ? ??????? ?????????, ???????????? TiCl4 ??? 20 °?
????????
(?? ?????????)
? ????? ???????
(?? ???????????)
Ti
72
66,3
36,2
53,8
Cl
14,6
Si
3
12,2
15,2
13,5
6
12,8
9,6
S
1,2
3,9
11
-
Fe
9,2
11,6
24,8
23,1
Cl/Ti
0,27
0,25
0,57
0,34
Ti/Fe
7,8
5,7
1,5
2,4
??????? 2. ????????????? ???????? ?????????? ????????? (??????? %) ? ??????? ?????????,
???????????? TiCl4 ??????????? ??? 100 °? ? ??????? 1 ?
????????
(?? ?????????)
? ????? ???????
(?? ???????????)
Ti
61,5
61,1
68,8
59,6
Cl
35
36
26,5
34,6
Al
3,4
2,9
4,7
4
K
-
-
-
0,9
Ca
-
-
-
1
Cl/Ti, ????/????
0,77
0,80
0,52
0,78
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
??????? 3. ?????????? ???? ? ???????? ?????????, ???????????? ????????????? ?????? ? ??????? 1 ?
???????
?????????? ????, %
???????? ????
4,8
????, ???????????? TiCl4 ??? 20 ??
10,9
????, ???????????? TiCl4 ??? 100 0?
11,2
??????? ?????? ???????????? ? ???????? ??????? ?????????? ?????????. ?????????? ??????????? ?????? ? ??????? ?? ????????? ????? 6 ???. % ? ????????? ?? ??????? ??????, ???????
????????? Cl/Ti ? ???????? ???????????? ????? 0,3.
??? 100 ?? ????? ?????????? ?? ??????????? ????????? ? ???? ?????????????? ?????? ?
?????? (???. 1). ?????????? ??????????? ?????? ? ??????? ?? ????????? ????? 6 ???. % ? ????????? ?? ??????? ??????, ??????? ????????? Cl/Ti ????? 0,8, ??? ? 2?3 ???? ?????? ?? ????????? ? ??????????? ? ???????? ??? 20 °?.
????????????? ?????????? ?????? ???????, ??? ??? ??????? ??????????? (100 °?) ????? ?????????? ?? ??????????? ??????? ????????? ? ????? ????????????????? ??????, ? ???
?????? (20 °?) ? ? ???????? ? ???? ??????.
??????? ???????? ???????????????? ????????? ????????? ???? ?? ??????????? ?????????????? ????????? ? ????????????? ??????. ???????????, ??? ?? ??????????? ???????,
?????????????? ???????????????? ????????? ??????? ???????, ??????????? ????????, ??????????, ??? ??????, ???????-????????? ?????? (???. 2).
? ??????????? ????????????????? ?????????????? ????????? ? TiCl4 ???????????, ?????
??? ? 10 ???, ?????????? ??????? ????????? Cl/Ti ?? 0,2 ?? 3,4 ? ?????????? ?????????????
???????? ??????(IV) (????. 4). ??? ????????, ??? ?????? ???????? ??????? ?????? ??????????????? ? ?????????????? ???????? ?????????, ??????? ???????? ?????? ????? Ti-O, ??-
???. 2. ???-??????????? ???????? ??????????????? ????????? ?????????, ???????????? TiCl4 ???
100 0? (????? ? 10 ???, ?????? ? 50 ???)
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Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
??????? 4. ?????????? ????????? (??????? %) ? ???????? ??????????????? ?????????, ????????????
TiCl4 ??? 100 °? ? ??????? 1 ?
????????
(?? ?????????)
? ????? ???????
(?? ???????????)
?????????????????
????????? TiCl4,
???
10
50
50
Ti
86,1
28,5
19,5
Cl
11,9
71,5
40,3
Al
1,9
-
-
Fe
-
-
12,2
Si
-
-
9,0
Cl/Ti
0,19
3,4
2,8
????? ????????? ???????. ??????????? ?????? TiCl4 ????????? ? ?????????????? ???????????? ???????????? ??????, ??????? ????????? ??????????? ? ???????????? ??????????
Cl/Ti [6].
?? ????? ???????, ????????? ????? ????????? ???????? ??????, ?????????? ????????????
?????? ?????? (????????? ??????? ????. 4) ?? ???? ????? ???????????? ??????? ???????????
?? 40 %. ??? ???????????? ????? ? ????????????? ??????? ?????????????? ????????? ??????? ? TiCl4 .
??? ???????? ???? ???????? (???. 2) ???????? ????? ?????? ?? ???????? ?????? (???. 3).
???????????? ?????? ?? ???????? ??????, ?????????? ??????????????? ??????????, ????? ?????????? ?????????????? ?? ????????? ? ????????, ??????????? ????? ??????????
?????????? ????????????? ?????? (50 ???). ????????, ?????????????? ????????????? ??????,
?????????? ?????????? ?????????? ????????????? ??????, ??????????? ??????? ?????????
?????, ???????????? ??? ???????? ?????????. ???? ????????, ? ????? ???????? ????? ???????????? ??????, ???????????? ??? ??????????????? ????????? TiCl4, ????????????, ??????????, ??? ???????????? ???????????.
??????? ??????? ???????????????? ????????? ?????????, ?? ??????????? ????????? ????????????? ?????? ? ?????? ??? 500 °?, ??????????? ???????? ??????? ????????
?????? ?? ???????? ?????? (???. 4). ?????????? ???????? (?????? ???????? ?????? ???)
??????????????? ???????? ???????????? 36 ? 2/? ? ??????? ????????? ??? 12 ??. ??? ?????????? ?? 1000 °? ???? ??????? ????????? ? ????? ? ??????????? ???????? ???????????
?? 5 ? 2/?.
?????????? ??????????, ??? ????????????? ???????? ????????? ???????? ??????? (??????? ?? ????? ? ???????? ???????? ?????????) ????? ??????? ?? ???????? ?????? ?????????
????? 10 ??? ? ???????? ?????? 1?2 ???. ??????????? ?????????? ????????, ?? ????????
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Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
???. 3. ???-??????????? ?????? ???????? ??????, ?????????? ??????? ?????????, ???????????? TiCl4
??? 100 0? (????? ? 10 ???, ?????? ? 50 ???)
????? ???????? ???????? ? [4] (??????? ??? ???????? ???????? ?? ?????????????????????????? ? ??????? ?????????? ?????), ? ????? ? [5] (????????? ?????????? ?? ?????? ????????????
?????? ? ??????? 1?48 ?).
# 500 #
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Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
???. 4. ???-??????????? ?????? ?? ???????? ??????, ?????????? ??????? ??????????????
??????????????? ?????????
??????? ????????? ?????????? ????????? ????????? ??????. ?????? ????????, ???
????????? ??? ????????? ?????? ??????, ? ??? ????? ???????????? ??????, ???????????? ??????????, ?????????? ? ??????????? ?????????????? ??????????????? ?????? ? ???????? ?
???????? ???????????? ????? ???????? [8, 10]. ???????? ????? ???????? ? ?????????? ??????????? ?? ???????????. ??????????????, ??? ??????????? ????? ???????????? ? ????????????
?????? ???? [TiOCl-n ? C+] [11]. ???? ?????????????? ????????????? ? ??????? ???????????
????? ? ???????????? ???????????? ?????????????? ?????? O-C-Cl:
...
OH
CH2OH O
O
OH
OH
O...
O
CH2OH
+ TiCl4
...
CH2OH O
OH
OH
OH
OH
Cl + Cl3Ti
O
OH
O...
O
CH2OH
???????????????? ????? ????? ??? ?????????? ????????? ?????? ?? ???? ????????: ????????, ???? ???? ??????????? ??????, ??-??????, ???????????? ????? C-Cl ???????????? ?????????????? ?????? ????? ???????????? ? ???????????? ?????? ? ??????????? ????????
?????????? ????????.
?? ???? ???????? ?? ??????? ??????? ??????????? ??????????? ????? ?? ??????????
?????? ? ????????. ??????????? ???????????? ????????? ? ????????? ? ????????, ??????? ??
????? ??????????? ?????? ? ????? ??????????.
? ??-??????? ????????, ???????????? TiCl4 (???. 5), ???????????????? ?????? ??????????, ??????????? ??? ????? ?-Cl (750 ??-1), ???????????? ??? ??????? ??????????? ?????. ?
??-???????? ???????? ? ??????? ? ??????????? ???????????? ?????? ????? ????? ?? ??????????. ????? ???????? TiCl4 ?? ????????? ?????????? ???????? ????? ?-Cl ?? ??????????????.
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0.8
0.6
4
0.2
0.4
Absorbance Units
1.0
1.2
1.4
Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
0.0
3
4000
3500
2 3000
2500
2000
Wavenumber cm-1
1500
1000
1
???. 5. ??-?????? ????????, ???????????? ???????? ?????? (IV): 1 ? TiCl4; 2 ? TiCl4+????????, ????????
24 ?; 3 ? TiCl4 + ???????? ??? ????????; 4 ? TiCl4 + ????????, ?????? ??? 60 °? ? ??????? 1 ?
????? ???????, ??????? ????????, ??? ??????????? ????? ? ???????? ????????? ??? ????????? ???????????? ?????? ????? ???????????? ? ???????????? C-Cl-????? ????????????
?????????????? ??????.
????????????? ???????????? ??????? ?????? ????????? ????? ??????? ?? ???????? ?????? ????? ???? ??????? ??? ???????? ?????? ? ???????? ????????? ????????? ?????????????? ??????????? ????????? ? ??????????????? ??????????.
?????? ???????????? ????. ????. ???? ?.?. ????????? ? ?.?. ??????? ?? ??????????
??????????-???????????????? ????????????, ????. ???. ???? ?.?. ???????? ? ????. ????.
???? ?.?. ??????? ?? ?????? ? ???????????? ??????? ??? ? ????????? ??????????? ????????????? ????????.
?????? ??????????
1. ???????? ?.?., ?????? ?.?., ?????????? ?.?., ?????????? ?.?. ?????????? ?
??????????? ????????????? ??????? d-????????: ?????? ? ????????????? // ?????? ?????.
2005. ?.74. ???.7. ?. 651?685.
2. Hsin-Hung Ou, Shang-Lien Lo. Review of titania nanotubes synthesized via the hydrothermal
treatment: Fabrication, modification, and application // Separation and Purification Technology. 2007.
V.58. P. 179?191.
3. Rahman M., Tajabadi F., Shooshtari L., Taghavinia N. Nanoparticulate hollow TiO2 fibers as
light scatterers in dye-sensitized solar cells: layer-by-layer self-assembly parameters and mechanism //
ChemPhysChem. 2011. Iss.12. P. 966?973.
4. Animian M. Kh., Taghavinia N., Iraji-zad A., Mahdavi S.M., Chavoshi M., Ahmadian S. Highly
porous TiO2 nanofibers with a fractal structure // Nanotechnology. 2006. V. 17. P. 520?525.
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Valery ?. Tarabanko, Marina A. Smirnova? Obtaining of Hollow Fibers of Titanium Dioxide by Interaction?
5. Imai H., Matsuta M., Shimizu K., Hirashima H., Negishi N. Morphology transcription with
TiO(2) using chemical solution growth and its application for photocatalysts // Solid State Ionics. 2002.
V.151. Iss.1-4. P. 183?187.
6. Hider S., Marchessault R.H. Studies on Alcohol-Modified Transition Metal Polymerization
Catalysts. II. Interaction of TiCl4 with Cellulose and Model Compounds // J. Polym. Science: Part C.
1965. ? 11. P. 97?105.
7. ??? ?.?. ??????????????????? ????????????????? ?????????. ?., 1981.
8. ??????? ?.?., ????? ?.?. ?????????? ????????? ????????? ????????? ?????? ? ?????
????????? ?????????? ????????? // ?????? ?????????? ?????. 2008. ?. 81. ???.1. ?. 152?
156.
9. ????????????? ?.?., ???????? ?.?. ????????? ??????????????? ?????? ????????? //
?????? ?????????? ?????. 1972. ?. 45. ? 4. ?. 857?861.
10. ????????? ?.?., ????????? ?.?., ?????? ?.?. ?????????? ?????? ?????? ? ?????
????????? // ?????? ?????. 1977. ?. 26. ? 8. ?. 1395?1410.
11. Afanasev V.A., Sarybaeva R.I., Sultankulova A.S. Cellulose sorbents obtained by the action of
Lewis acids // Pure and Appl. Chem. 1989. V. 61. Iss.11. P. 1993?1996.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 504-509
~~~
??? 536.63
High Temperature Heat Capacity
of Bismuth-gallium Sillenite
Liubov T. Denisova, Liliya A. Irtyugo,
Vladimir P. Shereb and Viktor M. Denisov*
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
Received 16.09.2014, received in revised form 24.10.2014, accepted 09.11.2014
Bismuth gallium oxide (12:1) of sillenite structure was obtained by the solid-phase synthesis. The
heat capacity of this compound was determined with the use of differential scanning calorimetry
at 340?920 K. From experimental data, the thermodynamic functions of the solid oxide were
calculated.
Keywords: bismuth-gallium sillenite, heat capacity, thermodynamic properties.
??????????????????? ????????????
??????-?????????? ?????????
?.?. ????????, ?.?. ??????,
?.?. ?????, ?.?. ???????
????????? ??????????? ???????????
??????, 660041, ??????????, ??. ?????????, 79
???????????? ???????? ??????? ??????-????????? ????? (12:1) ?? ?????????? ?????????.
??????? ???????????????? ??????????? ???????????? ???????? ??? ???????????? ?
????????? 340?920 ?. ?? ????????????????? ?????? ?????????? ?????????????????
??????? ???????? ????????? ??????????.
???????? ?????: ??????-???????? ????????, ????????????, ????????????????? ????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: antluba@mail.ru
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Liubov T. Denisova, Liliya A. Irtyugo? High Temperature Heat Capacity of Bismuth-gallium Sillenite
????????
??????? ???????? ???? ?? ?????????? ?????????? ???????????? ? ???????????? ?????- ?
????????????????????, ?????????? ? ???????????????? ?????????? [1, 2]. ???????? ?? ???, ?????????? ? ????????????????? ????????? ????? ?????????? ????????????. ???????? ? ???????????? ?????????? Bi12MxO20±? (M ? Si, Ge, Ti, Ga, Fe, Zn; x ? 1; 0 ? y ? 0.7) ????????? ? ?????? [3].
??? ???? ????????, ??? ????????????? ?? ?????? Ga, Fe ? Zn ????? ?????????? ? ??????????
?????????????? ???? ??? ??????????? ?? ????????? ? ?????????. ? ???????? ????????? ????????
?????????????? ???? ? ? ???? Bi2O3. ?? ??????? ?????? ?? ???????????? ????? ??????????, ? ???
??????????????? ??????????? Cp(T) ??? ?????????? Bi25GaO39 [3]. ?????? ? ?????????????? ?????????? ? ???????? ???????????????? ???????? ?????????? ? ??????? [4, 5].
?? ?????? ????? [1, 6], ????????? ????????? ??????? Bi2O3 ? Ga2O3 ??????????????? ???????? ?????????? ?? ?????????? ?????????, ??????????? ????????????? ??? ??????????? 1083 ?
? ?????? ???????? ?????????? ? ???????? ?? 25:1 ?? 20:1. ? ?? ?? ????? ?????? [1] ?????????, ???
? ?????? ??????? ????????-???? ????? ????? ?????? 12:1 (Bi24Ga2O39). ??? ???? ??? ????????
??????? ? ?????????? Bi2Ga4O9, ??????????? ? ??????????? ???????? (??. ??. Pbam) ? ???????????? ??????????????? ????????? 1353 ?. ????? ????????? ??????? ?????????? ?? ??????????
?????????, ??-????????, ????????????? ????????? ??? ????????? ??? ????????? ?????? ????.
?????? [3] ???????, ??? ????? ????? ????????, ????????? ??????? ???????????????? ??????????? ??????????. ?? ???????, ??? ? ??????? ????????????? ??????? ? ???????????? ?????????
(???????????, ?????, ??????) ????????? ???????? ?????????? ???????.
???? ?????? ? ????????? ??????????????????? ???????????? ? ??????????? ?? ???? ?????? ????????????????? ??????? Bi24Ga2O39.
????????????????? ?????
?????????? Bi24Ga2O39 ???????? ?? ???????????? ?????????? ? ???????? ???????????
??????? ??????? ? ????????. ?????? ????????? ?? Bi2O3 ? Ga2O3 («??.?»). ??? ????? ???????
???????? ??????????? ?????????? ? ???????? ?????? ? ??????? 15 ???. ????? ????? ????????? ?????????? ??????????? ? ??????? 30 ??? ??? ??????????? 1223 ?. ?????????? ??????? ??????? ????????? ??????????. ???????????? ???????? ???????? ? ????????? ???? ?
????????? ??????? ? ??????? 100 ? ??? ??????????? 1003 ? ? ???????? ?????????????? ?????????????. ?????? ??? ?????????????? ?????? (??????????????? ??????). ????? ????? ??
???????????????, ?????????? ?? ??????? Shimadzu, ?????????????? ?????? ????????, ?????????? ?????????? Bi24Ga2O39. ???????, ??? ???????? ???????????? ?????? ????? 10.176
?, ??? ????????????? ?????? ??? ?????????? 12Bi2O3:1Ga2O3, ??????????? ? [1]. ????? ?????
???????? ?????????. ????? ??????? ?????????? ??????? Bi25Ga O39 ?? ???????? ???????????
25Bi2O3:1Ga2O3 ???? ?????? ????????????? ??????? Bi24Ga2O39 ? Bi2O3.
???????????? (Cp) ???????? ? ?????????? ?????? ??????? ???????????????? ??????????? ???????????? ?? ??????? STA 449 C Jupiter (NETZSCH). ???????? ????????????? ??????? ????????? ???? ????? [7]. ????????????? ???????? ???????????? ???????????????????
???????????? ???????? ?? ?????? ???????????? ???????????? (???????????????? ??????????? ??????). ????????????????? ?????? ???????????? ? ??????? ?????? NETZSCH Proteus
Thermal Analysis ? ????????????? ???????????? ??????????? Systat Sigma Plot 12.
# 505 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Liubov T. Denisova, Liliya A. Irtyugo? High Temperature Heat Capacity of Bismuth-gallium Sillenite
?????????? ? ??????????
????????????????? ?????????? ?? ??????? ??????????? ?? ???????????? Bi24Ga2O39 ???????? ?? ???. 1.
?? ???? ?????? ???????, ??? ? ?????????? ????????? ?????????? ???????? Cp ??????????? ?????????????. ?????????? ???????? Cp(T) ????? ???? ??????? ???????????? ?????? ?
????? [8]
CP
a bT cT 2 ,
(1)
??????? ??? Bi24Ga2O39 ? ????????? ????????? ?????????? ????? ????????? ???
(??/???? ?)):
C?
1394.0 326.5 �103 ? 13.53 �105 ? 2 .
(2)
??? ???? ??????????? ?????????? H0(T) ? H0(340 K) ? S0(T) ? S0(340 K) ?? ????????? ????????????????? ??????????. ?????????? ?????????? ????????? ? ???????.
?? ???. 1 ??? ????????? ????????? ? ?????? [3]. ?????, ??? ???????? Cp, ?????????? ????
? ? [3], ????????? ??????????? ????? ?????.
?????? ???????????? Cv ????? ?????????, ????????? ?????? ????? [9]. ?????? ??? ???????? Cp ? Cv ?????????? ????????? ??????????? [10]
Cp ? Cv = ?2VT/?
(3)
Cp = Cv(1 + 3?G ?T).
(4)
??? [12]
Cp, ??/(????�?)
1750
1
1700
2
1650
1600
3
1550
1500
1450
300
400
500
600
700
800
900
1000
?, ?
???. 1. ???????????? ?????????? ??????? Bi2O3 ? Ga2O3: 1 ? Bi25GaO39 [3], 2 ? Bi24Ga2O39 (???? ??????),
3 ? Bi24Ga2O39 (?????? ?????)
# 506 #
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Liubov T. Denisova, Liliya A. Irtyugo? High Temperature Heat Capacity of Bismuth-gallium Sillenite
???????????? ? ????????????????? ??????? Bi24Ga2O39
?, ?
Cp, ??/(???? ?)
H0(T) ? H0( 340 K), ???/????
S0(T) ? S0(340 K), ??/(???? ?)
340
350
370
390
410
450
500
550
600
650
700
750
800
850
900
1494
1498
1505
1513
1520
1535
1552
1569
1586
1603
1620
1637
1653
1670
1687
?
78.67
109.1
139.7
170.3
232.0
309.8
388.3
467.6
547.7
628.6
710.3
792.7
876.0
960.1
?
239.1
322.6
402.0
477.8
620.0
782.6
931.3
1069
1196
1316
1428
1534
1635
1731
? ?????????? (3) ? (4) ? ? ??????????? ????????? ??????????, V ? ??????? ?????, ? ?
??????????? ???????????? ???????????, ?G ? ?????????? ??????????. ????????? ??? ????,
????? ??????????????? ??????????? (3) ? (4), ?? ??????? ????????? ?????? ??? ??????????
Bi24Ga2O39, ?? ? ?????? ??????????? ??????, ??? ??????? ????? Cp ? Cv ????. ????????? ????????? ???? ???????? ?????????????????? ??????????? ????? ?D = 460 ? ? ????????????????
????????? ??????? ????? (?D /?) [11], ??????? ??????? Cv, ??????? ??????? ???????? ? Cp. ???
?????? ? ????????????? ? ?????????????????? ???????????? ????????? ?? ???. 1. ?????, ???
???????? ????? ????????????????? ? ????????? ??????? ?????????? ? ??????????? ~ 550 ? ?
????????????? ? ?????? ?????????.
??????? ???????? ?? ????????? ????. ?????????? ?? ?????????? ?????????
Bi12M xO20±? ??????????????? ? ?????????? ???????? [1, 13]. ???????????? ?????? ???????????? ????? ???, ? ?????? ? ???????? ???????? ??????????? ????? ? (??????? 2?), ?????????????? ???????????????? ??????????. ???????? [13] «?????????» ???????????????
??????? ????? Bi12GeO20, ????? ??? ? Bi12TiO20 ???????? 10 % ?? ?????? ????? ???????
2? ????????. ???????????, ??? ?????????? ???????? ??????????????? ???????????????
??????? ?????????? ? ????????? ? 3+ ??? ? 2+ (Bi 25Ga 3+ O39, Bi38Zn 2+ O59). ??? ??????? ???????? ?????????? ???????????? ????? ???????????? ????????????? ??????????? ? ??????????????? ??????? [12, 14, 15]. ?????? ??????????? ???????? ? ?????????????, ???????
[11], ??? ?????????? ???????????? ? ??????????? ????????? ?????????? ??????????? ????????????
2
'C
§4 ·
§ 4
R Ё E ё exp Ё E
T
©
№
© T
·
ё,
№
(5)
??? ?? ? ?????????????????? ??????????? ?????????. ????????????? ?????????? ????????
?? ? ??????????? ln(?CT2) = f(1/T) ???? ?????? ?? ????????? ???????????? ??????????, ?????? 0.9942 (???. 2).
# 507 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Liubov T. Denisova, Liliya A. Irtyugo? High Temperature Heat Capacity of Bismuth-gallium Sillenite
ln ('CT2)
18
17
16
15
14
10
12
14
16
-4
18
-1
1/T, 10 K
???. 2. ????????????? ?????????? ???????????? ???????? ????????? ??? T << ?E
?????????? ??????? ???? (5), ?? ?????? [11], ????????, ??? ????????????? ?????? ?????????? ????????? ?????????? ????? ?????????????? ?????????? ????, ??????? ?????????? ?
????????????? ????????, ???? ????? ?????? ??????????? ??????????? ????????. ?????? ????
?????, ?????? ?????????? ???????????? ?????? ??????? ? ???, ?? ????? ???? ??????????.
??????????
??????? ???????????????-??????????? ???????????? ??????? ??????????????????? ???????????? Bi24Ga2O39 ? ????????? ?????????? 340 ? 920 ?. ????????, ??? ????????????
????????? ?????? ? ????? ?????? ????????? ??????? ??????????? ???????????? ?????????
??????????.
?????? ??????????
1. ?????? ?.?., ?????? ?.?., ?????? ?.?. ? ??. ????????? Bi12M xO20±? ?? ??????????
?????????. ??????, ????????, ????????. ?.: ????, 2004. 316 ?. [Kargin Y.F., Burkov V.I., Maryin
A.A. et al. Kristally Bi12MxO20±? so strukturoj sillenita. Sintez, stroenie, svojstva. Moscow, IONKh.
2004. 316 p. (In Russ.)]
2. ??????? ?.?., ????????? ?.?., ??????? ?.?. ? ??. ???????????????? ?????????:
???????? ? ?????? ? ?????????? ????????. ????????????: ??? ???, 2000. 526 ?. [Denisov V.M.,
Belousova N.V., Moiseev G.K. et al. Materials bismuth-containing: structure and physicochemical
properties. Ekaterinburg. UrO RAN. 2006. 526 p. (In Russ.)]
3. Suleimenova G.S., Skorokov V.M. Thermochemical study of gamma bismuth oxide based
single crystals // Thermochim. Acta. 1992. V. 196. P. 203 ? 211.
4. ????? ?.?. ?????????????? ????????? ? ???????? ???????????????? ????????. ?.:
???? ?????, 2003. 163 ?. [Shereb V.P. Metastable states in bismuth-containing oxide systems. M.:
MAKS Press, 2003. 163 p. (In Russ.)]
# 508 #
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Liubov T. Denisova, Liliya A. Irtyugo? High Temperature Heat Capacity of Bismuth-gallium Sillenite
5. Shereb V.P., Skorikov B.M. Metastable states in bismuth ? containing oxide systems // Inorganic
Materials. 2003. V. 39. Suppl. 2. P. 121?145.
6. ???????? ?.?., ?????????? ?.?., ????? ?.?. ? ??. ??????? ????????? ??????? ?????
??????? ? ????? ?????? // ????. ?????. ?????. 1971. ?. 16. ? 2. ?. 526 ? 529. [Safronov G.M.,
Speranskay E.I., Batog B.N. et al. Phase diagram of gallium oxide-bismuth oxide // Zh, Neorg. Khim.
1971. ?. 16. ? 2. P. 526 ? 529 (In Russ.)].
7. ??????? ?.?., ?????? ?.?., ???????? ?.?. ??????????????????? ???????????? ???????
??????? GeO2 ? PbO // ???. 2011. ?. 53. ? 4. ?. 642 ? 646. [Denisov V.M., Irtyugo L.A., Denisova
L.T. High-temperature heat capacity of oxides in the GeO 2-PbO system // Fizika Tverdogo Tela. 2011.
?. 53. ? 4. P. 642 ? 646. (In Russ.)]
8. Maier C.G., Kelley K.K. An equation for the representation of high-temperature heat content
data // J. Am. Chem. Soc. 1932. V. 54. ? 8. P. 3243 ? 3246.
9. ?????? ?. ???????? ? ?????? ???????? ????. ?.: ?????, 1978. 791 ?. [Kittel C. Introduction
to Solid State Physics. Moscow. Nauka. 1978. 791 p.(In Russ.)]
10. ?????? ?.?., ???????? ?.?., ???????? ?.?. ?????????? ???????? ???????? ? ???????.
?.: ???????????, 1980. 320 ?. [Livshic B.G., Kraposhin V.S., Lineccki Y.L Fizicheskie svoistva
metllov i splavov. M. Metallurgia. 1980. 320 p. (In Russ.)].
11. ?????? ?.?., ???????? ?.?., ?????????? ?.?. ? ??. ??????????????????? ????????????
?????????????? Al63Cu25Fe12 // ???. 2008. ?. 50. ? 11. ?. 1933 ? 1935. [Prekul A.F., Kazantsev V.A.,
Shchegolikhina N.I. et al. High-temperature heat capacity of the Al63Cu25Fe12 quasicrystal . Fizika
Tverdogo Tela. 2008. ?. 50. ? 11. P. 1933 ? 1935. (In Russ.)]
12. ???????? ?.?., ??????? ?.?., ???????? ?.?. ??????????. ?. II. ?.: ???, 1966. 434 ?.
[Scuratov S.M., Kolesov B.P., Vorob,ev A.F. Termohimia. II. M. MGU, 1966. 434 p. (In Russ.)]
13. ?????? ?.?., ??????? ?.?., ????????? ?.?. ? ??. ??????????????? ?????????
Bi36MgP2O60-? // ????. ???????. ?????. 2011. ?. 56. ? 6. ?. 969 ? 974. [Avdeev G.V., Milenov T.I.,
Egorysheva A.V et al. Crystal structure of Bi 36MgP 2O 60-? // Russian Journal of Inorganic Chemistry.
2011. V. 56. ? 6. P. 913-918].
14. ??? ?.?., ?????? ?.?. ???????????? ???????????????????? ?????????? ???????
Pb5(Ge1-xSi x)3O11 // ???. 2004. ?. 46. ? 5. ?. 875?880. [ Bush, A.A., Popova, E.A. Heat capacity of the
Pb5(Ge1-xSix) 3O11 ferroelectric system // Fizika Tverdogo Tela. ?. 46. ? 5. P. 875 ? 880. (In Russ.)]
15. ????? ?.?. ??????????????, ??????????, ??????? ? ??????? ??????? ? ??????? ????.
?.: ?????????, 2007. 855 ?. [ Gusev A.I. Nestehiometria, besporyadok, blijnii i dalnii poryadok v
tverdom tele. M.: Fizmatlit, 2007. 855 p. (In Russ.)].
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 510-518
~~~
??? 543.54:543.42.062:546.72
Application of Zirconium Oxide and Titanium Oxide
Sequentially Modified with Polyhexamethylene Guanidine
and 4,7-diphenyl-1,10-phenantrolinedisulfonic Acid
for Preconcentration and Determination of Iron(II)
in Natural and Mineral Waters
Svetlana L. Didukh and Vladimir N. Losev*
Scientific Research Engineering Centre ?Kristall?
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 20.09.2014, received in revised form 18.10.2014, accepted 16.11.2014
Sorbents based on zirconium oxide and titanium oxide sequentially modified polyhexamethylene
guanidine and 4,7-diphenyl-1,10-phenantrolinedisulfonic acid were synthesized. The sorbents
quantitatively extract the iron(II) from solutions of pH 4.0 ? 7.0 (recovery ratio 98 ? 99 %). Intensely
colored iron(II) complexes are formed on the sorbents surface during the adsorption process. Diffuse
reflectance spectra have maximum at 540 nm. The sorbent based on zirconium oxide has more intense
color. These reactions were successfully applied for developing of sorption-photometric method
of iron(II) determination. The detection limit was 0.05 ?g per 0.1 g of the sorbent. The calibration
function was linear up to 8 ?g per 0.1 g of the sorbent. The method was used for the determination of
iron in natural and mineral waters.
Keywords: adsorption, modified zirconium oxide, modified titanium oxide, 4,7-diphenyl-1,10phenantrolinedisulfonic acid, Iron(II), Diffuse reflectance spectroscopy.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: semdid@mail.ru
# 510 #
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Svetlana L. Didukh, Vladimir N. Losev. Application of Zirconium Oxide and Titanium Oxide Sequentially Modified with?
?????????? ??????? ???????? ? ??????,
???????????????? ??????????????????????????
? 4,7-???????-1,10-???????????????????????????,
??? ???????????????? ? ??????????? ??????(II)
? ????????? ? ??????????? ?????
?.?. ?????, ?.?. ?????
??????-????????????????? ?????????? ????? «????????»
?????????? ???????????? ????????????
??????, 660041, ??????????, ??. ?????????, 79
??? ??????????-???????????????? ??????????? ??????(II) ?????????? ???????? ?? ??????
??????? ???????? ? ??????, ??????????????? ???????????????? ??????????????????????????
? 4,7-???????-1,10-???????????????????????????. ???????? ????????? ??????(II) ??
????????? ? ?? 4-7 ?? ???????? ?????????? 98-99 % ? ???????? ???????????? ????????????
??????????, ?? ??????????? 10 ???. ??? ??????? ?? ??????????? ????????? ??????????
?????????? ?????????? ????????? ??????(II), ??????? ? ??????? ?????????? ?????????
??????? ?????? ? ?????????? ??? 540 ??. ????? ??????????? ??????? ??????????? ??? ????????
?? ?????? ?????? ????????. ??????????? ?????????? ?????????? ??????(II) ?? ???????????
???????? ???????????? ??? ?????????? ???????? ??? ??????????-????????????????
???????????. ?????? ??????????? ?????????? 0,05 ??? ?????? ?? 0,1 ? ????????. ??????????
??????????????? ??????? ??????????? ?? 8 ???/0,1 ?. ???????? ???????????? ??? ???????????
?????? ? ????????? ? ??????????? ?????.
???????? ?????: ??????????? ????????????????, ???????????????? ????? ????????,
????? ??????, 4,7-???????-1,10-???????????????????????????, ??????(II), ????????????????????????? ???????????.
?????? ???????? ????? ?? ???????????????? ??????????? ????????? ? ???????? ???. ???
??????????? ?????? ?????? ???????????? ??????????????? ????? [1]. ? ???????? ????????? ??? ???????????????? ??????????? ?????? ?????????? ??????????????? ???????? N-?????????????????
?????????: 1,10-???????????, 2,2?-????????? ? ?? ???????????, ?????????? ?????????? ?????????? ? ??????? ???? ????????? ? ???????(II) [1]. ? ?????????????? ?????? ????????? ??????????? ???????? ??????????? ?????? ?????????? ??????, ? ????? ?????? ? ??????? ????????? +2 ?
+3. ??? ???????? ?? ??????????? ?????????? ??????(II), ?????????????? ??????(III), ??????????????? ? ?????, ?? ??????(II) ? ??????????? ?????? ?????????? ??????. ?????????? ??????(III)
??????? ??? ??????? ????? ????? ??????????? ?????? ? ??????????? ??????(II) [2, 3].
??? ??????????? ?????? ???????????? ??????????-??????????????? ????? [2-6], ?????????? ?? ??????????? ???????????????? ??????(II) ?????????? ????????? ??????? ? ???
??????????? ??????????????? ??????????? ??????????????? ? ???? ????????. ???????? ?
# 511 #
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Svetlana L. Didukh, Vladimir N. Losev. Application of Zirconium Oxide and Titanium Oxide Sequentially Modified with?
??????????????? ???????? 1,10-????????????, 2,2ґ-?????????? ? ?? ??????????? ????????
?????????? ???????????? ????????? ?? ??????????? ??????????? [4] ??? ????????????????
????????? ? ????????????????? ??????? [5], ??????????????? ? ?????? ??????? ??????? [6].
????????????? ??? ????????? ????????? ??????????? ???????????? ??????????? ? ??? ??????????? ???????, ???????? ??????????????????? ??????????? ?????. ?????? ???????????
????????????????? ???????????? ????????? ?? ??????????? ??????????? ?????????? ??-??
????????? ???????????? ????????????????? ????????? ????? ????????? ? ?????????????
????????????? ?????. ???? ????? ???? ???????? [7], ??? ??????????????? ????????? ??????????? ?????????? ?????????????????????????? ????????? ??????? ?? ??????????? ????, ??
??????? ?????????? ??????????? ????????????????? ???????????? ????????? ??? ?? ????
??????????????????? ??????????????, ??? ? ?? ???? ??????????? ?????????? ????? ? ????????????? ????. ?????? ?????? ??????????? ????????????????? ???????????? ????????? ????????? ???????????? ? ???????? ?????? ? ?????? ????????????? ? ???? ?????????????? ??????,
??????? ????????????? ????????????? ??????, ? ????????? ?????? ???????? ? ??????.
?? ??????????? 1,10-???????????? ???????? ?????????????? ????????? ?? ??????(II)
???????? 4,7-???????-1,10-??????????? (???????????????), ??????? ??????????????? ????????????????? ? 4,7-???????-1,10-??????????????????????????. ??????????????? ????????
? ?????????????? ???????????????? ??????????? ?????????????? ??????? ? ??????????????
1,10-???????????? [8].
???? ????????? ?????? ? ?????????? ??????? ??????????-???????????????? ??????????? ?????? ? ????????? ????? ? ??????????? ????????? ?? ?????? ??????? ???????? ? ??????, ??????????????? ???????????????? ?????????????????????????? ? 4,7-???????-1,10???????????????????????????.
????????????????? ?????
???????? ???????? ??????(II) ? ??????(III) ? ????????????? 1 ??/? ???????? ???????????? ?????? ??????? ??????????????? ????? FeSO4 ? Fe2(SO4)3 ? 0,1 ? ???????? H2SO4 ???
?????????????? ?????????. ?????? ???????????? ????????? ????????????? ??????????????? ? ???? [9]. ??????? ???????? ???????? ? ???? ?????????? ???????????? ????????????
????????? ???????? ?????????????? ?????.
0,1%-??? ??????? ????????????????????????? ???????????? (????) ???????? ???????????? ?????? ??????? ????????????? ????????? ? ?????????????? ????.
0,04%-??? ??????? 4,7-???????-1,10-?????????????????????????? (Batophen) ????????
???????????? ????????? ????? Aldrich ? ?????????????? ????.
? ???????? ?????? ??? ??????? ????????? ???????????? ????? ????????, ????????????
«?.?.» ? ???????? ???????????? ~100 ?2/? ? ????? ?????? ???????????? «??.?.» ? ???????? ???????????? ~ 6 ?2/?.
??? ?????????????? ??????(III) ?? ??????(II) ????? 0,1 ? ??????? ????????????? ?????????????? ? ????.
???????? ??l, H2SO4, HNO3, NaOH ????? ???????????? «??.?». ??? ???????? ???????????? ?? ????????? ????????? ???????? ???????.
??????? Seveneasy (Mettler-Toledo, ???????) ???????????? ??? ????????? ?? ?????????.
# 512 #
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Svetlana L. Didukh, Vladimir N. Losev. Application of Zirconium Oxide and Titanium Oxide Sequentially Modified with?
???????? ????????????. ?????? ????????? ZrO2-????-Batophen, TiO2-????-Batophen.
?????????????? ?????? ??????????? ? ???????? ??? ?? 10 ? ??????? 1?2 ? ??? ????????? ???????????. ????? ? ??????? (10 ?) ???????????????? ?????? ??? ????????????? ?? ?????????
1 ??/??? ????????? 100 ?? 0,1%-???? ???????? ????. ??????? ???????, ??????? ?????????
?????????????? ????? ? ?????????? ??? ??????????? 80 °?. ????? ? ??????????? ????????
(ZrO2-????, TiO2-????) ????????? 100 ?? 0,04%-???? ???????? Batophen, ????????????
10 ???. ??????? ?????????????, ??????? ?????? ????????? ?????????????? ?????, ????????
?? ???????? ??????????? ? ?????? ?????????? ??????? (ZrO2-????-Batophen, TiO2-????Batophen) ?? ??????? ? ??????? ?????.
??????? ??????(II, III). ??? ???????? ??????? ?????? ? ??????????? ?????? ? ?????????????? ???????? ? ????????? ??????? ??????? ??????? ??????(II) ??????????? ????????????,
????????? 1 ?? 0,1 ? ???????? ?????????????? ??? ?????????????? Fe(III) ?? Fe(II), NaOH ???
????????? ???????? ??????? ??? ???????? ???????????? ???????? ??. ??????? 0,1 ? ????????
(ZrO2-????-Batophen ??? TiO2-????-Batophen) ? ???????????? ? ??????? 1-10 ???. ???????
???????? ?? ???????? ???????????, ?????????? ?? ?????????????? ?????? ? ?????????????? ??????????? ?????????? ????????? (R) ?? ?????????????????????? «???????». ???????
?????????? ????????? (???) ????????? ? ???????????: ??????? ????????-???????-?????
(F(R)=(1-R)2/2R) ? ????? ?????, ??, ??? R ? ??????????? ?????????? ?????????.
???????? ?? ?????????????? ?????? ???????????? ?? ??????? ?????? ???? ????????????????? ? ?????????? ????????? ??????? ??????? ?? ???????????? Optima 5300 (PerkinElmer, ???).
?????????? ? ??????????
??????????? ???????????????? ??????. ??????(II) ????????????? (??????? ??????????
98-99 %) ??????????? ?????????? ZrO2-????-Batophen, TiO2-????-Batophen ?? ????????? ?
?? 4-7 ? ???????? ???????????? ???????????? ??????????, ?? ??????????? 10 ???. ? ??????????? ???????? ??????? ???????????? ????????????? ?????????? 5·103 ? 1·104 ??3/?. ??????? ????????? ???????????, ??? ?? ??????????? ????????? ZrO2-????-Batophen, TiO2-????Batophen ?????????? ???????? ???????????? Fe(II):Batophen=1:3, ??????? ??????? ??????? ?
?????????? ? ??? ??? 540 ?? (???. 1). ??????????? ???????? Fe(II) ? Batophen ?????????? ?
?????? ????????? [1].
????? ??? ? ????????? ??? ????????? ?? ??????? ?? ??????? ??????????????? ??????,
????????????? ??? ??????? ???????? (???. 1).
Batophen ???????? ?????????? ? ??????? ???? ???????? ?????? ? ??????? ? ??????? ????????? +2. ? ???????? ?????????????? ??????(III) ???????? ????? ????????? ?????????????.
?? ?????????????? ??????(III) ? ??????????? ??????????? ????????? Fe(II) ? Batophen ?????
????????? ??????? ??????? ?????????? ??????????????, ???????????? ??? ? ?? ????????.
??? ?????????? ?????????????? ? ???????? ??????(III) ? ?? 1-8 ? ?????????? ???????
???????????? ????????????? ??????? ????????? ??????????? ??? ?? 3-4. ??? ??????????
?? ?????? 5 ?????????? ?????????? ????????????? ??????? ???????? ?????? ?? ?? ???????
????????????, ??? ??????? ? ??????????? ???????? ????????? ? ???????????? ??????????????? ??????????????? ???? ??????(III).
# 513 #
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F(R)
0,4
0,35
0,3
1
0,25
0,2
0,15
2
0,1
3
0,05
0
380
480
580
680
O, ??
???. 1. ??????? ?????????? ????????? ????????? ??????(II) ?? ??????????? ZrO2-????-Batophen (1) ?
TiO2-????-Batophen (2) (?Fe, ???: 1 (1, 2), 0 (3); 0,1 ? ????????, ?? 5,5; 0,01 ? NH2OH)
' F(R)
' F(R)
0,3
0,08
1
2
0,06
0,2
0,04
0,1
0,02
0
0
1
3
5
7
9
??
???. 2. ??????????? ?F(R) ?????????????? ????????? ??????(II) ?? ?? ?? ZrO2-????-Batophen (1) ? TiO2????-Batophen (2) (?Fe= 1 ???; 0,1 ? ????????; V = 10 ??; 0,01 ? NH2OH)
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Svetlana L. Didukh, Vladimir N. Losev. Application of Zirconium Oxide and Titanium Oxide Sequentially Modified with?
' F(R)
1
2,5
2
1,5
1
0,5
2
0
0
2
4
6
8
?Fe, ???/ 0,1 ? ????????
???. 3. ?????????????? ??????? ??? ??????????? ??????(II) ? ?????????????? ZrO2-????- Batophen (1)
? TiO2-????- Batophen (2) (0,1 ? ????????, ?? 5,5; 0,01 ? NH2OH)
??? ?????????????? ?????? ???????????????, ??????????? ????????? ?? ?? 1-8 ?
?????????? ??????? ???????????? ????????????? ??????? ?????????? ??????(II) ?? ??????????? ZrO2-????-Batophen ? TiO2-????-Batophen ??????????? ??? ?? 5-6 (???. 2) ?
??? ?? ????????? ??, ? ??????? ??????????? ?????????????? ?????????? ??????(II). ? ??????????? ?????? ??????????? ???????????? ????????????????? ??????????? ?????????????? [1]. ? ??????? ????????? ???????????? (1·10 -4 ? 5·10 -1 ?) ????????????? ?? ?????????
??????? ?? ????????????? ??????? ?????????????? ????????? ??????(II). ??? ?? < 4 ? ?? > 6
?????????? ???????? ????????????? ??????? ????????, ????????? ? ?????????? ???????? ?
???????????? ??????????? ????????? ??????(II) ? Batophen ? ????????.
??????????-??????????????? ??????????? ??????. ?????? ??????????? ??????????
????????????? ?????????? ??????(II) ? ???????????????? ?????????? ????????????? ??????? ????????? ? ??????????? ?????????? ?????? ?? ?? ??????????? ???????????? ??? ?????????? ??????? ??? ??????????-???????????????? ???????????.
?????????? ?????????????? ????????. ? ??? ?????????????? ???????? ? ??????????
???????? ??????? ???????, ?????????? ?? 0,1 ?? 10 ??? ??????(II), 1 ?? 0,1 ? ???????? ????????????? ??????????????, NaOH ? ????????? ???????? ??????? ?? ?? 5,5. ??????? 0,1 ?
???????? ZrO2-????-Batophen ??? TiO2-????-Batophen ? ???????????? 10 ???. ??????? ???????? ?? ???????? ???????????, ????????? ?????????????? ?????, ?????????? ?? ?????????????? ?????? ? ???????? ??????????? ?????????? ????????? ??? 540 ??.
?????? ???????????, ???????????? ?? 3S-????????, ????? 0,05 ??? ?????? ?? 0,1 ? ???
ZrO2-????-Batophen ? 0,1 ??? ?????? ?? 0,1 ? ??? TiO2-????-Batophen. ?????????? ????????# 515 #
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Svetlana L. Didukh, Vladimir N. Losev. Application of Zirconium Oxide and Titanium Oxide Sequentially Modified with?
??????? ??????? ??????????? ?? 8 ??? ?????? ?? 0,1 ? ZrO2-????-Batophen ? ?? 1,5 ??? ??????
?? 0,1 ? TiO2-????-Batophen. ?????????? ?????????????? ??????????? (???. 3) ???????????
???????????
?F(R) = 0,3794·? (r2=0,9950) ??? ZrO2-????-Batophen;
?F(R) = 0,0812·? (r2=0,9988) ??? TiO2-????-Batophen,
??? ? ? ???????????? ?????? ?? 0,1 ? ????????.
????????????? ??????????? ?????????? ??? ??????????? ????? 0,5 ??? ?????? ?? 0,1 ?
???????? ?? ????????? 0,07.
????? ????? ???????? ?????????? ??????????????? ??????? ? ????? ??????? ?????? ??????????? ??? TirO2-????-Batophen ??????????? ???????????????? ?????? ??????: ??????
???????? ???????? ??????????? ? ????? ????, ??????????????? ??????????????? ????.
????????? ????????????? ???????? ?? ?????? ?????? ???????? ??????????????? ?????????? ????????????????? (S=?F(R)/?CFe) ? ????? ?????? ???????? ???????????, ?? ZrO2-????Batophen ????????? ??? ??????????? ?????? ? ???????? ????????.
??? ???????? ????????????? ??????????-???????????????? ??????????? ?????? ????????? ???????? ???????, ?????????? 0,5 ??? ??????(II) ? ?? 0,5 ?? 500 ??? ?????? ????? ???????? ? ???????. ???????????? ?????????? ?????????, ?? ???????? ??????????? ??????,
????????? ? ????. 1. ?????????? ??????? ?? ??????????? ?????? ????????? Cu(II) ? Zn(II),
????????? ????????????? ??????? ????????? ? ???????? ??? ??? ??????? ????????????.
??? ????????? ????????????? ???????????? ???????????? ????? ???? ? ???? ?????????????.
???????????? ?????????? ? ??????????-???????????????? ??????????? ??????(II) ??
?????? 0,001 ? 0,05 ? ???????? ????, ??? ??? ??????(II) ???????? ? ????????????????? ?????
?????????? ???????? (lg?FeBatophen = 25) [10], ??? ???????? ? ???? (lg?FeY2- = 14,2) [11].
??????????? ? ?????? ????????? ?? ???????? ??????????? ?????????? ? ???????(II) ? ??
?????? ??? ???????????. ? 0,01 ? ???? ??????????? ?????? ?? ?????? 10-??????? ?????????? ?????(II), ? ? ??????????? 0,5%-??? ??????????? ? 10-??????? ?????????? ????(II).
????????????? ??????????-??????????????? ???????? ???????????? ??? ???????????
?????? ? ????????? ? ??????????? ?????.
???????? ??????????? ?????? ?????????? ?????? ? ????????? ? ??????????? ?????. ? 100 ??
????????? ???? ????????? ????????????????? HNO3 ?? ?? 1 ? ??????? 30 ??? ??? ??????????
???????????? ??????????. ???????? ????????? ??? ??????????? ???? (3 ?? ??? ?????????? ?????? ?????? 1 ??/? ??? 1 ?? ??? ?????????? ?????? ?????? 1 ??/?) ?????? ? ?????????????? ???????? ? ????????? ???????, ????????? 1 ?? 0,1 ? ???????? ????????????? ??????????????, NaOH
? ????????? ???????? ??????? ?? ?? 5,5, ???? ?? 10 ??. ?????? 0,1 ? ???????? ZrO2-????-Batophen
? ???????????? 10 ???. ??????? ???????? ?? ???????? ???????????, ????????? ???????????????? ?????, ????????? ?? ?????????????? ?????? ? ???????? ??????????? ?????????? ?????????
??? 540 ??. ?????????? ?????? ??????? ?? ??????????????? ???????. ?????????? ???????????
????????? ? ????. 2. ???????????? ???????? ????????? ??????? «???????-???????» ? ?????????????? ? ????????????, ??????????? ??????-????????????? ??????? (???).
# 516 #
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Svetlana L. Didukh, Vladimir N. Losev. Application of Zirconium Oxide and Titanium Oxide Sequentially Modified with?
??????? 1. ??????? ???????? ? ??????? ?? ??????????? 0,5 ??? ??????(II) (0,1 ? ????????, 10 ?? ????????,
n=5, P=0,95)
???
???????????? ????, ???/??
???????????? ??????, ???/0,1 ?
????????
Na(I)
100
0,52 ± 0,02
K(I)
100
0,52 ± 0,02
Ca(II)
100
0,50 ± 0,02
Mg(II)
100
0,49 ± 0,02
Sr(II)
100
0,50 ± 0,01
Cr(III)
50
0,48 ± 0,02
Al(III)
30
0,51 ± 0,02
Bi(III)
0,5
0,49 ± 0,02
Pb(II)
0,5
0,48 ± 0,02
Hg(II)
0,5
0,49 ± 0,02
Cu(II)
0,05
0,27 ± 0,01
Zn(II)
0,05
0,31 ± 0,01
Cu(II) +0,5 % ???????????
0,5
0,50 ± 0,01
Zn(II) + 0,002 ? ????
0,5
0,51 ± 0,01
Cl
500
0,52 ± 0,02
SO42-
500
0,53 ± 0,02
-
??????? 2. ?????????? ??????????-???????????????? ??????????? ?????? ? ????????? ? ???????????
????? (n=5, P=0,95)
??????? ??????, ?±tpS/?n, ??/?
??????? ????
??????????-??????????????? ?????
???
0,068 ± 0,004
0,070 ± 0,002
«???????»
0,055 ± 0,005
0,058± 0,002
???? ????????? (???????)
0,22 ± 0,02
0,21 ± 0,01
???? ???????? «????»
???? ??????????? ????????? ????????
???? ???? (???????)
0,14 ± 0,02
0,12 ± 0,01
???? ??????? (???????)
0,40 ± 0,02
0,40 ± 0,01
????????????? ??????????-??????????????? ???????? ????????? ???????? ?????????? ?
??????????????? ??????????, ? ???????? ????????? ???? ??????????? ???????????? ??????? ?
???????? ??? ??????????? ?????? ? ????????? ?????.
?????? ??????????
1. ???????? ?. ????????? ?. ?????? ????????????????? ? ?? ? ??????? ???????? ?
?????????????? ??????? / ???. ? ??????. ?.?. ???????. ?.: ?????. ??????????? ??????, 2007.
711 ?.
# 517 #
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Svetlana L. Didukh, Vladimir N. Losev. Application of Zirconium Oxide and Titanium Oxide Sequentially Modified with?
2. Alaa S. Amin, Ayman A. Gouda. Utility of solid-phase spectrophotometry for determination of
dissolved iron(II) and iron(III) using 2.3-dichloro-6-(3-carboxy-2-hydrixy-1-naphthylazo)quinoxaline
// Talanta. V.76. 2008. P. 1241-1245.
3. Jianrong Chen, Jianjun Lin. Determination of dissolved iron(II) and iron(III) in water with
5-Br-PAN-S by solid phase spectrophotometry // Analytical letters. V.34. 2001. P. 2169-2178.
4. ???????? ?.?., ?????? ?.?., ????????? ?.?. I????i?i???i? 1-10-?????????i?? ??
2,2ґ-???i?????? ?? ???????i SiO2 // ??????? ?? ????. ???. ?. 1984. ?11. ?. 54-60.
5. ?????????? ?.?., ????????? ?.?., ?????????? ?.?. ??????????? ??????????????? ????????????????? ??????? ? ???????? ?????????? ??? ???????????? ??????????? ??????(II, II)
// ????????? ? ????????. ?. 7. 2003. ? 1. ?. 50-53.
6. ??????? ?.?., ????? ?.?., ?????????? ?.?., ?????????? ?.?. ??????????? ???????????????? ???????????????? ?? ?????????. ?.: ?????, 2007. 320 ?.
7. ????? ?.?., ????? ?.?., ????????? ?.?. ??????????-??????????????? ???????????
?????? ? ?????????????? ????????? ?? ?????? ?????????????? ??????? ? ??????????????? ???????? 4,7-???????-1,10-???????????? // ???????? ?????. ????? ? ???. ??????????.
2009. ?. 52. ? 7. ?. 32-36.
8. ????? ?. ???????????? ????????????? ????????. ?.: ???, 1967. 407 ?.
9. ?????????? ?., ?????? ?. ?????????????????????? ??????????. ?.: ?????, 1970.
360 ?.
10. Perrin, D. D. Stability constants of metal-ion complexes. Part B: Organic ligands. Pergamon
press, 1979. 1263 p.
11. ????? ?.?. ?????????? ?? ????????????? ?????. ?.: ?????, 1989. 448 ?.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 519-526
~~~
??? 543.545, 541.49
Application of Capillary Electrophoresis
for Determination of Stability constants of Complexes
of Iron (III) with Sulfosalicylic Acid
with a 1:1 and 1:2 Stoichiometries
Olesya V. Popovaa, Viktoriya V. Sursyakovaa,
Galina V. Burmakinaa, b and Anatoliy I. Rubayloa, b*
a
Institute of Chemistry and Chemical Technology
Siberian Branch of the Russian Academy of Sciences
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 14.10.2014, received in revised form 22.11.2014, accepted 07.12.2014
Capillary electrophoresis was employed for the determination of stability constants of complexes of
iron (III) with sulfosalicylic acid with a 1:1 and 1:2 stoichiometries. Sulfosalicylic acid was used as
background electrolyte and ligand in order to prevent occurrence of system peaks. In the pH range
of background electrolyte from 2,5 to 3, the experimental dependences of electrophoretic mobility
complexes on ligand concentration were obtained. The ratio of the stability constants lg (?2 / ?1) for
complexes of iron (III) with sulfosalicylic acid was calculated. The obtained value was 10,7 ± 0,1,
which agrees well with literature data.
Keywords: stability constants, iron (III), sulfosalicylic acid, capillary electrophoresis.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: popova-olesya25@yandex.ru
# 519 #
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Olesya V. Popova, Viktoriya V. Sursyakova? Application of Capillary Electrophoresis for Determination of?
?????????? ?????? ???????????? ?????????????
??? ??????????? ???????? ????????????
?????????? ?????? (III) ? ????????????????? ????????
? ??????????? 1:1 ? 1:2
?.?. ???????, ?.?. ??????????,
?.?. ??????????,?, ?.?. ????????,?
?
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50, ???. 24
?
????????? ??????????? ???????????
??????, 660041, ??????????, ??. ?????????, 79
????? ???????????? ????????????? ???????? ??? ??????????? ???????? ????????????
?????????? ?????? (III) ? ????????????????? ???????? ? ??????????? 1:1 ? 1:2.
????????????????? ??????? ?????????????? ? ???????? ???????? ???????? ??????????? ?
??????? ??? ????, ????? ????????? ??????????? ??????????? ????????? ?????. ? ???????
???????? ?? ???????? ???????? ??????????? ?? 2,5 ?? 3 ???????? ?????????????????
??????????? ??????????????????? ???????????? ?????????? ?? ???????????? ???????,
?? ????????? ??????? ?????????? ????????? ???????? ???????????? lg(?2/?1) ??????????
?????? (III) ? ????????????????? ????????. ?????????? ???????? ????????? 10,7±0,1, ???
?????? ??????????? ? ????????????? ???????.
???????? ?????: ????????? ????????????, ?????? (III), ????????????????? ???????,
??????????? ????????????.
????????
???????????? ????????? ??????????? ?????????? ????? ?????? ???????? ? ?????????? ????????????? ????????? ?? ?????? ???????????? ??????? ???????, ?? ? ????? ???????????? ?????????? ? ????????? ??????????????? ?????????, ??????????? ???????????
?????????? ?????, ?????????? ??????? ???????????, ??????? ????? ? ?.?. ? ?????? ?? ????????? ??????????, ??????????????? ??????? ????????????????????, ????????? ????????? ????????????, ??? ??????????? ??????? ???? ????? ??????????? ???????????? ????????????????? ? ?????????????????????? ?????? [1?3]. ? ????????? ????? ????????? ??????,
? ??????? ??? ??????????? ???????? ???????????? ?????????? ???????????? ???????????
????? ???????????? ????????????? (??) [4?11]. ?????? ????? ?? ? ???????? ???????????
??? ???????? ?????????? ? ??????????? ????????????????????? ? ???????? 1:1, ????????
?????????? ????? ??????? ?????? ??????????? ???????? ?????. ?? ??????????? ????????
???????????? ?????????? ?????????? ???????? ??????? ?? ??????? ???? ????????? ??????.
# 520 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olesya V. Popova, Viktoriya V. Sursyakova? Application of Capillary Electrophoresis for Determination of?
????? ?????? ?????? ???????? ?????? ??????????? ??????????? ???????? ????????????
??????? ?? ?? ??????? ????? ????????? ??????? ???????? ?????????? ?????? (III) ? ????????????????? ???????? ? ??????????? 1:1 ? 1:2.
????????????? ?????
OH
COOH
???????? ? ?????? ?????? (III) ??? ???????????????????? ??????? (H3L) HO3S
????? ?????????? ?????????? ??????????? ??????????, ???????????? ???? ?? ????? ??
???????. ??????????????? ??????? ???????????????????? ????? ??????????? ?????????
??????????:
? ????? ? ?????? ? ??????????? ????? ?
(1)
??? n = 1, 2 ??? 3.
??? ?? 2-4 ? ???????? ?????????? ??????-?????????? ???????? ? ??????????? ?????? ?
????????????????? ???????? 1:1, ? ????? ? ?? 2-8 ? ???????? ??????? 1:2 ??????-???????????
?????, ? ??? ?? 8-11 ???????? ???????? ??????? ????? ? ???????????? ??????????? 1:3. ???
?? 12 ??????????????? ?????? ???????? ??????????? ? ?????????? ?????? ???????? ????? ?
?????????? ?????? [12?16].
????????? ???????????? ?????????, ????????????? ?? ??????? M + jL ?MLj, ????????
?????? ??????????? ???? ??? ???????? ?????? ???? ?????
?? ?
?????? ?
?
????? ? ??????
(2)
??? ?j ? ????? ????????? ???????????? ????????? MLj; [MLj], [L] ? [M] ? ??????????? ???????????? ????????? j, ?????????? ??????? ? ?????????? ??????? ??????????????.
???????? ??????????????????? ??????????? ????????? ???? ????? ???? ????????? ??
?????????? ?????????:
???? ?
?????? ? ?????? ?
?
?
? ??
?????? ????
?
(3)
??? L??? ? L??? ? ??????????? ? ????? ????? ?????????; U ? ??????????? ??????????; t??? ?
t? ? ??????? ???????? ???????????????????? ?????? (???) ? ????????? ??????????????.
??? ????????? ?????? ???? ?????? ?????? ?????????? ????????????? ???? ???, ??????????????????? ??????????? ???????? ???????? ???????????????? ???? ????????? ?? ?????:
?
???? ? ? ?? ? ??????? ??
(4)
???
??? ?j ? ??????? ???? ????????? MLj; ?(MLj) ? ??????????????????? ??????????? ?????????
MLj (??? ?????????? ??????? ? ??? j=0).
????????, ??? ??????? ???? ??? ?????? ?????? ????? ?????????? ?j ?????????? ???
# 521 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olesya V. Popova, Viktoriya V. Sursyakova? Application of Capillary Electrophoresis for Determination of?
??????? 1. ????????? ???????????? (lg ?) ?????????? ?????? (III) ? ???????????????-(L3-) ? ???????????????
????????
[19]
[20]
14,05
15,0
[FeL2]3-
24,33
25,8
[FeL3]6-
33,10
32,6
[FeL]
0
[FeOH]
11,8
11,0
[Fe(OH)2]-
22,33
21,7
[Fe(OH)3]
30
25,1
-
34,4
2-
0
[Fe(OH)4]+
???. 1. ????????? ????????????? ?????????? ?????? ? ????????????????? ????????: 1 ? [FeL]o;
2 ? [FeL2]3-; 3 ? [FeL3]6-. ?????? ???? 0,05
??
?????? ?
?????? ?
?? ? ??????
? ?
?
?
????
?????????? ? ? ? ????? ?? ? ??????
(5)
??? ?? ? ????? ???????????? ???? ??????????? ???? ???????, ????? ??????????? ????????
??????????????????? ??????????? ????, ??????????? ???? ?????? ?????? ??????????, ?
??????????? ???????????? ? ????????????? ??????? ??????????? ??????????
???? ????? ?
????? ? ? ?????? ? ??????? ?
?
? ? ????? ?? ? ??????
(6)
??? ????, ????? ????????? ??????????? ??????????? ????????? ????? [17, 18], ?????????????? ????? ???????????? ??????? ?????????? ?? ?????? ?????? ???????. ?? ???????????? ?????? ? ?????????? ???????????? ?????????? ?????? ? ????????????????? ???????? ?
# 522 #
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Olesya V. Popova, Viktoriya V. Sursyakova? Application of Capillary Electrophoresis for Determination of?
?????????-?????? (????. 1) ? ?????????????? ????????? (5) ????????? ????????? ????????????? ??? ?????????? ?????? ? ??????????? ?? ?? (???. 1).
??? ????? ?? ???. 1, ??? ?? ?? 1 ?? 7 ?????????? ?????? ????????? ?????? ? ????????????????? ????????, ????????????????? ([FeOH]2+, [Fe(OH)2]+, [Fe(OH)3], [Fe(OH)4]-) ? ??????
??????? ?? ??????????. ?????????????, ??????????? ??? ??????????? ???????? ????????????
?????????? ?????? (III) ? ????????????????? ???????? ? ??????????? 1:1 ? 1:2 ???????? ???????? ?? ? ????????? ?? 2 ?? 4, ????????? ? ?????? ?????? ?????????? ?????? ??? ??????????? ????? ?????? ? ????????????????? ???????? ([FeL]o ? [FeL2]3-). ? ???? ??????? ????????
?? ??????????????????? ??????????? ??????????? ???? (????), ?????? ?? ????????? (6), ?????????????? ?? ?????????
???? ?
??????????? ? ? ?? ? ?????? ?
?
?? ? ?? ? ?????? ?
(7)
???????? ??????? ???????? ??????????? ??????????? ??? ?? = ???. ????????? ??????????? ?? ?????? ??????? ??? ????????????????? ??????? ?????????? ???2 = 2,51 [19], ?????????????, ?? ???????? ???????? ??????????? ?????? ?????? ? ????????? 2,51±1,00.
????????????????? ?????
??? ????????? ????????? ?? ??????? ????? ?? ??? ? ??????? ?? ? ??????-?????????
?????????? Agilent 3DCE G1600A (Agilent Technologies, Waldbronn, ????????). ???????????? ?????????????????? ????????? ???????? ? ?????????? ????????? 50 ??? ????? ?????? 64,5
?? (??????????? ?????? 56 ??). ???????? ???????????????? ??? ??????????? 25 0?. ?????????????? ????????? ? ??-??????? ??? 254 ??. ?????? ????????? ???????????? ??? ??????
??????????? ???????????? ??????????? HP ChemStation Rev.A.10.02. ???? ????? ????????????????? ???????????? ??? ???????? 50 ????.
???????????? ???????? ?? ???? ?.?.?. ??? ???????? ???????? ? ??????????? ?????????????? ????, ?????????? ??? ?????? ??????? ??????? ???? Direct-Q 3 (Millipore, ???????) ?
??????????????????? ????? 0,1·10 -6 ??-1??-1.
????? ??????? ???????? ??????????????? ????????? 0,1 ? ????????? ? ??????? 5 ???,
????? ?????? ?? 5 ??? ? ?????????????? ?????, 10 ??? ? ????????? ???????? ???????????,
????? ????????? ? ????????? ???????? ??????????? ? ??????? 5 ???.
?? ???????? ??????????? ?? ?????? ????????????????? ??????? ???????? ?? ????????
2 - 3,5 ????????? ???. ????????? ?? ??????????? ? ?????????????? ??-????? ? ????????
«??????? - 001». ?????? ???? ???????? ???????? ??????????? (I) ?????????? ???
? ??? ??? ??? ??? ? ? ??? ? ??? ? ?? ??? ? ? ????? ? ???? ? ? ? ??????? ? ? ? ? ?????? ???
(8)
???????? ????????? ???????????????????? ??? ????????? ??????? ([K+]+[H+]=[H2L]+2[HL2-]+3[L3-]+[OH-]), ????????? (8) ????????????????? ? ?????????
? ??? ?? ? ?????? ? ? ? ?? ? ?????? ? ? ? ?? ? ?????? ? ??? ? ????
(9)
??? ?H3L ? ????? ???????????? ????????????????? ???????; ?1, ?2, ?3 ? ??????? ???? ??????????? ???? ????????????????? ???????, ????????? ?????? ?? ?? ????????. ?????? ????
# 523 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olesya V. Popova, Viktoriya V. Sursyakova? Application of Capillary Electrophoresis for Determination of?
???????? ???????? ???????? ??????????? ???????????? ?????????? (I = 0,05), ????? ???????????? ????????????????? ??????? ???????????? ?? ????????? (10)
?????? ?
? ??? ??? ? ???
?
?? ? ? ? ?? ? ? ? ??
(10)
?????????? ? ??????????
???????? ????????????????? ?????????? ?????? (III) ? ????????????????? ????????
??? ?????? ???????????? ??????? ? ??????? ??????????? (???. 2). ??? ????? ?? ???????, ? ??????????? ?? ?, ??????????????, ??????????? ??????????? ???????????? ???????????????????? ? ???????? ????? ???????? ?????????? ???????????, ? ??????????????????? ??????????? ????????????? (????????? 3).
??? ?????? ????? ????????? (7) ????? ???? ????????????? ? ????????? (11), ?? ?????????
???????? ???????? ??????????? ??????????? ????????? ?? ???????????? ???????????????????? (???. 3) ? ?????????? ????????? ???????? ????????????. ?? ???????? ???? ??????? ?????????? ????????????????? ??????????? (???. 3) ? ?????????????? ????????? (11) ??????????
????????? ???????? ???????????? ?????????? ?????? ? ????????????????? ???????? lg(?2/?1)
??????? ??, ??????? ????????? 10,7±0,1 (n=3, P=0.95). ?????????? ???????? ?????? ??????????? ? ????????????? ??????? (10,3 [19] ? 10,8 [20]).
??
?
?
?
?
?
??
??
??? ????????? ? ? ? ?? ? ?? ??? ????????? ??? ?
(11)
????? ???????, ?????????? ?????? ????????? ??????? ?????, ??? ????? ?? ???????? ???
??????????? ???????? ???????????? ?????????? ?????????? ???????? ? ??????????? ????????????????????? ? ???????? ??????, ??? 1:1. ?????? ??? ???? ?????????? ????????? ???
???????? (??, ?????????????????, ?????? ???? ? ?.?.), ??????? ????? ?????? ?? ??? ??????????? ???????? ???????????? ??????????? ??????.
???. 2. ????????????????? ?????????? ?????? (III) ? ????????????????? ???????? ?? ?? 2,5 ?? 3,5
# 524 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olesya V. Popova, Viktoriya V. Sursyakova? Application of Capillary Electrophoresis for Determination of?
???. 3. ??????????? 1/? ??? ?? 1/[L3-]
?????? ??????????
1. ???????? ?.?., ??????? ?.?. ???????? ???????? ???????????????????? ??? ? ??????????????? ????????? // ???????? ?????. ??-??. 2009. ?. 9. ?. 33?36.
2. Khalil M.M. Complexation Equilibria and Determination of Stability Constants of Binary
and Ternary Complexes with Ribonucleotides (AMP, ADP, and ATP) and Salicylhydroxamic Acid as
Ligands // J. Chem. Date. 2000. Vol. 45. P. 70?74.
3. Kalman F.K., Kirбly R., Brьcher E. Stability Constants and Dissociation Rates of the EDTMP
Complexes of Samarium (III) and Yttrium (III) // Eur. J. Inorg. Chem. 2008. P. 4719?4727.
4. Sladkov V. Uranyl complexation with acetate studied by means of affinity capillary
electrophoresis // J. Chromatography A. 2013. V. 1289. P. 133?138.
5. Petit J., Geertsen V., Beaucaire C., Stambouli M. Metal complexes stability constant determination
by hyphenation of capillary electrophoresis with inductively coupled plasma mass spectrometry: The
case of 1:1 metal-to-ligand stoichiometry // J. Chromatography A. 2009. V. 1216. P.4113?4120.
6. Ehala S., Toman P., Makrlik E., Rathore R., Kasicka V. Affinity capillary electrophoresis
and density functional theory applied to binding constant determination and structure elucidation
of hexaarylbenzene-based receptor complex with ammonium cation // J. Chromatography A. 2011.
V. 1218. P. 4982?4987.
7. Rasmussen B.W., Bjerrum M.J. Ca2+ and Na2+ binding to high affinity sites of calcium-containing
proteins measured by capillary electrophoresis // J. Inorganic Biochemistry. 2003. V. 95. P. 113?123.
8. Erim F.B., Boelens H.F.M., Kraak J.C. Applicability of capillary zone electrophoresis to study
metal complexation in solution // Analytica Chimica Acta. 1994. V. 294. P. 155?163.
# 525 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olesya V. Popova, Viktoriya V. Sursyakova? Application of Capillary Electrophoresis for Determination of?
9. Cirri M., Meastrelli F., Orlandini S., Furlanetto S., Pinzauti S., Mura P. Determination of stability
constant values of flurbiprofen-cyclodextrin complexes using different techniques // J. Pharmaceutical
and Biomedical Analysis. 2005. V. 37. P. 995?1002.
10. Macka M., Nesterenko P., Andersson P., Haddad P.R. Separation of uranium (VI) and lanthanides
by capillary electrophoresis using on-capillary complexation with arsenazo III // J. Chromatography A.
1998. V. 803. P. 279?290.
11. Topin S., Aupiais J., Baglan N., Vercouter T., Vitorge P., Moisy P. Trace metal speciation by
capillary electrophoresis hyphenated to inductively coupled plasma mass spectrometry sulfate and
chloride complexes of Np (V) and PU (V) // Anal. Chem. 2009. V. 81. P. 5354?5363.
12. ???? 4011-72 ???? ????????. ?????? ????????? ???????? ???????????? ?????? ??????. ?.: ??? ???-?? ??????????, 2003. ?. 381?388.
13. ????????? ?.?., ???????? ?.?., ??????? ?.?. ???????????? ??????????? ???????????
?????? ???????????? ????? ?????? (III) ? ????????? ????? ??????????????? ??????? ? ??????????? ????????????????? ??????? // ????. ??????????? ??-??. 2010. ???. 1. ?. 67?73.
14. Cui Y., Chang X., Zhu. X., Jiang N., Hu Z., Lian N. Nanometer SiO2 modified with
5-sulfosalicylic acid as selective solid-phase extractant for Fe (III) determination by ICP-AES from
biological and natural water samples // Microchemical J. 2007. V. 86. P. 23?28.
15. Pozdnyakov I.P., Plyusnin V.F., Grivin V.P., Vorobyev D.Y., Bazhin N.M., Pages S., Vauthey
E. Photochemistry of Fe (III) and sulfosalicylic acid aqueous solution // J. Photochemistry and
Photobiology A: Chem. 2006. V. 182. P. 75?81.
16. ???????? ?.?. ?????????????????????? ??????: ????. ??????? ??? ???. ?????. ?????????: ???????????? ????? ?????, 2011. 34 ?.
17. ????????? ?.?., ??????? ?.?., ????????? ?.?., ??????? ?.?. ????????? ???? ? ??????????? ??????? ?????????? ??????? ? ?????? ???????????? ????????????? ? ????????????
??????????????????? ???????// ????. ??????. ?????. 2012. ?. 67. ? 9. ?. 871?877.
18. Sursyakova V.V., Kalyakin S.N., Burmakina G.V., Rubaylo A.I. System peaks in capillary
zone electrophoresis of anions with negative voltage polarity and counter-electroosmotic flow//
Electrophoresis. 2011. V. 32. ?. 210?217.
19. ????? ?.?. ?????????? ?? ????????????? ?????. ?.: ?????, 1989. 448 ?.
20. ?????? ?. ?????????? ?????????? ? ????????????? ?????. ?.: ???, 1979. 376 ?.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 527-536
~~~
??? 544.478: 547.313: 661.715.3
Direct Synthesis of Propylene from Ethylene
over PdO-Re2O7/So42-/Zro2 Catalyst
Luiza F. Sayfulina*, Evgeniy A. Buluchevskiy and Alexandr V. Lavrenov
Institute of Hydrocarbons Processing SB RAS
Neftezavodskaya str., 54, Omsk, Russia, 644040
Received 12.09.2014, received in revised form 16.10.2014, accepted 24.11.2014
An influence of the preparation method and rhenium oxide content in the PdO-Re2O7/SO42-/ZrO2
system was studied. Optimal method of catalyst preparation is impregnation of support by solution of
palladium precursor and then by solution of rhenium precursor. The maximum yield of propylene (49
wt. %) is achieved on the PdO-Re2O7/SO42-/ZrO2 catalyst with 1.87 wt. % Re2O7 at the temperature of
80?C and weight hourly space velocity of 0.5 h-1.
Keywords: palladium, rhenium, sulfated zirconia, ethylene, propylene, dimerization, metathesis.
????????????? ????????? ?????????
?? ??????? ?? ???????????? PdO-Re2O7/So42-/Zro2
?.?. ?????????, ?.?. ???????????, ?.?. ????????
???????? ??????? ??????????? ????????????? ?? ???
??????, 644040, ????, ??. ??????????????, 54
??????? ??????? ??????? ????????????? ? ?????????? ?????? ????? ?? ??????????????
???????? ??????? PdO-Re2O7/SO42-/ZrO2 ? ???????? ?????????????? ??????? ?????????
?? ???????. ????????, ??? ??????? ??????????????? ?????????? ???????? ???????,
?????????? ???????????????? ?????????? ??????? ????????, ? ????? ?????. ????????????
????? ????????? (49 ???. %) ??????????? ?? ???????????? PdO-Re2O7/SO42-/ZrO2, ??????????
1,87 ???. % Re2O7, ??? ??????????? 80 ?? ? ???????? ???????? ?????? ??????? 0,5 ?-1.
???????? ?????: ????????, ?????, ???????????????? ??????? ????????, ??????, ????????,
???????????, ?????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: luiza@ihcp.ru
# 527 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
????????
???????? ? ????????? ????? ???????? ??????? ???????? ??????????? ???????????????? ? ????????????? ???????. ??????? ???????????? ????????? ????????? 80 ??? ? ? ??? ? ?????????? ?? ????? ??? ?? 6 % ???????? [1]. ????? 30 % ??????????????? ????????? ???????????? ??? ???????????? ?????????????, ????? ???????????? ?????? ????? ????? ??????????? ??
????????? ?????????????? ? ??????????? (?? 8 %), ????????????? (7 %), ?????? (4 %) ? ??????
?????? ???????.
???????????? ???????? ???????? ? ??????????????? ???????? ??????????????? ?????, ??
???? ??????? ?????????? ????? 80 % ???????? ???????????? ?????????, ?? ????????? ? ?????? ???? ????????????? ???????? ????? ???????????????? ?????, ????????? ?????????????
??? ?????????????? ????????? ???????? ??????? ?????????. ??? ?????????? ???????? ??????? ??????? ??????? ?????????, ? ????? ??????? ????????? ???????? ?????????????? ???????,
?????????????? ???????, ????????? ? ??. ???????? ?????? Chemical Market Associates Inc., ?
2006 ?. ?? ???? ????? ????????? ??????????? ????? 6 % ?? ???????? ???????????? ?????????,
? 2011 ?. ??? ???? ???????? ?? 13 %, ? ? 2016 ?. ?????????????? ?????????? ?????? 20 %.
? ????? ????? ????????? ??????? ??????????????? ???????? ????????? ????????? ??
???????. ? ??????????? ??????? ?????? ?????????? ???????????? ????? ????-, ??? ????????????? ????????, ?????? ??????? ??????? ?????? ??????????? ??????? ? ?????-1. ?????? ?
?????? ?????? ? ??????????? ???????????? ??????-1 ? ??????-2 ? ????????? ???????-2 ? ???????? (????????) ? ????? ?????????? ? ????? ???????? ?? ???????????????? ????????????. ? ????????? ????? ???????? ???????????? ? ?????? ??????? ???? ? ??????????? ?????? ???????????? ??????????????????? ????????????, ??????????????? ?????????? ???? ???? ??????? ??
????? ????????. ? ????????? ?????????? [2-4] ? ???????? ????????????? ?????????????? ??????? ????????? ?? ??????? ???????????? ??????????????? ???????, ?????????? NiO [1] ???
PdO [5], ??????????? ??? ?????????? ??????? ??????????? ???????, ? ????? MoO3 [2, 3], Re2O7
[1] ??? WO3 [3], ?? ??????? ????????? ??????? ??????????. ????????? ??? ????? ????????????? ???? ????? ?????? ????? ????????, ?? ??????????? ???????? ?????????? ????????????
??????-1 ? ??????-2. ????? ????????, ??? ??????????????? ??????????? ?????????????? ???????? ???????? ?????????????? ?????? (F-, BO33-) [4] ???????? ? ????????????? ?????????
?????????? ????????????.
????? ???? ???? ??????????? [6], ??? ??????? PdO/SO42--ZrO2 ???????? ??????????? ????????????? ?????????????????? (?? ???? 100 °C) ??????? ??????????? ???????. ?????? ?????? ????????? ?????? ????????????? ??????? PdO-Re2O7/SO42--ZrO2 ??? ??????????????????? ???????????? ?????????????? ????????? ????????? ?? ???????. ? ?????? ?????? ???????
???????????? ??????? ?????? ????????????? ???????????? ?? ??? ??????????, ???????????
???????????? ?????????? ????? ? ???????????? ? ?????? ??????? ??????? ???????? ?? ???
???????? ??????????.
????????????????? ?????
???????????????? ??????? ???????? ???????? ??????? ????????? ????????? ?? ???????? ??????????? ???????? (150-300 ? ZrO2/?) ????????? ??????? (65-70 ?/?) ? ???????????
????????? ???????? ?? 10. ?????????? ?????? ???????? ????????????? ? ????????? ??????# 528 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
?????????? ????? ?? ????????????? ??????? ?? ??????-????. ??????????????? ???????????? ????? ????????? ?????? ????????? ?????? ??????? (150-170 ?/?) ?? ??????? ????????????
?????????? SO42- ? ??????? ????????? 10 ???. %. ????? ??????????????? ????????? ?????
(120 °?) ? ???????????? (650 °?).
? ???????? ???????????????? ?????? ???????? ? ?????? ????? ???????????? H2PdCl4 ?
HReO4 ??????????????. ????????? ???????????????? ???????? ??????????? ????????????
?? ?????? ????????? ??????? ???????? ?? ????????????. ??????????? ?????????? ????????
? ????????? ?? PdO ?? ???? ???????? ?????????? 1 ???. %. ????? ???? ????????????? ??? ?????
????????, ???????????? ??????????????????? ????????? ???????????????? ???????? ???????????. ? ????? Pd-Re-? (? ? ?????????? ?????? ?????) ? ??????? ??????? ??????? ????????, ? ????? ?????. ? ????? Re-Pd-? ???????? ????? ? ???????? ???????????? ? ????????
??????????????????, ? ? ????? Mix-PdRe-? ??? ?????????? ??????? ?? ?????? ????????????
????????. ??????????? ?????????? ????? ? ??????? ?? Re2O7 ??? ???? ????? ?????????? 2, 5 ?
10 ???. %. ????? ???????? (? ??????? ????????????????? ????????? ? ????? ?????? ????????)
??????? ?????????? ??? 120 ?? ? ??????????? ??? 500 ??.
?????????? ?????? ?????????? ???????? ??? ????????? ??????? ??????-???????????
????????????? (??????????? VARIAN 710-ES). ????????? ????? ? ???????? ? ???????? ????????? ??????? ????????????? ??????????????? ?????????????? (????) ? ??????????? ???????????????? ???????????? KRATOSES 300. ? ???????? ?????????? ????????? ??????????????
K?-????? ?????? (hv = 1253.6 ??). ?????????? ? ????????? ????????? ????????? ??????????
????? ????????? ???????????? ???????? ????????? ??????????????? ??????? ? ????? 0.1 ??
??? ??????? ??????????? ??????????? HV 25 ??. ?????????? ??????????? ???????????? ????????????? ?? Au4f- ? Cu2p-??????? ????????????? ?????? ? ???? ? ???????????????? ??????????? 84,0 ? 932,7 ??. ?????????? ?????????? ???????? ???? ?? ?1s-?????, ??????? ?????
??????? ??????????? ?????? 285,0 ??.
????????? ???????? ???????????? ? ????????? ???????? ? ??????????? ????? ????????????. ??????? ???????????? ????????? ? ??????? ? ???? ??????? ? ???????? ?????? 0,2-0,5 ?
? ????? ??????? ????????? ???????????? ? ?????? ?????? ??????? ??? 500 °? ? ??????? 1 ?.
??????? ??????????? ??? 40-80 °?, ????????, ??????? ? ????????????, ???????? ???????? ?????? ??????? (????) 0,5-4,0 ?-1.
? ???????? ????? ???????? ???????????? ?????? ?????? (99,9 ???. %). ?????? ?????????
??????????? ????????? ? on-line ?????? ?? ??????? ???????????? «???? 800» ? ????????????????????? ?????????? ? ??????????? ???????? HP-PONA (19091S-001). ??????????????
? ???????????? ????????????? ? ??????? ???????????? ??????????? «???? - ????????».
?????????????? ?????? ????????? ??????????? ??????? ?????????? ????????????? ???????? ????? ??????????????? ????? ????????????? ? 100 %.
??????? ??????????? ??????? (?), ????????????? ??????????? ????????? (S), ? ????? ??
?????? (Y) ???????????? ??????? ???????? ?????? ?? ??????? ????????? ????????.
?????????? ? ??????????
?????????? ??????????? ??????? ?????????? ???????? ????????????? ???????????? ?
????. 1. ??? ????? ?? ????. 1, ??????????? ?????????? ???????? ?????????? 1,07-1,13 ???. %,
# 529 #
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Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
??????? 1. ?????????? ?????? ?????????????
???????
???????????
?????????? Re2O7,
???.%
???????????
?????????? Re2O7,
???.%
???????????
?????????? PdO,
???.%
Pd-Re-2
2,0
1,87
1,12
Mix-PdRe-2
2,0
1,33
1,10
Re-Pd-2
2,0
1,82
1,12
Pd-Re-5
5,0
3,60
1,08
Mix-PdRe-5
5,0
2,20
1,10
Re-Pd-5
5,0
2,30
1,12
Pd-Re-10
10,0
4,13
1,07
Mix-PdRe-10
10,0
3,63
1,13
Re-Pd-10
10,0
2,83
1,12
??? ????????????? ?????????? ?????????? ????? ??????????. ?????????? Re2O7 ???????????
?????????? ?? ?????????? ?????????? ?? ?????????????????? ???????? ???????????????? ???????? ??????????? ? ???????????. ??? ???? ??????????? ????????? ? ???????? ???? ?????,
??????????? ? ???????? ? ?????? ?????????? ?????????? ????? ??????????. ???, ? ????????????? ? ??????????? ??????????? Re2O7 2,0 ???. % ???? ????? (? ????????? ?? Re2O7) ?????
???????????? ?????????? 67-94 % ?? ??????????, ??? ??????????? ?????????? ????? 5 ???. %
? 46-72 %, ? ??? ???????? ? ???????? ????? ????? 10 ???. % ?? ????????? 41 %. ????? ???????? ??????????? ????? ???????????? ????????? ?????? ????? ? ??????????? ???????????? ???
????????????. ???? ?????? ????? ? ???????? ?????????????? ????? ?????????? ? ??? ??????,
?????????????? ? ?????????????? ?????? ?????????. ????????, ? ?????? [7] ????????????
?????? ????? ??? ???????????? ????????, ??????????????? ?? ?????? ?????? ???????? ?
????????? ?????????????. ?????? ?????? ? ??????, ??? ?? ??????????? ????????? ? ?????
??????? ???????????? ????? ????? ???????????? ????, ??? ?? ????? ?????????. ???????????????? ????? ???????? ???????? ??????? ???????????? ??????????? ?? ????????? ? ???????????????. ? ????, ????????, ? ??????? ????? ???????????? ?????? ????? ??? ?????????????? ?????????????.
?????????? ????????? ?????????? ???????? ? ???????? ?????????????? ???????????
??????? ? ???????? ???????????? ?? ???. 1 (?, ?). ??? ????? ?? ???. 1, ???????? ??????? ??????? ????? Re-Pd-? ? Mix-PdRe-?. ??? ???????????? ??????????? ?????? ??????????? ???????
??? ??? 40, ??? ? ??? 80 ?? (???. 1, ?). ?????? ???????? ?????? ????????? ?? ??? ?? ?????????
1 ???. % (???. 1, ?). ???????? ???????????? ???????? ?? ???? ????????????? ???????? ??????????????, ??????? ? ??????? ????????? ??????????? ??????? ?????????? 26-32 % ??????? ?
67-72 % ????????????? ?5+.
??????? ??????????? ??????? ?? ???????? ????? Pd-Re-?, ?????????? ????????????????
????????? ???????? ??????? ???????????????? ????????, ? ????? ???????????????? ?????,
????, ??? ??? ???? ?????? ?????, ? ?????????? 65-75 % ??? 40 ?? ? 80-85 % ??? 80 ??. ??????
???????????? ???? ????? ????????? ?????????? ? ? ??????? ??????????, ??? ???????????? ??# 530 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
?)
X, %
40?C
80?C
100
80
60
40
20
0
Pd-Re-2 Mix-PdRe-2
Re-Pd-2
Y ?3=, ???.%
Pd-Re-5 Mix-PdRe-5 Re-Pd-5
40?C
Pd-Re-10
Mix-PdRe-10
Re-Pd-10
?)
80?C
60
45
30
15
0
Pd-Re-2 Mix-PdRe-2
Re-Pd-2
Pd-Re-5 Mix-PdRe-5 Re-Pd-5
Pd-Re-10
Mix-PdRe-10 Re-Pd-10
???. 1. ??????????? ??????? ??????????? ??????? (?) ? ?????? ????????? (?) ?? ?????????? ?????? ?????
? ??????? ????????? ???????? ???????????
????????? ?????????. ????? ????????? ?? ?????? ???????? ?????????? 42-52 ???. % ??? 40 ??
? 48-62 ???. % ??? 80 ?? ? ??????????? ?? ??????? ?? ?????????? ????? ? ????????. ?????
??????? ?? ????????? 25 ???. % (????. 2). ????? ??????????? ????? ???????????? ???????,
????????? ? ??????? ? ??????????? ????? ?????? ?????? ? ????????????. ????? ??????? ????????, ??? ?????????? ????????????? ?5+, ???????????? ? ???????? ???????? ?????????, ??
????????? 8 ???. %, ??? ????????????? ?? ?????? ?? ?????? 7 ???. %. ????? ???????, ?????????? ?????? ??????????????? ? ??????????? ???????????? ????????? ????????? ?? ??????? ??
???????????? PdO-Re2O7/SO42-/ZrO2, ?????????????? ? ?????????????? ???????????????? ???????? ???????? ?????????? ??????????????? ????????, ? ????? ?????.
??????????? ????????? ???????? ? ????? ? ???????? ????????????? ???? ????? ? ??????????? ??????????? ????? 2,0 % ???? ???????????????? ??????? ???? (???. 2 ?, ?). ???
??????? ?? ??????????? ????????, ???????? ????????? ???????? ?? ???? ???????? ????? ????# 531 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
??????? 2. ?????? ????????? ??????????? ??????? ??? ????????????? ? ????????? ???????? ?????????
???????? ??????????? (80 °C, ???? 0,5 ?-1)
???????
C?????????, ???.%
Pd-Re-2
Mix-PdRe-2
Re-Pd-2
????????
66,2
0,2
0,9
?????-1
1,4
0,9
1,1
?-?????-2
17,3
22,0
17,4
?-?????-2
7,1
10,1
9,1
?5+
8,1
66,8
71,5
?)
?)
336.9
335.5
44.4
42.9
46.2
a)
1
1
a)
2
b)
b)
2
335.9
c)3
c)
3
335 338 341 344
Binding energy, eV
40
45
50
Binding ?????,
energy,??
eV
???????
??????? ?????, ??
???. 2. ???-???????: ?) ??????? Pd3d ???????? 1 ? Mix-PdRe-2, 2 ?Re-Pd-2,3 ?Pd-Re-2; ?) ??????? Re4f
???????? 1 ? Mix-PdRe-2, 2 ? Pd-Re-2, 3 ? Re-Pd-2
??? ????? 336,9 ??, ??? ????????????? ???????????? ?????? PdO [8, 9]. ????? ???? ???? ????????, ??? ?????? ??? ????????? ???????? ??????????? ? ????????, ??????????? ???????
?????????? ? ?????????????? ??????? ? ?????????????? ?? ?????? ?????????????, ??????????????? ? ????????? ?????? ????????? [6].
?????????? ????????? ????????, ???????????? ??? ??????? Pd-Re-2, ???????????? ?????????? ????? ????????? ? ????????. ??? ??????? Re-Pd-2 ? ??????? ??????????? ????? ???????????????? ??????, ??????????????? ??????? ????? 335,9 ?? ? ?????????? ?????? ?????????
?????????????? ???????? [10, 11]. ??? ??????? Mix-PdRe-2 ???????? ?????? ?????? ????????? ? ??????? ??????? ????? 335,5 ??, ???, ?? ?????? [12], ??????? ? ??????????? ? ???????
????????????? ?????? ?????????????? ????????.
?????????? ???-???????? Re4f ????????, ??? ??????????? ??????? ????? ??????? ??????? ????? ????????????. ??? ??????????????? ? ??????????? ?? ??????????? ?????????????
# 532 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
??????? 3. ??????? ??????? ???????? ?? ??????? ??????????? ??????? (X, %) ? ?????????????
??????????? ????????? (S, %) ?? ??????? Pd-Re-2
????, ?-1
40 °C
60 °C
80 °C
?, %
S, %
?, %
S, %
?, %
S, %
0,5
70
64
66
73
75
65
1,0
54
82
49
74
59
64
1,5
34
85
42
71
40
50
2,0
35
80
28
68
49
59
4,0
23
74
23
65
27
33
?? ??????? ???? ???? ????????? ???? ?????. ????????????? ? ??????????? [13, 14] ????????? ??????? ?????????? ? ???????? ????? 42,9 ?? ? ????????? Re4+, ?????????? ? ????????
????? 44,4 ?? ? ? ????????? Re6+, ????? ??? ?????????? ??? 46,2 ?? ????????????? Re7+. ????????????? ?????????? ??????????????? ????? ??????????? ????????? ??? ???? ????????.
?????????? ????????????????? ????? ? ????????, ?????????? ???????????????? ?????????,
??????????? ????????? ? ???????? ? 1,5 ???? ??????, ??? ? ??????? Mix-PdRe-2. ? ?????? ???????????? ??????? ????????? ????? ???????? ??????????????? ? ? ??????? Mix-PdRe-2 ???
???? ??????????. ???????????? ?????????? Re+7 ??????????? ? ??????? Re-Pd-2, ? ?? ?????
??? ? ??????? Pd-Re-2 ??? ???????????? ????? ????????????? ????????.
????? ???????, ???????? ???????? ???????, ?????????? ????? ???????? ????????, ? ????? ?????, ???????? ???????? ??????????????? ? ?????, ???????? ? ???????? ???????????
???????. ??? ????, ?? ?????? ??????? ?????? [7], ?????????? ??????????????? ????????????? ?????????? ??????????? ????????????? ???????????? ?????????? ? ???????? ??????????????? ???? ?????. ????????, ??????????? ????????? ???? ???????? ?????????? ??????
??? ????????, ?????????? ????????? ????????.
??????? ???????? ???????? ?????? ????? ?? ??????? ??????????? ??????? ? ????????????? ???????? ??? ???????????? 40, 60 ? 80 °? ?? ??????? Pd-Re-2 ???????????? ? ????. 3.
??? ????? ?? ??????????? ??????, ??????? ??????????? ??????????? ????????? ? ??????
???????? ???????? ?????? ????? ?? 66-75 % ??? 0,5 ?-1 ?? 23-26 % ??? 4 ?-1. ????????????
????????????? ???????? ?? ????????? ??????????? ??? ??????????? 40 ?? ? ?????????? 8085 % ??? ????????? ??????? ??????????? ??????? 34-54 %. ??? ????? ? ??? ?? ???????????
? ?????? ??????? ????????, ? ?????????????, ? ??????? ??????????? ??????????? ?????????
? ???????? ?????????????. ????? ????????????? ????????? ? ?????? ??????????? ????????
??? ??????? ????????? ??????? ??????????? ???????.
?? ???. 3 ???????????? ??????????? ?????? ????????? ? ??????? ?? ??????? ???????????
??????? ??? ?????????? 40, 60 ? 80 °?. ??? ?? ??? ????????? ????????? ????????? ???????????, ?????????? ?? ?????? ????????, ????? ???????????? ? ?????? [15]. ??? ??????? ?????????????? ?????? ????????? ? ???????? ??????????, ??? ??????? ?????????????? ????????? ??????????, ? ?? ???????????? ????????? ???????? ?????-1. ? ???????? ???????? ???????????
??????? ???? ?????? ?????? ? ?????-1, ? ?????????? ??????????? ??????? ??????????????
??????? ??????????? ????? ???????????? ?????????? ??????????? ???? ???????????. ?????# 533 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
?)
?)
Y, ???.%
Y, ???.%
60
?)
Y, ???.%
60
60
????????
????????
40
????????
40
40
??????
??????
??????
20
20
0
0
?,%
50
20
0
0
0
?,%
50
0
50
?,%
???. 3. ??????????? ??????? ????????? ? ??????? ?? ??????? ??????????? ???????: ? ? 40 oC; ? ? 60 oC;
? ? 80 oC. ????? ? ???????????; ????? ? ?????? ?? ??????
Y C5+, ???. %
14
40
60
80
12
10
8
6
4
2
0
0
20
40
60
80
X, %
???. 4. ??????????? ?????? ????????? ?????????????? ?5+ ?? ??????? ??????????? ???????
?????? ?????? ??????? ???????????? ? ?????? ?????????? ??????? ???????????? ??????-1 ?
???- ? ?????-??????-2, ?????????? ???????-2 ? ????????. ????????? ??????? ??????????? ??????? ???????????? ?????? ?? ????, ??? ??? ???????? ???? ????? ???????????? ?? ???????.
??? ??????? ?? ??????????? ??????, ???????????? ????? ????????? ??????????? ???
??????????? 80 °? ? ??????? ??????????? ??????? 75 % ? ?????????? 49 ???. %, ??? ????????????? 81 % ?? ?????????????? ??????. ??? ???? ??????????? ?????????????? ? ?????????????????? ??????? ????????? ?????? ??? ???????? ??????????? ????????. ??????? ????????????? ??????????? ????????? ? ?????? ??????????? ????? ????????? ???????????????
?????????????????? ??????????? ??????? ? ???????. ??? ????? ?? ???. 4, ????? ?????????
?????????????? (??????? C5+) ??? ?????????? ??????? ??????????? ??????? ??????????? ?????????? ? ?????????? ???????????.
# 534 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
?????? ? ??????????????? ????????????????? ???????????? ?????????????? ???????
????????? ?? ???????, ??????????? ???????????? ? ?????? ??????, ??????????? ????????
????? ?? ???????? ??????????? ????? [16] ??? ??????? NiSO4/Re2O7/?-Al2O3. ????????
?????????? ???????? ??????? ??????????? ??????? 55-63 %, ?????? ??????????? NiSO4/Re2O7/?Al2O3 ???????????? ????????????? ??????????? ????????? ?? ????? 49 ???. %, ??? ?????????????
?????? ????????? 27-31 ???. %. ????? ???????, ??????????? ??????? PdO-Re2O7/SO42-/ZrO2 ??
???????? ?? ????? ?????????????? ????????? ????????, ????????? ? ??????????.
??????
1. ????????, ??? ??????? PdO-Re2O7/SO42--ZrO2 ????? ???? ??????????? ?????????????
?????????????? ??????? ????????? ?? ???????. ??? ???? ??????????? ???????? ????????????? ???????????? ???????? ???????????????? ???????? ?????????????????? ???????? ???????????????? ??????? ????????, ? ????? ????? ? ?????????????? ???????? ????? ? ????????????.
2. ???????????, ??? ??????????? ?????????? ?????? ????? ? ???????????? PdO-Re2O7/SO42-ZrO2 ??? ??????????? ??? ?????????? ? ???????? ?????????? ?????????? 1,87 ???. %.
3. ??? ???????? ??????? ??????????? ? ???????? ???????? ?????? ??????? ?? ??????????
???????? ??????? ????????? ?? ??????? ???????????, ??? ???????????? ????? ????????? 49
???. % ??????????? ??? ??????????? 80 ?? ? ???????? ???????? ?????? ????? 0,5 ?-1. ???????
??????????? ??????? ??? ???? ?????????? 75 %.
?????? ????????? ??? ?????????? ????????? ??????????? ????? ???????????????
???????????? (????? 13-03-12258 ???_?).
?????? ??????????
1. ??????? ?.?., ???????? ?.?., ?? ???? ?????????? ?????????????? ????????????????? ?????????? ???????? ????????? ????????? // ?????????????? ?????????? ? ????????. 2009.
? 10 (78). ?. 99-121.
2. ???. ? 2292951 (?????????? ?????????). ?????-???????? ??????????? ??????????
?????????? ?????????????, ?????? ??? ????????? ? ?????? ??????? ????????? ? ??? ?????????????? / ?.?. ?????????, ?.?. ??????????????, ?.?. ??????? (??? «???????????? ?????
???????????? ? ??????????»). 2007.
3. ???. ? 2370314 (?????????? ?????????). ??????????? ? ?????? ????????? ?????????
/ ?.?. ?????????, ?.?. ??????????????, ?.?. ??????? (??? «???????????? ????? ???????????? ? ??????????»). 2009.
4. ???. ? 2427421 (?????????? ?????????). ???????????, ?????? ??? ????????? ? ??????
?????????????? ??????? ????????? ?? ??????? / ?.?. ????????, ?.?. ?????????, ?.?. ??????????? (???? ?? ???). 2011.
5. Pat. ? 3728415 (US). Production of n-butenes from ethylene / R.P. Arganbright (Petro-Tex
Chemical Corporation). 1973.
6. Sayfulina L.F., Buluchevskiy E.A., Lavrenov A.V., Gulyaeva T.I., Trenikhin M.D., Protasova
O.V., Gerasimov E.Yu., Gulyaev R.V., Drozdov V.A. Direct Synthesis of Propylene from Ethylene over
# 535 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Luiza F. Sayfulina, Evgeniy A. Buluchevskiy? Direct Synthesis of Propylene from Ethylene over?
Palladium Containing Catalysts: Influence of the Support Nature // Adv. Mater. Res.. 2014. Proceedings
of «PFSD 2014». In press.
7. Phongsawat W., Netiworaruksa B., Suriye K., Dokjampa S., Praserthdam P., Panpranot J.
Role of support nature (?-Al2O3 and SiO2-Al2O3) on the performances of rhenium oxide catalysts in the
metathesis of ethylene and 2-pentene // J. Nat. Gas Chem., 2012, 21, 158-164.
8. Pillo T., Zimmermann R., Steiner P., Hьfner S. The electronic structure of PdO found by
photoemission (UPS and XPS) and inverse photoemission (BIS) // J. Phys-Condens Mat., 1997, 19,
3987.
9. Ivanova A.S., Slavinskaya E.M., Gulyaev R.V., Zaikovskii V.I., Stonkus O.A., Danilova I.G.,
Plyasova L.M., Polukhina I.A., Boronin A.I. Metal?support interactions in Pt/Al2O3 and Pd/Al2O3
catalysts for CO oxidation // Appl. Catal. B-Environ. 2010. 97. 57-71.
10. Mason M.G. Electronic structure of supported small metal clusters // Physical Review B.
1983. 27, 748-762.
11. Wertheim G.K. Zeitschriftfьr, Physik D Atoms, Moleculesand Clusters 12, 1989, P. 319-326.
12. Gulyaev R.V., Stadnichenko A.I., Slavinskaya E.M., Ivanova A.S., Koscheev S.V., Boronin
A.I. In situ preparation and investigation of Pd/CeO2 catalysts for the low-temperature oxidation of CO
// Applied Catalysis A: General. 2012. 439?440, 41-50.
13. Yuan Y., Iwasawa Y. Performance and Characterization of Supported Rhenium Oxide
Catalysts for Selective Oxidation of Methanol to Methylal // J. Phys. Chem. B. 2002. 106, 4441-4449.
14. Okal J., Tylus W., Kepinski L. XPS study of oxidation of rhenium metal on ?-Al2O3 support //
Journal of Catalysis, 2004. 225, 498?509.
15. ??????????? ?.?., ???????? ?.?., ????????? ?.?., ????????????? ????????? ????????? ?? ??????? ?? ???????????? NiO-Re2O7/B2O3-Al2O3. ????????????????? ?????? ? ???????????? ?????? ???????? // ????? ? ????????? ??????????? ????????. 2014. 6. ?????????? ?
??????.
16. Lu Li, Radostina Dimitrova Palcheva, Klaus-Joashim Jens, Conversion of Ethene to Propene
by a Dual Function NiSO4/Re2O7/?-Al2O3 // Top Catal, 2013. 56, 783-788.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 537-546
~~~
??? 661.78
5-Butoxymethylfurfural Catalytic Hydrogenation
over Palladium Catalysts
Irina L. Simakova*a, ?ndrey ?. Morozovb,
Valery ?. Tarabankob and Mikhail Yu. Chernyakb
a
Boreskov Institute of Catalysis SB RAS
5 Lavrenteva, Novosibirsk, 630090 Russia
b
Institute of Chemistry and Chemical technology SB RAS
50-24 Akademgorodok, Krasnoyarsk, 660036 Russia
Received 29.09.2014, received in revised form 14.10.2014, accepted 18.11.2014
The 5-butoxymethylfurfural (5-BMF) catalytic hydrogenation process has been studied using SIBUNIT
and zirconium dioxide supported palladium catalysts in tetrahydrofuran and butanol, respectively.
5-BMF dibutylacetal is the main product of heating the solution of 5-BMF without both catalyst
and hydrogen. Butyl ester of 5-butoxymethyl-2-furan carboxylic acid and butanal dibutylacetal traces
have also been detected. In the first step, processes of the furan ring hydrogenation to tetrahydrofuran
derivatives using palladium catalysts occur. Hydrogenation of the dibutylacetal group occurs slower
than the furan ring conversion. Hydrogenolysis and migration of the furan ring substituents have also
been observed.
Keywords: 5-butoxymethylfurfural, catalytic hydrogenation, palladium catalysts, 5-butoxymethylfurfural dibutylacetal.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: simakova@catalysis.ru
# 537 #
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Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
?????????????? ????????????
5-????????????????????? ?? ??????????? ?????????????
?.?. ?????????, ?.?. ????????,
?.?. ???????????, ?.?. ???????
?
???????? ???????? ??. ?.?. ????????? ?? ???
??????, 630090, ???????????, ??. ????. ???????????, 5
?
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50-24
?????? ??????? ??????????????? ???????????? 5-????????????????????? (5-???) ??
??????????? ?????????????, ?????????? ?? ?????????? ???????? c?????? ? ??????? ????????
? ???????????????? ? ???????? ??????????????. ??? ?????????? ???????? 5-??? ? ????????
??? ????????????? ? ???????? ???????? ????????? ???????? ?????????????? 5-???, ?
????????? ????????????? ???????????????? ????? ????????? ???? 5-????????????2-??????????????? ??????? ? ?????????????? ????????. ? ??????????? ???????????
????????????? ? ?????? ??????? ????????? ???????? ???????????? ?????????? ??????
? ??????????????????? ??????????? ? ??????????? ????????????????? ???????????.
??????????? ????? ???????? ????????????? ? ???????? ???????????? ? ????????? ??????.
???????? ?????: 5-????????????????????, ?????????????? ????????????, ???????????
????????????, ?????????????? 5-?????????????????????.
????????
?????????? ??????? ????????? ??????? ? ?????? ?????????? ?????????? ?? ???????????? ???????? ? ????????? ????? ???????? ??????????? ?????????? ??????????????. ???????? ?????? ???? ???????? ???? ?????????????? ???????? (??????, ??????? ? ??.), ????
??????????? (???????? ????????, ????????? ? ??.). ????????-?????????????? ????????
??????????? ????????? ??????????????? ???????????? ???????? ?????????? ?? ?????????
? ???????????????, ? ?? ????????? ? ?????????? ???????? ? ????? ??????? ?????????. ?
???????? ??? 5-????????????????????? (5-???), ??????????? (4-??????????????) ??????? ?
???????? ?? ????????? ???????.
?????????? ?? ?????? ?????????, ?????? ?????????? ???????? ????????-??????????????
????????? ????????? ?????????, ?????? ???????? ??????????????? [1]. ????????????? ? ?????????? ????????? ????? (??) ????????????????? ????? (?? = 110) [2], ???????????????????
? ?????????????????? ?????? (113 ? 97 ??????????????). ???? ?? ???????? ?????????????
????????? ???????????? ?????????, 2-??????????, ? ????? ? ???????? ??????? ?????? ???????? ????????? (90 000 ??) [3].
?????????????? ????????????? 5-?????????????????????? ? ??? ?????? ???????? ????????????? ??????? ? ???????? (2,5-????????????, ????????? ????? 119) [3, 4] ? ?????????
# 538 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
???????? (??????????????, ????????????). ??????????????? ??????????? ?????? ?????????
5-???????????????????? [5].
??? ???????????? 5-??? ? 2,5-???????????? ?????????? ?????-?????????? ???????????? ?? ?????????? ???????? [4]. ??????????? Ru/C ???????? ? ??????????? ? ???????? ????????? ???????????? ?????????? ??????, ??????????? CuCrO4 ?????? ???????????????. ???????????? ???????? 2,5-?????????????????????? ? 1-???????? ?? ?????-?????????? ????????????
? ??????? ???????????? 3:1 ??? 453 ? ???????? ? ????????????? ?????? ????????????? ?
????????????? ??????????? ????????????? 71 %, ????????????? ?????? 4 % ? ?????? ????????? 20 % ??? ????????? 5-?????????????????????? 52 % [3]. ? ???? ?????? ?????? ? ????????
????????????? ???????????? ???????????? ????? ??????????? ? ?????? ???????????? [6-9].
?????? ?????????? ??????????? ???????? ? ????????? ?????? ???????? 5-?????????????????????, ???????? 5-???????????????????? [10], ?????????? ? ??????????? ????????????????? ?????? ????????? ????????????? ?????? ? ???????? ????????????:
HOH2C
OH
O
HO
CH2OH
C4 H9 OH, NaHSO4
OHC
O
CH2 O C4 H
4H2 O
OH
???? ????????? ?????? ??????????? ? ???????? ????????? ??????????????? ???????????? 5-????????????????????? ?? ??????????? ?????????????.
????????????????? ?????
?????? 5-?????????????????????.. 100 ?? ???????????? ????????, ??????????? 150 ?/?
???????? ? 560 ?/? ?????????? ??????, ???????? ? ??????????? ?????, ????????????? ???????? ?????????????, ???????? ?????????????, ? ????????? 200 ?? ????????. ???????????
????? ???????? ?? ??????? (102?103 °?) ? ????????? ? ??????? 6 ?, ????? ????????? ? ???????? ???????????? ????, ??????? ????? ?????????????? 10%-??? ????????? ??????????? ?????? ?? ?? 6-7 ? ?????????? ???????????? ??????????????? ???????? ????? 5-??? ???????
?????????????? ?????????????. ????? ???????? ?????????????????? ????? ? ??????????
?????????? ?????????? ??? ???????? (2 ?? ??. ??.) [10].
?????? ????????????? ????????????. ???????????? ???????? ?????????? ????????
??????????? ?? ?????????? ???????????? ???????? ??????? (S?? = 355 ?2/?) [11] ? ????????
???????? ZrO2 (S?? = 96 ?2/?) ??????? 40?70 ???.
??????????? 6%-??? Pd/C ????????????? ??????? ???????? ??????????? ???????? ??????? ????????? PdCl2 ? ??????????? ??????????????? ?? ?????????????? ???????? ? ???? ???????? ??? ?????????? ?? ??????????? 250 °? ?? ????????? ??????? 1,5 °?/???.
?????????? ??????????? 2%-??? Pd/ZrO2 ??? ??????????? ??????? ???????? ?? ????????????. ??????????? ??????????????? ? ???????????????????? ?????? ??? ??????????? ??
628 K.
?????? ??????????? ?????. ????????????? ???????????????? ????????? ???????????? ??????? ???????-????-????????????? ?? ???????? VG-7070 GC/MS (??????? 30 ? ? 0,2 ??
# 539 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
Silicone SE-30) ? Agilent 5973N EI/PCI (??????? 30 ?? ? 0,25 ?? HP-5ms). ?????????????? ?????? ??????????? ?????? ????????? ??????? ?????????????? ????????????? ?? ????????????
???-80 (??? «??????????») ? ????????-????????????? ?????????? ? ????????? ?????????? ???????? 2,0 ? Ч 2,0 ??, ??????????? ????????? Chromosorb 101, ???????????????? 5%??? FFAP. ???-???????? ? ????. ????????? ???????????? ????????????? ? ??????? ??????
???????? «??????».
??????????? ??????????? ?????????? ??????? ?? ?????????? ???????? ????????? ???????????????????? ??????? ?? ?????????????? ??????????? VRA-30 c Cr-?????? ????????????? ??????.
???????? ??????????? ???????? ?????????? ??????? ???????? ????????? ????? ? ?????????????? ??????????? ???????? ??????????? Sorptomatic 1900.
??????? ???? ???? ???????? ?? ??????????????? ???????????? SPECS ? ?????????????? ???????????????????????? ????????? AlKa (hn = 1486,61 ??, 205 ??). ????? ??????? ?????
(???) ???? ?????????????? ????????????? ?? ????????? ????? ???????? ??????? ?????????????? ?????? ? ????: Au4f7/2 (84,0 ??) ? Cu2p3/2 (932,67 ??). ?????? ??????????, ???????????
? ???????? ??????????? ??????????, ????????? ? ??????? ?????? ??????????? ?????????, ?
???????? ???????? ???????????? ????? C1s (284,5 ??) ???????? (???????) ??? Zr 3d5/2 ?????
???????? (??? = 182,3 ??) ? ??????? ?????? ZrO2. ???????? ??????? ?????????? ??? ???????
??????????? ??????????? ? 50 ??, ????????? ???????????? ?????? ? 10 ? 20 ??.
?????? ??????? ????? ????????? ?? ?????????????? ??????????? ?????????? ???????? ?????????? JEM-2010 (??????) ? ??????????? ?? ??????? 0,14 ?? ? ?????????? ??????????? 200 ??. ??????? ??????? ?????? (?? ????? 250 ??????) ???????????? ?? ?????????
???????:
¦ (x d )
,
¦x
i
dm
i
(1)
i
i
i
??? xi ? ????? ?????? ? ????????? di.
?????????? ?????? ??????????? ???????? (EDX) ????????? ? ???????????????????
????????????? ?????????? EDAX DX-4 ????? Ametek Inc., ???. ??????? ?????????????
??????????? ?????????? 150-300 ??2.
???????????? 5-?????????????????????. ???????????? ?? ???????????? ???????????? 5-????????????????????? ? ???????? ????????? ? ????????? (150 ??) ?? ???????????
????? ??? ????????? ???????? 10 ??? ??? 200 ?? ? ?????????????? ????????? ?? ??????? ???????????? ????. ???????? ?-???????? 19 ?, 5-????????????????????? ? 1 ?. ????? ???????????? ? ????????????????? ???????????? ??????? ????? ?? ??????.
???????????? 5-????????????????????? ? ???????????????? ????????? ? ??????????
???????? ? ???????? ????????????? ??? ??????????? 60 ??. ? ??????? ????????? ??????????? (??????????? ??????? 0,2 ?) ? ??????????? ?????????????? ? ??????? 1 ? ? ???? ???????? ??? ??????????? 473 ?. ? ???????? ???????? ??????????? ????? ???????????? ???????
5-????????????????????? (1 ?) ? ???????????? (19 ?). ??? ?????????? ??????? ? ????????????????? ????????? ??????? ?? ??????? ?????????????? ?????????? ????? ??????? ? Ni-Cr# 540 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
????????????? ??? ??????? ?? ???????? ????????? ? ????? ??????? ? ????????? ??? ???????
?? ???????? ???? ? ????? ???????? ? ???????. ???????? ??????? ???????? ? ????????????? ? ????????????? ??????? ??/?? ? ?????????????? ????????????? (???). ?? ???? ???
?????????? ????????????? ?????????? ?????? ??????????????? (??????? ???? 3?6 % ??
??????? ??????? ????????????, ????? ??????????? 14,5 ???), ?????????????, ????????, ???
???????? 5-???.
??? ????????? ?????? ???????????? ??????????? 5-????????????????????? ?????????
???????? ??????????? ? ???????????? ???????? ? ?????????? ????????????.
?????????? ? ??????????
??????????? ??????????? 5-?????????????????????. ? ???????????? ????????????, ???????????????? (???? 65 °?), ????????????? ???????? 5-????????????????????? ?????
???????????? ? ?????????????? ??????????? ???????? ???????? ?????? ??? ????????? ????????.
??????????????????? ???????? 5-??? ? ???????? ???? ???????? 5-??? (??????? ????
18,3 % ?? ???? ????????), ???????????? ?????????? ??? ?????????????? (5-???-???, 15,7 %)
? ????????? ??? ??????????????? (????. 1).
????? ?????????? ???????? 5-??? ? ???????? ??? ???????????? ? ???????? ?????????? ??
?? ????????, ?? ?????? ??????????????? ? ?????? ???? ????????? ?????????? ??????????????????? ????????? ????????, ? 5-???-??? ? ? ??? ????. ? ????????? ??????????? (0,8 %)
?????????????? ????????? ???? 2-????????????-5-??????????????? ???????.
??????? ????????, ??? ???????????????? ????-???????????? ? ????????????? ????????? ????????? ???????? ? ?????? ??? ????, ??? ? ????????: ????? ???????? ?????????
????????? ?????????? 45 % ?? ??????? ????????, ? ?? ?????????? ? ????? 5 ???. %. ?????????? ??????????? ??????? ? ?????????? ?? ????????? ????? ?????????? ?????? ?????????
? ??????????????? ????????. ??? ?? ?????, ???? ?????????, ??? ? ???????????? ? ?????????????? 5-???-??? ???????? ???????? ????????? ??????????? 5-???, ?? ?????? ?? ??????????? ????. 1 ??????????, ??? ???????????????? ??????? ? 5-???-??? ? ??? ???? ????,
??? ? 5-???, ? ????????? ???????? ? ???? ??????? ????? ?????????? ???????? ????????? ??
?????? 40 %.
?????????? ?????????? ??????????, ??? ???????? ??????? ??????????? ???????????
5-????????????????????? ? ???????? ??????? ? ??????????? ??????????????, ? ?????????? ??
???? ? ?????????? ???????-????-????????????:
R-Fur-CHO + 2 BuOH = R-Fur-CH(OBu)2 + H2O.
(2)
??????? ????????, ??? ??????????? ???????? ??? ???????????? ?? 100 ?? ??????????? ??
???? ??-?? ????????????????? ??????????? [12]. ? ??????????????? ????????????? ????????? ??????? 200 ?? ??? ??????????? ???????? ???????????.
??????????? ? ??????????? ????? ???????? ?????????????? ???????? (???????????????) ? ?????????? ????? 2-????????????-5-??????????????? ??????? ????? ???? ???????????
??????????? ???????? ??????? ???? ??????????-????????-?????? (????????? ???????? ??????????) ? ?????????? ??????????????.
# 541 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
??????? 1. ?????? ????????? ??????????? 5-??? (? % ??????? ???? ? ????????????? ??????? ???????
????) ??? ?????????????
?
??????? 5-??? 5-??? 1,1-?????????????????? ????
?????
????????????
2-????????????-5???????
??????????????? ???????
1
100
18.3
15.7
0.9
2
100
13.5
31.2
3.9
????? ?????????
???????????
0,8
34
45,5
* ????? 1 ? ??????? 1 ? 5-??? ? 19 ? ????????, ????? 2 ? ?? ??, ????? ?????????? ? ????????? ? ??????? 4,5 ?.
?????????????? ?????????????. ??? ???????????? 5-????????????????? ???? ?? ????????? ??????? ???????????? ?????? ???? ??????? ? ???????????? ??????????? ???????????? Pd/ZrO2 ? Pd/?.
?????? ??????? ????? ??????????, ??? ??????? 6%-???? Pd/C ???????? ???????
??????? ?? ??????? ???????? 3,2 ??, ?????????? ?????????????? ?? ??????????? ??????????? ????????. ?? ?????? ????, ??????????? ???????? ? ???????? ?????????????
??????? ? ?????????????? ???????????? ??????? ? ????????????? ?????????? ?????????.
??????????? 2%-???? Pd/ZrO2, ?? ?????? ???, ????? ??????? ??????? ?? ??????? ???????? 2,9 ??, ?????????? ?????????????? ?? ??????????? ?????? ???????? (???. 1). ???????? ?????? ????, ??????????? ???????? ? ???????? ????????????? ??????? ? ?????????????? ???????????? ??????? ? ????????????? ?????????? ????????? (???. 1).
??????????????
????????????
5-?????????????????????.
????????????
5-????????????????????? ? ???????????????? ? ??????????? ???????????? 6 %-???? Pd/C
????????? ??? 60 ??, ???????? ???????? 1 ??? ? ??????? 3?17 ?. ??? ????? 3 ? ???????????? 5-???????????????????? ? ???????? ?? ??????????????. ????? ????????? ????????????
??????????? ???????????????? ??????? ?????? 2,5-?????????????????????? ? 2,5-???????????? (????. 2). ???????????? ?????????? ??????? ?? ??????? ? ?????????? ???????????? ?
??????????????? ??????????????? ? ?????? ???????????????????? ????????.
3 3 5 .1
3 3 6 .0
30
335
340
? ? ? ? ?? ? ? ? ? ? ? , ? ?
345
350
???. 1. ?????-?????? ???????????? 2%-???? Pd/ZrO2 (?????), ????-?????? ???????????? 2%-????
Pd/ZrO2 ?? ??????? (??????)
# 542 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
??????? 2. ?????? ??????????? ????? ???????? 5-????????????????????? ? ???????? ???????????? ?
??????????? ???????????? 6 %-???? Pd/C. ????????????????? ???????????? 3 ? 17 ?
????? ???????????,
???
???????
????, %
(3 ?)
???????
????, %
(4,5 ?)
???????
????, %
(17 ?)
??????????
3,771
100
100
100
???????????????
4,25
-
0,93
1,19
2,5-??????????????????????
4,312
5,95
3,36
1,93
2,5-????????????
?????? ????????? ???????????? 5-????????????????????? ? ??????????? ???????????? 2%-???? Pd/ZrO2 ????? ?????? ? ???????????? (????. 3). ???????? ?????? ????, ???
?????? ????????? 5-??? ????????? ?????? ????????? ??????????? ?????????? 21,1 %
? ??????????? ?? ????????? ??? ?????????? ????????????????? ???????? ? ?????? ????.
??? ???????? ??????? ???? ???????????, ?????????? ?? ???????????? Pd/C, ? ????????
?? ?????????? ??? ????????????????? ????????. ?????????????, ???????????? ?????????? ?????? ? ????????? ????????? ?? ????????-??????????? ???????????? ?????????????.
? ?????? ???????, ???????????? ?????????? ?????? ???? ?????? ??????????: ?????????
???????????, ?? ??????????? ?????????? ????? 5-????????????-2-??????????????? ???????, ? ????? ???????????, ? ??????????? ???????????????? ??????????.
????? ????, ???????? ?? ???? ???????? ??????? ? ????? ???????? ?????????? ????????
????????? ? ??????????????????? ??????, ?.?. ?? ???? ???????????? ??????? ????????? ???????? ???????? ????????????. ? ????? ?????-???? ???????????? ??????? ? ??????????????? ??????? ???????????.
?????????? ??????????????? ? ??????? ????????? ???????????? ? ???????? ??????????
?????? ? ??????????? ?? ??????? c 54 ?? 38 %, ?.?. ???????????? ??? ?????????, ?? ?????????, ??? ????????? ??????. ????????, ???????????? ???????? ? ??????? (159 ?.?.?.) ????????????????? ??????????? ????????????? ??????????? ???????? ? ? ?????????? ?????
?????????????? ????????? ???????????? 5-??? ? ???????? ??????????? ??????????? ????
?? ????????? ? ????????? ? ????????????????. ? ?????? ???????, ???????? ????????????
????????????????? ??????????? ? 2,5-????????????????????????????? (? ??? ??????) ? ???????????????? ? ???????????? ??????????? (????. 3).
???????-????-??????? ?????????????????? (?? ?? ????????? ? ????? ??????) ??????????:
5-????????????????????, 17,66 ???. 182(15, ?+), 153(23, (?-???)+), 110(21),
109(100, (?-?4?9?)+), 97(71, (????2?4?2?)+), 81(31, (??3?4?2?)+), 69(6,5), 57(5,8, ?4?9+),
53(21, ?4?5+).
5-????????????? ??????????????, 19,06 ???. 240(10, M+), 168(10), 167(70, (M-BuO)+),
127(1), 112(10), 111(100, (M-BuO-Bu+H)+ ), 95(1), 81(1), 57(1).
2,5-???????????????????, 21,03 ???. 240(36, ?+), 167(100, (?-O?4?9)+), 153(17,
(?-CH2O?4?9)+), 111(29, (HOCH2-(C4H2O)??2)+), 97(84, (H???2(?4?2?))+), 96(32), 94(40), 83(51),
57(52).
# 543 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
??????? 3. ?????? ??????????? ????? ???????? 5-????????????????????? ????? ???????????? ?
??????????? ???????????? 2%-???? Pd/ZrO2 (0,3 ?) ? ??????? 3 ? 13 ?
4.263
S ????, %
(3 ?)
100
6
6.897
1.42
20
12.781
3.55
5,0
2-????????????, ??????????-5-????? ?????
21
12.887
0.63
0,53
2-????????????, ??????????-5-????? ???-??????
23
14.382
1.19
1,9
1,1-??????????????
26
17.059
3.39
3,6
???????????????-2-??????????????? ??????????????
27
17.288
0.74
0,92
???????????????-3-??????????????? ??????????????
30
18.904
1.71
0,53
31
19.117
1.03
0,30
33
21.113
3.04
3,52
5-????????????????????-2-???????????????
??????????????
??????????????????????????????????? ??????????????
??????
2,5-?????????????????????????????
34
21.192
0.59
0,66
2,5-????????????????????????????? ??????
35
23.809
1.08
0,98
36
24.883
0.54
-
37
25.084
0.41
-
38
25.671
2.67
1,34
5-????????????-2-??????????????? ???????, ?????????
????
?? ? ? ?? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ?? ? ? ? ? ? ? ? ? ?? ? ? ? ? ? ? ? ?
?????????????? ??????
?? ? ? ?? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ?? ? ? ? ? ? ? ? ? ?? ? ? ? ? ? ? ? ?
?????????????? ??????
5-???????????????????????????-2-???????????????
-
-
0,54
0,38
??????????????
???? ??????????????? ? ????? ????????? ???????????
-
-
19,38
17,38
????? ????????? ???????????
?????
????
1
t??, ???
S ????, %
(13 ?)
100
1-???????
2,4
??????????
n-????????? ????
????????? ???? 5-????????????-2-??????????????? ???????, 23,81 ???. 254(17, ?+),
198(6,5, (?-?4?8)+), 181(97, (?-?4?9?)+), 153(44, (?-????4?9)+), 126(26), 125(88, (???2(?4?2?)
??)+), 108(12), 97(100, (???2?4?2?)+), 81(32, (??2?4?3?)+), 69(7,1), 57(12), 52(12).
?????????????????????????????????????????? ?????????????? ??????, 24,88
???. 244(2,6, (?-C4H9O), 243(15, (?-C4H9O-?)+), 230(11), 229(79, (?-C4H9O-C?3)+), 173(20,
(CH3(C4H6O+H)CH2OC4H9)), 155(5,8), 117 (19, (HOCH2(C4H6O+H)CH3), 99(100, (??CH2(?4?6?)
CH2)+), 87(13), 71(10), 57(39, ?4?9+), 55(10).
?????????????????????????????????????????? ?????????????? ??????, 25,08 ???.
244(2,6, ?-C4H9O), 243(12, (?-C4H9O-?)+), 229(73, (?-C4H9O-C?3)+), 173(21, (CH3(C4H6O+H)
CH2OC4H9)), 155(5,8), 117 (18, (HOCH2(C4H6O+H)CH3)), 99(100, (??CH2(?4?6?)CH2)+), 87(9,7),
71(10), 57(32, ?4?9+), 55(8,4).
5-???????????????????????????-2-??????????????? ??????????????, 25,67 ???.
244(1, (?-C4H9O)+), 243(6, (?-C4H9O-?)+), 229(3), 160(6,5), 159(64, (CH(OC4H9)2)+), 113(8,7), 103(58,
(HOCH2(C4H7O))+), 99(6), 57(100, ?4?9+).
# 544 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
5-???????????????????? ??????????????, C14H24O3, 25,68 ???. 312 (1, ?+), 240(16,
(?-?4?8O)+), 239(100, (?-?4?9O)+), 184(9,7), 183(88, (?-?4?9O-?4?9)+), 169(5,8), 125(5,2), 110(19),
109(49, (????4?2???2)+), 97(8,4), 81(7,8), 57(14, ?4?9+).
5-????????????????????, 17,66 ???. 182(15, ?+), 153(24, (?-???) +), 110(22), 109(100,
(?-? 4?9?) +), 97(72, (???? 2? 4? 2?) +), 81(31, (?? 3? 4? 2?) +), 69(6,5), 57(6, ? 4?9+), 53(20,
? 4?5+).
??????????
?????????? ?????????? ??????????, ??? ????????? ???????? ? ????????? ????????????
5-???????????????????? ? ???????? ??? 200 ??, ??????????? ? ??? ?????????????, ????????
???????????? 5-??? ? ??????????????? ??????????????.
?? ??????????? ????????????? ?????? ?????????? ???? ???????????? ??????????
??????: ????????? ???????????, ?? ??????????? ?????????? ????? 5-????????????-2??????????????? ???????, ? ????? ???????????, ? ??????????? ???????????????? ??????????. ?????? ??????? ?? ???? ????????????? ???? ? ???????? ???????? ????????????.
?????????? ???????? ???????????? ????????????????? ??????????? ? 2,5-????????????????????????????? ? ??? ??????. ? ????? ?????-???? ???????????? ??????? ? ??????????????? ??????? ???????????.
??????? ?????????? ??????????????? ? ??????? ????????? ???????????? ? ???????? (38 ?
54 %) ??????????, ???, ????????, ???????????? ???????? ? ??????? ????????????????? ??????????? ????????????? ??????????? ???????? ? ? ?????????? ????? ?????????????? ????????? ???????????? 5-????????????????????? ? ???????? ??????????? ??????????? ???? ??
????????? ? ????????? ? ????????????????.
?????? ????????? ??? ?????????? ????????? ??????????? ????? ???????????????
????????????, ????? ? 13-03-00754.
?????? ??????????
1. ??????????? ?.?., ??????? ?.?., ???????? ?.?. ?????????????? ?? ???????????????
?????. ?????????? ??????? // ??????? ???. 2009. ?. 79. ? 7. ?. 595?604.
2. J.-P. Lange, Evert van der Heide, Jeroen van Buijtenen, R. Price. Furfural ? A Promising
Platform for Lignocellulosic Biofuels // ChemSusChem 2012, 5, 150?166.
3. Yu. Roman-Leshkov, C. J. Barrett, Z. Y. Liu, J. A. Dumesic. Production of dimethylfuran for
liquid fuels from biomass-derived carbohydrates. //NATURE 447(2007) 982?986.
4. David Martin Alonso, Jesse Q. Bond and Dumesic J.A. Catalytic conversion of biomass to
biofuels // Green Chem. 2010. V. 12. P. 1493?1513.
5. Jia XQ, Ma JP, Che PH, Lu F., Miao H., Gao J., Xu J. Direct conversion of fructose-based
carbohydrates to 5-ethoxymethylfurfural catalyzed by AlCl3 center in ethanol // J. of Energy Chemistry.
2013. V. 22. Iss. 1. P. 93?97.
6. D. E. Resasco, S. Sitthisa, J. Faria, T. Prasomsri, M. P. Ruiz. Chapter 5. Furfurals as chemical
platform for biofuels production. in Heterogeneous Catalysis in Biomass to Chemicals and Fuels, 2011.
Editors: D. Kubi?ka, I. Kubi?kova. P. 1?33.
# 545 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Irina L. Simakova, ?ndrey ?. Morozov? 5-Butoxymethylfurfural Catalytic Hydrogenation?
7. M. Balakrishnan, E. R. Sacia, A. T. Bell. Etherification and reductive etherification of
5-(hydroxymethyl)furfural: 5-(alkoxymethyl)furfurals and 2,5-bis(alkoxymethyl)furans as potential
bio-diesel candidates // Green Chem. 2012. 14. P. 1626-1634.
8. Malinowski, D. Wardzi?ska. Catalytic conversion of furfural towards fuel Biocomponents //
CHEMIK. 2012. 66, 9. P. 982?990.
9. Vargas-Hernandez D., Rubio-Caballero J.M., Santamar?a-Gonzalez J., Moreno-Tost R.,
Merida-Robles J.M., Perez-Cruz M.A., Jimenez-Lopez A., Hernandez-Huesca R., Maireles-Torres P.
Furfuryl alcohol from furfural hydrogenation over copper supported on SBA-15 silica catalysts. //
J. Mol. Cat. A: Chem. 383-384 (2014) 106-113.
10. ?????????? ?.?., ???????? ?.?., ?????? ?.?. ???????????? ????????-??????????????
????????? ????????? ? ??????????? ????????????? ??????? ??? ????????? ???????????? //
????? ? ????????? ??????????? ????????. 2005. 13. ?. 551?558.
11. O.A. Simakova, P.A. Simonov, A.V. Romanenko, I.L. Simakova. Preparation of Pd/C catalysts
via deposition of palladium hydroxide onto sibunit carbon and their application to partial hydrogenation
of rapeseed oil // React. Kinet. Catal. Lett. 95 (1) (2008) 3?12.
12. ?????????. ????????? ?? ???????????? ?????: ???. ? ???. ?.: ???, 1979. ?. 2. ?. 64.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 547-555
~~~
??? 54.05
Study of Structure of Product?s Obtained
by Sulfation of Arabinogalactan from Larch Wood
with Chlorosulfonic Acid in Pyridine
Natalia Yu. Vasilyevaa,b, Alexander V. Levdanskya,
Anton A. Karacharova, Elena V. Mazurovaa,
Galina N. Bondarenkoa, Vladimir A. Levdanskya,b,
Alexander S. Kazachenkoa,b and Boris N. Kuznetsova,b**
a
Institute of Chemistry and Chemical Technology SB RAS
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 24.10.2014, received in revised form 26.11.2014, accepted 02.12.2014
The structure of the arabinogalactan (AG) and its sulfates was characterized by method of FT Raman
spectroscopy. It was established, that after sulfation of AG with a chlorosulfonic acid in pyridine, there
was an introduction of sulfate groups in arabinogalactan chain. As shown by X-ray diffraction (XRD),
initial samples of MCC had amorphous structure, and in the course of sulfation there was a further
amorphization of the structure of a material. By use of scanning electron microscopy (SEM) and
atomic-force microscopy (AFM) was shown, that sulfated arabinogalactan synthesized in pyridine,
have different morphologies from starting arabinogalactan.
Keywords: arabinogalactan, sulfation, sulfated arabinogalactan, chlorosulfonic acid, pyridine, FT
Raman spectroscopy, X-ray diffraction, scanning electron microscopy, atomic-force microscopy.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru
# 547 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Natalia Yu. Vasilyeva, Alexander V. Levdansky? Study of Structure of Product?s Obtained by Sulfation of?
???????? ???????? ?????????
??????????????? ????????????????
?? ????????? ??????????? ??????????????? ????????
? ????????
?.?. ??????????,?, ?.?. ???????????, ?.?. ??????????,
?.?. ?????????, ?.?. ???????????, ?.?. ???????????,?,
?.?. ??????????,?, ?.?. ?????????,?
?
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50-24
?
????????? ??????????? ???????????,
??????, 660041, ??????????, ??. ?????????, 79
??????? ???????? ????????? ????? ????????????????? ???????????????? (??) ?????????
???????????, ?????????? ???????????????? ?? ??????????????? ???????? ? ????? ????????.
???????? ?????????? ????? ? ????????? ?? ???????????? ?????????? ? ??-???????? ?????
????? ?????????? ?? ????????? ?? ????????? ????????? ????????????. ??????? ?????????????
?????????????? ????????, ??? ???????? ??????? ???????????????? ????? ????????
????????; ? ???????? ??????????????? ?????????? ?????????? ??????????? ?????????
?????????. ? ??????? ????????? ??????????? ??????????? (???) ? ??????-???????
??????????? (???) ????????, ??? ?????????? ??????????? ? ????? ???????? ?????????????????
?? ??????????? ?????????? ?? ?????????? ????????? ????????????????.
???????? ?????: ???????????????, ???????????????, ???????????????? ???????????????,
??????????????? ???????, ???????, ??-?????????????, ????????????? ??????????????,
????????? ??????????? ???????????, ??????-??????? ???????????.
????????
? ????????? ????? ??????? ??????? ????? ???????????? ???????? ??????? (???) ????????????? ?????????????. ??? ? ?????? ??????? ??????? ? ???, ??? ???????????? ???????? ???????? ????????????? ????????????? ????? ????? ???????? ?????????? ??????
????????????? ?????????? ? ??????????? ?? ????????? ????????? ???????? ?? ?????
????????. ?????? ????????, ??? ???????????????? ???????????? ????? ??? ????? ????? ??????????????? ??????????, ? ????????? ???????????? ??????? ????????????????
?????????? ? ?????? ???? ??????????????? ??????????, ????? ??? ???????????????, ???????????????????, ??????????????????, ?????????????????? ? ??. [1-10]. ?????? ??
????? ????????????? ? ????????? ??????? ????????????? ????????????? ??????? ???????????????? ??????????? ?? [7, 8]. ???????????????? ??????????? ????????????????
????????? ??????? ???????????????? ? ?????????????????? ??????????, ??? ??????
# 548 #
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Natalia Yu. Vasilyeva, Alexander V. Levdansky? Study of Structure of Product?s Obtained by Sulfation of?
????????????? ?? ?????????? ??? ???????????? ? ??????? ????????-?????????? ???????????. ???????????????? ??????????? ???????????????? ??????? ???????? ? ??????????????? ??????????????????, ???????? ????????? ????????????? [11]. ????????? ???????
????????????? ??????? ?????? ???????????? ? ??????????? ???????? ??? ?????????????? ????????????????? ? ?????????????? ?????????, ?????????? ????????? ????????
????????? ? ?????????, ? ????? ???????? ????????? ??????. ? ?????????, ??????????
???????? ?????????????? ? ????? ????????????? ???????? ????????, ????? ??? ??????????, ???????????????, ?????????? ? ??. ? ???????? ?????? ???? ?????????? ?????????
? ???????? ???????????, ? ????????? ?????????? ???????, ???????? ???????, ????????
1,3-L-?????????? ??????? ??????????????, ???????????????? ?????? ?????????? ? ?.?.
[1, 9]. ????? ????????????? (??) ????????????? ? ????? ?????????? ????????????? ????????? ??? ?????? ??????????? ????? ? ??? ????????? ????????????? ??????? ? ?????????? ?????? ???????? ????????.
????????, ??? ???????????????? ?????????? ???????????????? ????????????? ???????? ??????? ?? ?????? ???????????????, ????????? ?? ??????? ???????????????, ????????
???????????? ?????????? ?????, ???????????? ????? ? ??. [9-20]. ???, ??????????, ???
???????????????? ?????????? ???????? ??????? ? ????????????? ???????? ??? ????????.
??? ??????????? ???????? ??????? ???????????????? ?????????? ?????????? ???????????? ??????: ?????? ? ????????? ????????, ?????????????? ??????????? ? ???????????
????????? (?????? ?? ?????), ????? ????????????? ????????, ? ????? ??????-??????????
??????: ??? ???? ????????????? ???????? ?????????? ????????? (???), ???????-?????????????????, ??????????? ? ??????-??????? ???????????. ????????? ????? ? ????
????? ???????????? ????????? ??????????? ???????? ??????????????? ? ????? ??????,
???????????? ??? ??????????? ???????????? ?????????? ????? ? ???????????? [18].
???????? ?? ???????? ???????????? ?? ???????????? ?????????? ????? ?????????? ?
????????????? ??????????? ???????????????? ??????? ?? ????????? ?????????? ?, ? ?????????, ????????????????? ????????????????, ??????????? ????? ?????????? ? ????????????? ??????????? ???????????????? ???????, ??????? ??????? ????????, ? ????????? ?????
??????? ???????????? ? ????????? ?? ??????.
??? ??????????? ???????????? ??????????? ????? ????????? ? ????????????? ??????????? ???????????????? ??????????? ??, ?????????? ????????????? ???? ???????? [21], ?
?????? ?????? ????????? ?? ??????-?????????? ???????????? ???????? ????????????? ??????????????? ????????? (??), ????????????? ??????????????, ????????? ??????????? (???)
? ??????-??????? ??????????? (???).
????????????????? ?????
? ???????? ????????? ????? ???????????? ??????????????? (??) ????????? ???????????
????????? (Larix sibirica Ledeb.) ???????????? ??? «????? ?????????» (???????, ??????) ???
????????????? ????????? «?????????»
????????? ????????? ?? ???????????? ?? ???????? [21] ???????????????? ????????????????????? ?? ??????????????? ???????? ? ???????? ? ??????????? ?????????? ????????
????????? ? ???? ????????? ???? (?????????? ???? 13,2 % ???.). ?????????? ?????? ??????# 549 #
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Natalia Yu. Vasilyeva, Alexander V. Levdansky? Study of Structure of Product?s Obtained by Sulfation of?
?????????? ???????? ?? ???????? ?????????? 6-7%-??? ?????? ????????? ?? ??????? ?????????? ????????.
??-??????? ???????? ???? ????? ?? NXR FT-Raman ?????? ??? ??-????? ???????????? Nicolet 6700 ? ??????????? ?????? ?????? Ge ?????? ? ???????? ?????????. ? ????????
????????? ????? ??? ??????????? ???????????? ????????? ????????? Cw-Nd: YAG-?????
? ???????????? ?????? 1,064 ??. ??-??????? ???? ???????? ? ????????? 200-3500 ??-1
? ?????????????? ???????? ????????????? ?????????? 8 ??-1. ???????? ???????? ??????
?????????? 100 mW. ?????? ??????? ??? ?????? ??????????????? ??? ?????????? ????????, ? ???? ????????? 400 ?????????. ??????????? ?????? ??? ??????????? ??? ????????????? ?????? ???????????????? ???????, ? ????????? ????????? ?????????? ???????.
?????????????? ????? ??????????? ? ??????? ????????????? ???????????????????
???????????? ??????????? OPUS Ver. 6.0 (Bruker Optik GmbH, ????????? ????????). ?????? ?????? ??? ???????? ? ??????? OriginPro 7.0 (OriginLab Corporation, ???????????
???).
??????????????? ?????? ???????? ?? ????????????? ????????????? ????-3 ? ?????????????? Cu K? ?????????????????????? ????????? (? = 0,154 ??), ?????????? U 30 ??, ????
???? 25 ??. ??? ???????????? 0,02 ????., ????? ?????????? ? ????? 1 ?. ?????? ????????? ?
????????? ??????????? ????? 2? ?? 5,00 ?? 70,00 ????.
??????????? ??????????????? ???????? ?? ????????? ??????????? ?????????? ??-1000
HITACHI (??????) ? ?????????? ??????????? 15 kV ? ? ??????????? ?? 100 ?? 10 000 ???? ?
??????????? 30 ??.
???????????? ?????? ????????????????? ?? ??????? ??? ? ?????????????? ???? ????????? ? ?????????????? ?????????????? ???????????? ????????? ?????????? Solver P47
(??-???, ??????), ??????????? 14 ??? ???????? (???????????? ????????) ? ????????????
???????? (?????? SKM). ???????????? ???????? ?????????????? ?? ??????? ??? ?????????
???????????. ? ?????? ???????????? ?????????? ????????????? ??????????? NSG11 (?????, ??????) ? ???????? ??????????? ???????? ????????? ????? 170 ??? ? ?????????? ????????? ?20 ?/?; ????? ????? ?????????? 10-15 ???, ?????? ???????? ???? ??? ????? 10 ??.
???????????? ????????????? ?? ????? ??? ? 3-4 ?????? ?? ?????????? ?????????. ????????
???????????? ?????????? 1,5-2 ??, ?????????? ??????????? ??????????? 256Ч256 ?????. ???
???????, ??????????? ??? ???? ????????? ???????????, ?? ??????????? ?????? ???????????
??????? ???????, ?? ?????????.
?????????? ? ??????????
? ??????????? ?????? ?? ???????? ??????????????? ???????????????? (??), ??????????? ?? ????????? ??????????? ??????????????? ???????? ? ????????, ??????? ???????? ?
???????? ????????? ????? ?????????? ????????? ??.
????????? ?? ????????? ??????????? ? ???????????????? ??????????? ???????????
??????? ??-????????????? (???. 1).
???????? ?????????? ?????? ? ????????? ?? ?????????????? ?????????? ? ??-????????
????????? ????? ???????????????? ???????? ?? ????? ????? ?????????? ? ???????? 418-422,
588-592, 823-843, 1074-1078, 1263-1267 ??-1.
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Natalia Yu. Vasilyeva, Alexander V. Levdansky? Study of Structure of Product?s Obtained by Sulfation of?
???. 1. ??-??????? ????????: ? ? ????????? ??; 1?4 ? ???????????????? ???????? ??
?????? ?????????? ? ??????? 418-422 ??-1 ????????????? ?????????????? ??????????
SO3 ????? ?(SO3), ? ?????? ??? 588-592 ??-1 ????? ???? ???????? ? ?????????????? ?????????? ?(O=S=O). ?????? ?????????? ? ??????? 823-843 ??-1 ??????? C?O?S-????????? ?????????? ?(C?O?S). ?????? ?????????? ? ????????? 1074-1078 ??-1 ?????????? ? ??????? ? ??????? ???????????? ????????? ?????????? ?s(O=S=O). ?????? ??? ??? 1263-1267 ??-1 ????????
???????? ????????????? ????????? ????????? ?as(O=S=O).
??????????? ?????? ? ??????? 1097 ??-1, ??????????? ? ???????????? ????????? ?????????? ??????????? ?????? ?s(COC), ??????????? ? ???????? ??, ?????? ? ???????????????? ???????? ??-?? ???????? ?????????? ????? ?? ????????????? ????????? ? ??????
????????.
????????????????????? ?????? ?? ???????? ???????? ???????? ????????????, ?? ??????? ????? ???????????????? ???????? ???? ?? (???. 2). ???????? ???????? ?? ????? ???????? ? ??????? [22, 23].
???????? ?????????? ????? ? ????????????????? ????????? ?? ???????? ? ?????????
???? ??????????????. ???, ?? ?????????????? ????????????????? ??????? ?? ???????????
??????????? ???? ? ????????? ????? ?? 15 ?? 25° ?, ??? ??????? ? ???, ??? ?????????? ?????????? ??????????? ????????? ?????????.
??????? ????????? ??????????? ??????????? ????????? ???????????? ???????? ?? ?? ?
????? ???????????????. ??? ???????? ?? ???. 3?, ?? ??????? ?? ?????????????? ? ?????????
?????? ????????? ????? ? ???????. ??????????????? ??????? ????? ??????????? ?????
? ????????? ?? 10 ?? 90 ???. ????????? ??????? ??????? ? ??????????, ?????? ??????? ????????? 300 ???.
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Natalia Yu. Vasilyeva, Alexander V. Levdansky? Study of Structure of Product?s Obtained by Sulfation of?
???. 2. ?????????????? ???????? ????????? (1) ? ????????????????? (2) ??
?
?
???. 3. ???-??????????? ???????? ????????? ?? (?) ? ????????????????? ?? (?)
????? ??????????????? ??????? ????? ??????????, ????????? ???????? ?? ?????????
??. ??? ????? ?? ???. 3?, ???????????????? ?? ??????? ?? ??????????? ??????, ??????????
?????????? ?? ???????? ????????? ????? 2-10 ???. ??????? ????????? ?????? ????????? ?
????????? ?? 5 ??? ? ?????.
? ?????????, ??????? ??? ?????????? ?????? ?????????? ?????? ?????? ???????????
????????, ???????? ?????????????, ??????? ??????????????? ?????? ????????????????? ??
????????? ??????????? ???? ??????? ??????? ??? ? ?????????????? ???? ?? ???????, ??????? ????????? ?????????? ?? ?????? ??????????? ??????? ????????, ?? ? ?? ?????? ? ????????? ?? 0,1 ?? [24]. ?????????? ?????? ????????? ?? ???. 4? ? 4?.
??? ????? ?? ???. 4? ? 4?, ??????????? ????????????????? ?? ??????? ?? ??????????
????????????, ??????? ??????????? ????? ? ????????? ???????? 100-200 ??. ???????????
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Natalia Yu. Vasilyeva, Alexander V. Levdansky? Study of Structure of Product?s Obtained by Sulfation of?
?
?
?
?
???. 4. ???-??????????? ?????? ????????????????? ??????? ?? (? ? ??????, ? ? ??????? ????????,
? ? ??????? ??????????? ??????? ????? ????? ?? ??????????? ?, ? ? ?????? ? 3D)
??????????? ?????????? ?? ??????????? ??????? ? ?? ???????? ?????????. ?????? ?????????????????? ????????????? ?? ??????? ??????????? ??????? (???. 4?) ???? ???????? ????????
80 ??.
???? ?? ??????????? ???????? ????????? (???. 4?), ??????????? ?????? ????????????????? ?? ?????????? ????????? ?? ?????? ???????? ??????? ? ?? ???????? ??????????? ????????. ????? ???????, ????? ?????? ? ??????? ???????? ????????, ?????????? ?? ???????????
????????, ?????????????? ? ??????????? ????????.
??????
1. ???????????? ??-??????? ?????????? ????????? ????? ????????????????? ????????????????, ??????????? ?? ????????? ??????????? ????? ??????????????? ??? ??????????????? ???????? ? ????? ????????. ???????? ?????????? ????? ? ????????? ????????????
???????????? ?????????? ? ??-???????? ????? ????? ?????????? ? ???????? 418-422, 588-592,
823-843, 1074-1078, 1263-1267 ??-1.
# 553 #
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Natalia Yu. Vasilyeva, Alexander V. Levdansky? Study of Structure of Product?s Obtained by Sulfation of?
2. ??????? ????????????? ?????????????? ????????, ??? ???????? ??????? ?? ?? ????????? ??????????? ????? ???????? ????????, ? ? ???????? ??????????????? ??????????
?????????? ??????????? ????????? ?????????.
3. ? ??????? ????????? ??????????? ??????????? (???) ? ??????-??????? ??????????? (???) ????????, ??? ???????? ??, ?????????? ? ??????? «??????????????? ??????? ? ???????», ????? ??????????, ???????? ?? ????????? ??. ??????????? ????????????????? ??
??????? ?? ?????????? ????????????, ??????? ??????????? ?????.
?????????????
? ?????? ????????????? ??????? ????????????? ????????????? ?????? ?????????????
??????????? ?? ???.
?????? ????????? ??? ?????????? ????????? ???? ? ?????? ? 12-03-93117.
?????? ??????????
1. ?????????? ?.?., ???????? ?.?. ???????? ????????????? ? ?? ???????????????? ?????????? // ?????????? ???????? ? ?????????????. 2010. ?. 46. ? 3. ?. 291-298.
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???, ?????? ? ?????????, ?????????? ?? ????????? ?????, ????? ? ?????? ??????? // ????????????????? ? ??????????? ????????????. 2010. ?. 73. ? 6. ?. 5-9.
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22. ??????? ?.?., ???????? ?.?. ? ???????? ?????????????? ????????? ??????????? //
?????? ?????????? ?????. 1935. ?. 8. ? 6. ?. 1016-1022.
23. ????? ?.?., ???????????? ?.?., ???????? ?.?. ? ??. ???????????????? ???????????
???????? ?? ?????? ????????????????: ????????? ? ???????? // ?????? ??????????? ?????.
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???????? ?????? ?????????????, 2004. 114 ?.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 556-566
~~~
??? 676.164
Study of Phosphates Sorption on the Porous Supports
from Birch Bark
?vgeniya V. Veprikovaa, Galina P. Skvortsovaa,
Svetlana ?. Kuznetsovaa,b , Nikolai V. Chesnokov a,b
and Boris N. Kuznetsova,b*
a
Institute of Chemistry and Chemical Technology SB RAS
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
b
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041, Russia
Received 13.11.2014, received in revised form 29.11.2014, accepted 06.12.2014
Processes of phosphates Na2HPO4 and KH2PO4 sorption from water solutions by porous supports from
inner birch bark and from birch bark were studied. The influence of salts concentrations in solution,
nature and size of support particles on sorption activity were established. It was shown that sorption
properties of a support from birch bark is higher than that of commercial active carbon from birch
wood. Kinetic features of phosphates sorption by porous supports from inner birch bark and birch
bark were discussed.
Keywords: birch bark, porous support, sorption, desorption, phosphates.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: inm@icct.ru
# 556 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
???????? ??????? ????????
?? ???????? ????????? ?? ???? ??????
?.?. ??????????, ?.?. ??????????, ?.?. ??????????,?,
?.?. ?????????,?, ?.?. ?????????,?
?
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50-24
?
????????? ??????????? ???????????
??????, 660041, ??????????, ??. ?????????, 79
??????? ???????? ??????? ???????? Na2HPO4 ? KH2PO4 ?? ?????? ????????? ?????????
?????????? ?? ???? ? ???? ??????. ??????????? ??????? ???????????? ????? ? ????????,
??????? ? ??????? ?????? ???????? ?? ??????? ???????. ????????, ??? ?? ????? ???????????
?????????? ???????? ???????? ?? ???? ?????? ??????????? ???????????? ???????? ???? ??
????????? ??????. ???????? ? ????????? ?????? ?? ???????? ??????? ???????? ?????????
?????????? ?? ???? ? ???? ??????.
???????? ?????: ???? ??????, ???????? ????????, ???????, ?????????, ???????.
????????
????????? ?????? ??????????? ?????? ???????????? ?? ???????????? ???????????????
??? ???????????? ????????? ??????????, ? ????? ?????????? ????. ??? ????????? ?????????
????????????? ?????????????? ?????? ????, ??????? ? ???????? ????????? ? ?????? ???
?????????.
?????????????? ???????????? ?????????? ???? ?????? ? ?? ???????????? (???? ? ???????) ???????? ??????????? ?????????? ??????????? ? ?????????? ???????????? ????????
??????? (????????, ???????? ? ??? ???????????, ???????????????? ?????????? ? ??.) ? ???????????????, ?????????? ??????? ??????????? ??????????? ? ????????? ??????? ??????
??????? [1?5].
?????????????? ?? ???? ? ???? ?????? ????? ????????? ? ???????? ???????? ????????
??? ????????????? ???????? ??????? ? ??????????, ??? ??????????? ????????? ??????? ??
?????????? [6]. ????????????? ???????? ?? ????? ???????? ????????? ????????? ???????
?????????????? ?????????, ?????????? ???????????????? ?????????????????? ?????????.
? ?????????? ???????? ??????????? ???????? ??????????? ?????????????? ? ??????????????? ??????????? ????????? ? ???????????????? ????????? ?? ?????? ?????????
????????. ????????? ???????? ?????????? ????????????? ?????????, ?????????? ? ???????
??????????? ??????? ???????? ??? ???????? ? ????????? ???????, ???????? ?????? ????????????????? ???????? [7?10]. ??????? ????????, ??? ???????????? ?????? ?????????? ?????
???????????? ?????????? ? ???? ??????????? ????????? ?? ?????? ?????????? ??-?? ??????# 557 #
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????? ????? ????????? ?????? ???????????? ? ????????????? ????? ? ???????????? ????????? ??????, ??? ???????? ? ??????????? ????????? ???. ?????????? ??????????? ?????????
? ???????????????? ????????? ????????? ?????????????? ??? ??????????. ?????? ????????
? ????? ?????? ??????????? ????????? ????? ????????? ? ??????? ?????? ? ?????????? ????,
??? ????????? ?????????? ???????? ?????????? ??????? ??????????? ???????????? ???????
?? ???? ?????????? ?????? [11]. ???? ?????????? ????? ???? ???????? ???????????, ????????,
??????????? ????????????????? ????????? ????????????????? ???????? ?? ?????? ?????
[12].
????????????? ????????? ???????? ???????? ??? ????????????? ??????????? ????????????? ????????? ???????? ????????????, ??? ??? ?????????? ???????????????? ???????? ?
????? ???????????? ????????? ?? ????????? ??????? [13]. ????? ????, ?????????? ??????????
? ??????? ???????????????? ????? ??? ????????? ???????? ????????? ??????? ?????????????
????????????.
????????, ??? ????????????? ????????????????? ???????? ??????????????? ?????????
??????? ?? ??????? ???????? ???????? ? ??????? ????????????? ????????? ????????. ??????? ??? ?????? ????????????? ?????? ??????? ????????? ????? ????????? ????????????? ??????? ??????????? ???????? ???????? ? ????????? ???????????? ????????.
???? ?????? ? ???????? ??????? ???????? Na2HPO4 ? KH2PO4 ?? ?????? ????????? ????????? ?????????? ?? ???? ? ???? ??????.
????????????????? ?????
? ???????? ????????? ????? ??? ???????? ???????? ???????????? ???? ?????? ????????
(Betula pendula Roth.) ? ?????????? ?? ??? ???, ????????????? ? ???????????? ?. ???????????.
????? ?????? ??? ????????? ??????????? ?? ????????-?????? ????????? (?????????? ????????? 7,5 ± 0,5 %), ?????????? ?? ?????????????? ????? «Nossen» (????????). ??? ????????
???????? ??????? ???? ? ???? ?????? ?????????? ???????????? ???????, ???. %: (0,25 ? 0,50)
?? ? 23,7; (0,50 ? 1,00) ?? ? 76,3. ?????????? ??????? ? ??????? ???? ?????? ?????????? 45
???. %.
??? ? ???? ?????? ????????? (???. % ?? ????? ????????? ?????? ???????? ??????????????) 42,5 ? 59,6 ??????? ? 21,6 ? 15,8 ?????????.
???????? ???????? (??) ?? ?????? ???? ? ???? ?????? ???????? ?????????? ?????
1,5%-??? ?????? ????????? NaOH ??? ??????????? (80±5) ??, ??????????? 5, ?????????????
(130±5 ??/???) ? ??????? 1 ? ? ??????????? ???????? ????? ? ?????????????? ?? ????????,
?????????????? ? ?????? [5]. ?????????? ???????? ???????? ?????? ??? (50±5) ??.
???????? ??????? ???? ???????? ? ??????????? ????????? ????????? Na2HPO4 ?
KH2PO4 ? ????????? ????????????? ??????? (? ????????? ?? ?2?5), ??????? ??????????? ??
0,01 ?? 3,0 ?/?. ? ????????? ????????????? ??? ???????? ??????? ???????????? ?????????
???????? ? ???????? ????????????? ?2?5 (2,2±0,05) ?/?.
??????? ????????? ? ??????????? ???????? ??? ???????????? (????????????? 120±10 ?????/???) ??????? ??????? ?? (0,2 ?) ? ?????????? ?????????? (50 ??) ??? ??????????? (20±1)
?
?. ???????? ??????? ??????? ???????, ???????? ????????????????? ???????? ?? 10 ??? ??
72 ?. ?? ???? ????????? ????????????? ????????????????? ??????? ?????????? 24 ?.
# 558 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
????????? ??????? ? ???????? ???????? ????????? ???????????????? ????? (?? 5,4)
??? ???????????? ? ?????????????? (120±10) ?????/???. ??????????? ?? ?? ???? ? ???? ?????? ? ???? ? ???????? ????????? ?????????? 0,25 ? : 25 ??. ????????????????? ?????????
??????????? ?? 1 ?? 72 ?. ??????? ??????????? ??????? ? ????????? ?? 20 ?? 90 ?? ? ????????????????? ???????? ????????? 1 ?.
????????? ???????????? ??????? (? ????????? ?? ?2?5) ? ????????? ????????? ? ???????? ??????? ? ????????? ?????????? ???????????????? ??????????????? ??????? ????????
???? 200851.2 ? 75. ??????????????? ??????? ????? ?????????? ??????? ????-?????????????
?? ??????? ICP-MS 7500 Agilent.
?? ????????? ???????????? ??????? ? ???????? ???????????? ??????????? ??????? (?,
??/?) ???????? ???????? ?? ???? ? ???? ?????? ? ???????? ????????? (D, ??/?). ??? ?????????????? ? ?????? ?????????? ???????? ??????????? ????????? ???? ?????????. ??????
??????????? ?? ????????? 5 %.
?? ????????? ???????? ??????? ????????, ???????????? ? ????????? ????, ?????????
?? ? ? L:
?-1 = (?? ? L)-1 Cp-1 + ??-1
(1)
,
??? ? ? ??????? ???????, ??/?; ?? ? ?????????? ???????, ??/?; Cp ? ??????????? ????????????
??????? (? ????????? ?? ?2?5), ??/?; ? L ? ????????? ????????? ????????.
??????? ?????????? ???????? ???????? (F) ?????????? ?? ????????? ?t ? ?????? ??????? t ? ??????????? ??????????? ??????? ? ? [14]:
F = ?t / ? ?.
(2)
?????????? ????? ??? (WS) ?????????? ?? ??????? ????? ??????? ? ??????????? ???????? ?? ???????? [15]. ???????? ??????????? (S??) ????????????? ??????? ??????????????????
????????? ????? ?? ??????? «????????????».
??????????? ??-???????? ???????? ???????????? ?? ??-????? ???????????? «Tensor
27» (Bruker, ????????) ? ??????? 4000-400 ??-1. ????????? ???????????? ?????????? ????
????????? ? ?????????????? ?????? ???????? OPUS, ?????? 5.5. ??????? ??? ????????? ?????????? ???????? ? ???? ???????? ? ??????? ?????????? ?????. ??????? ????????????? ???????? (???????????? ???????? ? ???????, ????? ????????????? ? ????????? ??????, ????????
???????????, ????? ??????????????) ???? ???????????.
?????????? ? ??????????
????????, ??? ?????? ??????????? ???????? ???????? ???????? ? ???? ?2??4- ? ???42-[16].
??????? ???????? ??????? ??????? ?? ???????? ????????? ?? ???? ? ???? ?????? ?????????
?? ????????? ????????? ???? ???????.
???????????, ??? ???????? ??????? ?2??4- ? ???42- ?????????? ?? ???? ? ???? ??????????? ?????????? ?????????????? ???? (???. 1? ? ?).
?????????? ??????? ?? ???? ?????????? ??????????? ???????????? ??????? ? ????????? ????????? ???? ????? ????????? ??????????? ??????????? ???????? ? ????????? ????????. ? ???? ???????????? ????????? ??????????? ????????? ???????, ????????????? ???????
# 559 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
25
30
2
25
???????, ??/?
???????, ??/?
20
15
10
5
2
20
15
1
10
5
1
0
0
0
500
1000
1500
2000
2500
0
3000
500
??????????? ???????????? ?2?5, ??/?
1000
1500
2000
2500
3000
??????????? ???????????? ? 2? 5, ??/?
?
?
???. 1. ???????? ??????? ?? ???????? ????????? ?? ???? (?) ? ???? ?????? (?) ?? ?????? ?????????
??2??4 (1) ? Na2HPO4 (2)
??????? 1. ????????? ???????? ???????? ??? ??????? ???????? ????????? ?????????? (??) ?? ????
? ???? ??????
????????
?max , ??/?
????????? ????????
??, ??/?
?L
R2
??????? ???4
2-
?? ?? ???? ??????
25,80
62,11
0,456
0,99
?? ?? ????
23,11
45,05
0,586
0,99
??????? ?2??4?? ?? ???? ??????
21,17
41,49
0,889
0,99
?? ?? ????
2,71
2,95
4,644
0,99
??????????. ? max ? ????????????????? ???????????? ???????; R ? ??????????? ?????????????.
2
????????????? ? ??????????? ???????????? ????????? ?????????. ????????, ??? ??????????
???????? ???????????? ???42- ?? 2,6 ?? 2,9 ?/? (? ????????? ?? ?2?5) ?????????? ?????????
????????? ????? ???????? ? ?????????? ? ??????? 24 ? ?????????? ?? 0,025 ?? 0,075 (364 ??,
????? ???? 10 ??). ??? ????????? ???????????? ?? ???????? ??????? ???????? ????????? ??
????????? ????????? ? ???????? ????????????? ?2?5 2,2 ?/?, ??? ???????????? ????????????
??????? ? ???????????? ????????.
?? ???. 1 ?????, ??? ??????? ????????????? ?????? ?2??4- ??????? ?? ??????? ????????.
???, ??????????? ???????? ?? ???? ? ??????? ?2??4- ????????????? ???? ?? ????????? ? ????????? ?? ???? ??????. ?? ??????? ???42- ???????? ?? ???? ? ???? ?????????? ?????????????. ??????? ????????, ??? ??????????? ?????????? ???????? ?? ????????? ???? ? ?????????
?????- ? ????????????? ??????? ????? ??????????????? ???????? ??????????.
??????? ??????? ??????? ???????? ???????????? ??????????, ???????????? ?????????? ???????????? ??????? ?max, ? ??????? ???????? ????????????? ??????????? ??????????
???????? (????. 1).
# 560 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
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3
???????, ??/?
25
2
20
1
15
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5
0
I
I
I
I
1?
2?
3?
4?
//
I
16?
I
I
24?
32?
?????, ?
???. 2. ???????? ??????? ???????? ?? ???????? ????????? ?? ?? ???? ? ???? ??????: 1 ? ???????
??2??4 ?? ?? ?? ???? ??????; 2 ? 3 ? ??????? Na2HPO4 ?? ?? ?? ???? ? ???? ?????? ??????????????
F
1
3
0,8
2
0,6
1
0,4
0,2
0
0
50
100
150
200
250
300
t-1/2
???. 3. ??????????? ??????? ?????????? F ???????? ???????? ?? ?? ???? ? ???? ?????? ?? t1/2: 1 ? ???????
??2??4 ?? ?? ?? ???? ??????; 2 ? 3 ? ??????? Na2HPO4 ?? ?? ?? ???? ? ???? ?????? ??????????????
?????? ?????? ? ?????? ??????? ?2??4- ????????? ?? ???? ????????????????? ????????
?max ?????? ? ?????????? ???????? ?????????? ??????? ??. ?? ????????? ???????? ?????????
?????????? ? L ????? ??????? ?????, ??? ?????????? ?2??4- ????????? ?? ???? ??????????????? ?????????? ???????? ??????? [17]. ? ????????? ??????? ????????? ? ?????????????????
???????? ??????? ?????????? ? 2?2,4 ????. ????????, ??? ??????????? ???????????? ????????
? ????????????????? ????????? ????????.
??????? ??????? ???42- ????????? ???????? ?? ????????? ?? ???? ? ???? ? ???????????
?????????? ??????????? ????? 24 ?. ??? ???? ?????? ?2??4- ??????????? ????????? ?? ????
??? ????????? ? ??? ?????????? ???????????? ????????? ????????? ?? ????? 26 ? (???. 2).
# 561 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
??????? 2. ??????? ??????? ?????? ???????? ?? ?? ???? ? ???? ?????? ?? ??????? ?2??4- ? ???42??????? ?? ?? ? ?????????
???????? ??????, ??/?
???????????
????????
????????
0,25 ? 1,0 ??
< 0,25 ??
?0,25-1,0 /?<0,25
?? ?? ???? ??????
?2??4-
21,17
30,64
0,69
?? ?? ???? ??????
???4
2-
25,80
43,18
0,59
?? ?? ????
???42-
23,11
36,69
0,63
??????????. ?0,25-1,0 , ?<0,25 ? ??????? ?? ????????? ? ??????????????? ???????? ??????.
??????? 3. ??????? ?2??4- ? ???42- ?? ????????? ? ????????? ???????? ?????????? (?????? ??????
???????? ????? 0,25 ??)
????????
?? ?? ????
?? ?? ???? ??????
S?? , ?2/?
Ws , ??3/?
??????? ?2??4- , ??/?
??????? ???42- , ??/?
2,4
0,11
4,62
36,69
3,2
0,10
30,60
43,18
???
524,6
0,31
?? ?????????
4,96
?? ? ?
717,8
0,41
14,98
43,47
??? ??????????? ???????????? ?????? ????????? ??????? ??? ???????? ?????????????????? ????? ?????????? ???????????? ??????? ?????????? ???????? ???????? F ?? t1/2 (???. 3).
???????? ???????? ???????????? ????????? ????????????, ??? ??????? ??????? ?2??4? ???42- ?????????? ?? ???? ? ???? ????????? ?? ??????????????????? ?????????. ???????
???????? ? ?????? ????? ??????? ??????????????? ?? ????????? ???? ?????????? ????????
?? ?????????? ???????? ??????? [14].
????????????????? ??????????, ??????????? ? ????. 2, ?????? ?????????????? ???????
?????????????????? ??????????? ? ???????? ??????? ?2??4- ? ???42-.
?????, ??? ?? ??????????????? ????????? (????? 0,25 ??) ??????? ??????????? ??????????? ????? ?????????? ?? ????? ?????????? ? ????????. ?????????? ?????? ?? ?????????? ??????? ?????? ??????????? ??? ??????? ???42-????????? ?? ???? ? ??????? ????????????? ????? 1,7 ????.
????????? ?0,25-1,0 /?<0,25 ?????????? ??????????? ??????? ?? ??????? ?????? ????????. ???
????? ??? ????????? ? ???????, ??? ?????? ?????????? ???????? ?????????? ??????? ??????? [14]. ????????, ?????? ????? ???????? ?????? ??? ???????? ?????? ?? ??????? ?2??4????????? ?? ???? ?????? (????. 2).
?? ??????? ???????? ????? ??? ? ??-? ??????????? ??????? ???????? ????????? ???????? ?? ??????? ?2??4- ? ???42- (????. 3).
??????? ????????, ??? ???, ???????? ?? ?????? ???????? ???????? ?????????, ?? ?????
??????????? ?????????? ???????? ?? ?????? ???????????? ???? ?? ? ?, ?? ? ???????? ????????? (??) ?? ???? ? ???? ??????. ??-????????, ??? ??????????? ??????????????? ????????
??? ??? ? ??????????? ??????.
# 562 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Absorbance Units
?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
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3
2
1
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3450
2940
2430
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390
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???. 4. ??-??????? ???????? ?? ???? ? ???? ?????? ?? ? ????? ??????? ???42- (?????? ?????? ????????
????? 0,25 ??): 1 ? ?? ?? ????; 2 ? ?? ?? ???? ????? ???????; 3 ? ?? ?? ????; 4 ? ?? ?? ???? ?????
???????
? ???????? ????????? ???????????? ???? ?? ? ? ? ??????? ?? ??? (V????0,08 ??3/?) ???????????? ??????????? ?????? ??????? ? V???? 0,27 ??3/? [18]. ??-????????, ???????? ???????????? ????????? ????? ???? ? ????????????? ??? ??????????? ?????????? ? ????????? ?2??4- ?
???42-.
? ?????? ???????? ???????? ?? ???? ? ???? ?????? ???????? S?? ? Ws ?? ??????????? ??
?????????? ??????? ?????? ???????. ???, ???????? ?? ????, ??????? ?????? ???????? S?? ?
Ws, ?? ??????? ???42- ???????? ? ?? ? ?, ? ?? ??????? ?2??4- ??????????? ??? (????. 3).
????? ????????????, ??? ???????? ????? ? ??????? ???????? ?? ????????? ?? ???? ?
???? ?????? ?????????????? ? ????????? ???????? ?? ?? ???????????. ????????, ??? ?? ??????????? ???? ???????? ? ??????? ??? ???? ?????????? ??????? ????????????? ????????????????, ????? Fe3+ ? Mn2+, ? ????? ?????????????? ??????????, ?????????? ??????? ??????????
???????????. ???????????, ??? ???????? ?? ???? ?????? ???????? ?????? ???????? ???????????????? ? ??????????? ?????? ????? Fe3+, ??? ???????? ?? ????. ????????, ??? ?????????????
??????? ??????????? ?????????? ???????? ?? ???? ? ????????? ??????? ????????.
??? ???????? ????????????? ?????? ??-???????? ???????? ?? ???? ? ???? ?????? ?? ?
????? ??????? ???42- (???. 4). ? ??-???????? ???????? ????? ??????? ???????? ?????????????? ?????????? ????????????? ?????????? ? ??????? 1100?1000 ? 1000?800 ??-1 ?? ????
????????? ?????? ?-?? [21].
??? ???? ? ???????? ???????? ?? ?????????? ?????? ?????????????????? ????? ??????????, ???????????? ??????? ?????? ???????. ????????, ? ???????? ??????? ?? ??????????
?????????????? ?????? ???42- ? ?????????????? ???????? ????????, ??????? ???????? ????????????? ? ??????? 4000-400 ??-1.
?? ??????? ???????? ?? ???? ? ???? ?????? (?????? ?????? ????? 0,25 ??), ?? ??????????? ??????? ???? ?????????????? ??????????? ???????? 36,69 ? 43,18 ?? ??????? (? ????
# 563 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
??????? 4. ????????? ???????? ? ???????? ???????? (??) ?? ???? ? ???? ?????? ??? ?????????
????????????????? ????????
????????
?????????, ???????, ??/?
?????? ?????? ????????,
??
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72, ?
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0,04
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?? ?? ????
?????????, ??/?
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2
30
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20
10
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20
40
60
80
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???????????, ?
???. 5. ??????????? ????????? ???????? ? ??????????? ???????? ?? ???? (1) ? ???? ?????? (2) ??
??????????? (?????? ?????? ???????? ????? 0,25 ??, ????? 1 ?)
???42-), ???? ??????? ????????? ????????. ???????????, ??? ?? ?????????? ??????????? ??????? ??? ??????????? (20 ± 1) ?? ??????? ????? ????????????? ????? ?????????? ?? ???????
?????? ???????? (????. 4).
????????? ??????????? ????????? ??????????? ????????? ????????? ???????? ? ??????????? ???????? ??? ? ??????? ????????? ??????? (???. 5).
????????, ??? ??????????? 60 ?? ? ???????? ?? ???? ? ???? ? ??????? ????????? 22,2 ?
24,1 % ????????????? ????????. ??? 90 ?? ????????? ? ???????? ????????????? ?? 96 %. ??
????????? ????????????????? ?????? ???? ?????????? ???????? ??????? ????????? ?? ?????????, ??????? ????? 103 ? 99 ???/???? ??? ???????? ?? ???? ? ???? ?????? ??????????????. ????? ???????? ?? ????? ??????? ?????????????? ???????? ?????????????? ???????? ?
????????? ???????? ????????.
??????????
? ?????????? ???????????? ???????? ???????? ??????? Na2HPO4 ? KH2PO4 ?????????
?????????? ?? ???? ? ???? ??????. ???? ???????????, ??? ??? ???????? ???????? ?????????
??????? ??????????? ?????????? ? ????????? Na2HPO4. ??????? ?? ???????? KH2PO4 ?????# 564 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
????? ?????? ?? ???????? ?? ???? ??????. ????????, ??? ?????????? ??????? ?????? ????????
? 0,5?1,0 ?? ?? < 0,25 ?? ???????? ? ?????????? ?? ??????????? ??????? ? 1,4?1,7 ????.
???????????, ??? ?? ????? ??????????? ?????????? ???????? ???????? ?? ???? ??????
??????????? ???????????? ???????? ???? ????? ??? ? ?? - ?.
???????? ????????????? ??????????? ????????? ???????? ? ???????? ?? ???? ? ???? ??????. ???????????? ???????? ??????? ????????? ???????? ????????? ????? 103 ? 99 ???/????
??? ???????? ?? ???? ? ???? ?????? ??????????????.
?????? ??????????
1. ???????? ?.?. ????????????? ???????? ???????: ?????????, ??????, ????????, ?????????? // ????? ?????????. 1994. ? 3. ?. 3-28.
2. ?????????? ?.?., ???????? ?.?., ????????? ?.?., ????????? ?.?., ?????????? ?.?.
??????? ????????? ???? ?????? ?????????? ????? ?? ????? ? ?????? ??????????, ??????????
??????? ? ????????? ???????? // ????? ????????????? ?????. 2005. ? 2. ?. 15 ? 20.
3. ???????? ?.?., ???????? ?.?., ????????? ?.?. ???????? ???????? ????????? ??????????? ??????? ?? ??????? ????????? ???? // ????? ????????????? ?????. 2008. ? 1. ?. 41 ? 44.
4. ????????? ?.?., ?????????? ?.?., ???????? ?.?., ????? ?.?., ???????? ?.?., ????????? ?.?. ????????? ????????? ???????, ?????????? ? ??????????????? ?? ???? ?????????
???? // ????? ? ????????? ??????????? ????????. 2005. ? 13. ? 3. ?. 401 - 409.
5. ????????? ?.?., ????????? ?.?., ???????? ?.?., ???????? ?.?. ???????? ???????????????, ?????????? ?? ??????????????????? ???? ?????? // ????? ? ????????? ??????????? ????????. 2012. ?. 20. ? 6. ? 673 ? 678.
6. ????????? ?.?., ????? ?.?., ????????? ?.?., ???????? ?.?. ???????? ??????? ??????? ???????? ??????? ? ???????? ?? ???????? ???????? ?? ???? ?????? // ??????? ? ??????????????. 2011. ? 2. ?. 72 ? 76.
7. ??????????? ?.?., ??????? ?.?., ???????? ?.?., ??????? ?.?., ????????? ?.?.
??????-?????????? ?????? ????????? ???????????????? ?????????????? // ????? ? ????????? ??????????? ????????. 1999. ?. 7. ?. 675 ? 679.
8. ??????????? ?.?., ??????? ?.?., ????????? ?.?. ? ??. ????????? ???????????????? ?????????????? ?? ??????????? ?????????? // ????? ? ????????? ??????????? ????????.
2005. ? 1. ?. 65 ? 69.
9. ???????? ?.?., ?????????? ?.?., ??????????? ?.?. ????????? ???????????? ?????? ?????????? ??????? ????????????????? ???????????? ??????? ? ?????????????? ??????? ???? // ??????????? ? ?????????????????? ????????. 2008. ?. 8. ???. 5. ?. 875 ? 880.
10. ?????? ? 2222514 ??. ??????-?????????? ????????? ????????????????? ????????
/ ?????????? ?.?., ????????? ?.?., ??????????? ?.?., ????????? ?.?., ????????? ?.?., ??????? ?.?. - ?????. 04.04.2002; ?????. 27.01.2004.
11. ????? ?.?., ????????? ?.?., ??????? ?.?. ??????? ??????????????? ? ????????????? ?????? ???? // ?????????. 1999. ? 9. ?. 79?90.
12. ????????? ?.?., ?????????? ?.?., ???????? ?.?. ??????????? ?????????????????
????????? ????????????????? ???????? ?? ?????? ????? // ????? ????????????? ?????. 1999.
? 4. ?. 53 ? 59.
# 565 #
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?vgeniya V. Veprikova, Galina P. Skvortsova? Study of Phosphates Sorption on the Porous Supports from Birch Bark
13. ????????? ?.?., ????????? ?.?., ????????? ?.?. ????????????? ??????? ???????????
?????????? ????????????????? ????? // ????? ????????????? ?????. 2010. ? 2. ?. 5 ? 16.
14. ??????????? ?.?., ???????? ?.?., ???????? ?.?., ??????????? ?.?., ???? ?.?. ????????????? ?????????? ??????? ??????? ???. ????: ????. ?????, 1981. 175 ?.
15. ??????? ?.?. ?????? ????????????? ???????. ?.: ?????, 1976. 512 ?.
16. ????????? ?.?. ????????? ? ??????????? ?????. ??????-??-????: ??????, 2000. 317 ?.
17. ???? ?., ???? ?. ?????????, ???????? ???????????, ??????????. ?.: ???, 1970. 306 ?.
18. ????? ?.?., ??????? ?.?., ?????? ?.?. ???????? ???? ??????. ?.: ???????????,
2000. 352 ?.
19. Infrared and Raman characteristic group frequencies: Tables and charts. G.Socrates. John
Wiley- Sons, 2004. 347 p.
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Journal of Siberian Federal University. Chemistry 4 (2014 7) 567-572
~~~
??? 547.725+547.724+544.472.2
Preparative 5-Hydroxymethylfurfural Oxydation
by Concentrated Nitric Acid
Andrey A. Morozov, Mikhail Y. Chernyak,
Valery E. Tarabanko and Alexand?r A. Kondrasenko*
Institute of Chemistry and Chemical Technology SB RAS
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
Received 22.10.2014, received in revised form 16.11.2014, accepted 30.11.2014
The 5-hydroxymethylfurfural oxydation process by concentrated nitric acid has been studied.
Temperature was ranging from -16 to +60 0C. 5-Hydroxymethylfurfural was converted to the oxidized
derivatives, 2,5-furandicarboxylic acid, 5-formyl-2-furancarboxylic acid, and 2,5-diformylfuran. 60%
total yield of oxidized derivatives was attained under optimized reaction conditions.
Keywords:
2,5-furandicarboxylic
5-hydroxymethylfurfural.
acid,
2,5-diformylfuran,
oxydation,
nitric
acid,
????????????? ?????????
5-?????????????????????? ??????? ????????
?.?. ???????, ?.?. ??????,
?.?. ??????????, ?.?. ???????????
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50-24
?????? ??????? ????????? 5-?????????????????????? ????????????????? ??????? ????????
? ????????? ?????????? ?? ????? 16 ?? 60 ??. ??????? 60%-??? ????????? ????? ?????????
?????? ? ??????????.
???????? ?????: 2,5-????????????????? ???????, 2,5-?????????????, ?????????, ???????
???????, 5-?????????????????????.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: veta@icct.ru
# 567 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey A. Morozov, Mikhail Y. Chernyak ? Preparative 5-Hydroxymethylfurfural Oxydation?
????????
????????????? ??????????????? ????????????? ????? ? ?????????? ?????????????? ?
??? ?? ?????? ??????????? ???????? ?????????? ??????????, ?? ? ??????????? ?? ?????????.
????????? ?????????? ? ???????????? ???????? ? ????????, ???????? ?? ?????????, ???????? ????????? ???????????? ????????? ?????????, ????????????. 5-????????????????????? (5-???), ?????????? ????????-?????????????? ????????????? ????????? ?????????, ???????? ???????? ?????????????? ????????????? ????????? ??????? ???????????????????
????????????, ????????????? ????? ? ?????????? ??????. ?????? ???????????? 5-??? ???????? ?????????? ?????????????? ??? ?????????? ??????? [1]. ???????? ????????? 5-???:
2,5-????????????? (???), 5-?????????????-2-??????????????? ??????? (????), 5-??????2-??????????????? ??????? (????), 2,5-????????????????? ??????? (????) ????? ?????????? ??????????, ??? 5-???, ??? ???????????? ? ???????? ????? ? ???????????? ?????????,
????? ?????????? ? ???????????????? ?????????? [1].
OHC
O
CHO
???
OHC
O
CH2 OH
HOOC
O
????
5-???
HOOC
O
CHO
HOOC
O
COOH
????
CH2 OH
?????
???? ?? ????? ?????????? ????????? ????????? 5-??? ? 2,5-????????????????? ??????? ????? ??????? ??? ????????? ??????? ????????????????????? ? ?????????????????,
???????? ????? ??????????????? ??????????????? ???????? [2, 3]. ?? ????? ????????? 2,5-?????????????, ??????? ???????? ???? ?????????? ??? ??????? ????????? ? ???????????
??????????? ???????? ?-?????? [3, 4]. ????? ???????? ????? ????? ?????????? ? ????????
???????????? ??????????? ? ??????????????? ? ? ?????? ??????????? ???????? [4]. 2,5-????????????? ????? ???????????? ????? ??? ??????? ??????????? ????????? ?????, ???????? ?????-??????, ??????????? ?????????? ? ??. [5-7].
???? ?? ?????? ??????? ????????? ??? ?????????? ????? ????????? 5-?????????????????? 60%-??? ??????? ???????? [8]. ??????? ????????? ??? ?????????? ?????????? ?? ?????? ??????? ????????? ??????? ????? (40-60 0?) ? ?????????? ??????? ???????????. ???
????????? ???????????? ??????????????? ?????? ??????????? ????? ???????????? ?????????? ?????. ??? ?????????????? ??????. ???????? ?????? ??? ?????? ?? ????????? ???,
????? ???????? ?? ????????? 25?30 % [8].
?????????? ? ???????? ?????????? ???????????? ????? ? ???????? ????? ????????? ???????? 2,5-????????????????? ??????? ?? 5-??? ? ??????? 50?75 % [9, 10]. ?????????? ?????
??????? ???? ???????? ??????? 2-??????-5-??????????????? ???????, ?????????? ???????
???????? ????? ???????????? ???????????.
?????? ?????????? ??????????? ?????? ???????????-??????????????? ????????? 5-???
[11]. ? ?????? [12] ???????? ??????????? ????????? 5-??? ? 2,5-????????????????? ???????
# 568 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey A. Morozov, Mikhail Y. Chernyak ? Preparative 5-Hydroxymethylfurfural Oxydation?
?????????? ? ?????-???????? ????? ?? ???????- ? ???????????????? ????????????? ? ?????????????? ?? 80 ? ???? 99 % ??? ????????? 5-??? 100 %. ?????? ???? 71 ? 79 % ?????????? ?? ????????????? Au/CeO2 ? Au/TiO2 [13-15].
????????? 5-??? ? ??? ???????? ?? ????? ???????? ????????????? (?? ????????? ?
?????????????? ????????? ????) ?? ?????? ??, Ce, Ru ? Pd [16-17]. ???????? ???????? ? ???????????? ?????????????, ???????? ? ???????????????????, ??? ???????????? ?? 120 ??.
???????????? ?????? ??? ????????? 80?92 %. ?????????? 5-??? ? ???????? ??????? ?
??????????? ???????? ???????? ? ???????? ???????? ?? 82?87 % ??? [18].
???????????? ???????????? ?? ?????? ????? ???????? ??????? ???? (II) ? ??????? ????????? ???????? 5-??? ?????????? ?????? ?? ??????????? ?????? ? ???????
5-??????????????????-2-?????????? ??????? ?? 80?90 % [19].
???????? ??????? ????????? ???????? ? ??????? ? ??? ? ?????????????? ???????????????? ?????????????, ??????, ???? ????????????? (??????????????? ????? ? ??????????
?????????? ???????????). ?????? 2,5-??? ???????????? ???????? ? 40?45 % ?? ???????? ?
20?30 % ?? ???????, ??? ??????????? ? ?????? ??????? 5-??? ??? ????????? ????????????
????????? [20].
??? ??????? ??? ?????????? 5-??? ????? ???????????? ????????????????? ??????????, ????? ??? NaOCl, Ba(MnO4)2, CrO3 ? ????????, ?????? ?????????? ???? ??????????? ????????? ? ??????????? ???????????????????? ???????. ???????? ?????????? ???? ???????????
??????? ? ?????? [21].
? ???????????? ????????? ?????????????? ????????? ????? ????????? ????????????
??? ????? ???????? ? ?????????????? ?????????????????? ????????????. ?? ?????? ?????????????? ??????? ????????? ????????? 5-??? ? ??????????? ????????????? ?????????????
???????????? ? ????????????? ?????????????, ? ?????? ??????? ?? ?? ??????? ? ????????????,
??????? ? ????????? ??????? ??????????? ??????????? ??????? ??????? ??? ???????? ?????????? ??????????. ??????? ??????? ???????????? ??? ????????? ???????? ??????? ?????????????
??????? ? ??????????, ?????????? ? ?????? ??????? [22]. ???????? ? ??????????? ?????????
5-?????????????????????? ??????? ???????? ? ??????????, ??????, ?? ???????.
???? ????????? ?????? ??????????? ? ?????????? ?????????????? ?????? ?????????
5-?????????????????????? ??????? ????????.
????????????????? ?????
5-????????????????????? ????????????? ?????????? ???????? ? ???????? ??????????
?????? [23].
? ?????????? ??????????? ????? ???????? 0,4 ???? 5-??? (50 ?) ? ????????? 100 ??
????????????????? (?=1,3 ?/??) ??????? ???????. ??????? ????????????, ?? ??????? ?????????? ?????????? ???????, ????? ???? (10-15 ???) ??????????? ????? ??????????????? ????????????? ?? 50?60 0?. ????? ?????? ??????? ????????? ????????? ????? ??????????? ?????
?????? ????????? ?? ????. ????? ??????????? ????? ????????????? ?? ?? 3?4 ? ????????????? ?? ?????????? ????????? ?????????. ??? ????????? ??? ??????????? ????? ????????????? ?? ?? 7 ? ?????????????? ??????? ?????????? ??????. ???????????? ?? ?????????
??????????? ? ??? ????????????? ????????????: 4 (1 ?) ? ?15 ?? (24 ?).
# 569 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey A. Morozov, Mikhail Y. Chernyak ? Preparative 5-Hydroxymethylfurfural Oxydation?
???????? ????????? ????????????? ??????? ??? 1?. ??????? ??? ???????? ?? ???????????? BrukerAvanceIII 600 MHz, (??? ??? ?? ???) ? ??????????? ????????????? ? ????????? ? ??????? ????????? ?????? ???????? ??????? (?????????? ????????).
?????????? ? ??????????
?????????? ???????? ????????? 5-?????????????????? ? ???, ????????? ? [8], ???
????????? 5-??? (?????????? ?????????? ? ????????????????? ??????? ???????? ?? ??????????? ??????? ????????? ????????? ?????, ????????????????? ????????? 40 ???) ????
????? ????????? ?????????, ? ??????? ??? ????? ???? 5 % ?? ????? ????? ?????????, ???
??????????? ???? ?? ????????? ? ?????????? 5-?????????????????? [8]. ???????? ????????
???????????? ??????? ???????????? ????????????????? ? ????????????????????? ??????,
? ?????????? ??????? ? [8] ?? ???????????.
?????? ???1? ??????????? ????? ????????? ?? ???. 1.
? [8] ????????? ???? ???????????? ????? ???????????? ????????? ??????????? ???
??????????????? ??????????? ??????? ? ??????? 80-90 %. ????? ???????, ????????? ?????
????????? ????????? ????????? 5-?????????????????? ?? ???????? 30 %.
????????????? ?? 5-??? ?????? 5-?????????????????? ? ??????????? ???????? ????
????? ??????? ????? ????????? ????????? ?? ???? ?????????? ????????? ?????? ? ???????? ????????? 5-??? ? ???: 0,08 ???? ??? (20 ???.%), 0,15 ???? (40 ???.%) ????? ???? ?
????.
???. 1. ??? 1? ??????????? ????? ????? ????????? 5-??? ? ?????? ????????????????? ????????? ??
35 ?? 60 °? (d6-????). ???: ? 7.67 (s, 2H); 9.82 (s, 2H), ????: 7.32 (s, 2H), ????: ? 7.40 (d, 1H); 7.59 (d,
1H), ? 9.73 (s, 1H)
# 570 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Andrey A. Morozov, Mikhail Y. Chernyak ? Preparative 5-Hydroxymethylfurfural Oxydation?
???????? ?????????? ????????? ? ???? ????? ???????? 2,5-?????????????. ??????????? ??????? ???????? (?????????? ?????????? ??????????? ????? ? ??????? ????????) ?????
????????? ??? ????????? 2,5-????????????????? ??????? ??????????????? ?????????? ?????????? 2,5-?????????????? ? ????????????? ?????????? ?? ??????? ????????????????????? ???????. ????????? ???????????? ?????? 2,5-????????????????? ??????? ????????
??????????? ?????????? ????? ????????? ???????????? ????? ? ???????? ?????, ?????? ? ?
???? ?????? ????? ??????????? ????????? (?? 40 ???.%).
??????? ?????????? ???????? ????????? ??? ??????????? 4 0? ?? ??????? ? ?????????
???????????. ????? ????????? ?????????? ? ??????????? ???????? ??? ??????????, ?? ????????????? ????????????????? ???????? (24 ?). ??? ????? 16 0? ??????? ????????? 5-??? ??
????.
????? ???????, ????????? 5-?????????????????????? ??????? ??????? ???? ? ??? ????
?????? ????????? ?????? ? ?????????? ?? ????????? ? ????????? ????????? 5-??????????????????.
?????? ??????????
1. Michael A. Lilga, Richard T. Hallen, Michel Gray. Production of Oxidized Derivatives of
5-Hydroxymethylfurfural (HMF) // Top Catal. 2010. No 53. ?. 1264?1269; DOI 10.1007/s11244-0109579-4.
2. Rodrigo Lopes de Souza, Hao Yu, Franck Rataboul and Nadine Essayem. 5-Hydroxymethylfurfural
(5-HMF) Production from Hexoses: Limits of Heterogeneous Catalysis in Hydrothermal Conditions
and Potential of Concentrated Aqueous Organic Acids as Reactive Solvent System // Challenges. 2012.
No 3. P. 212-232; DOI:10.3390/challe3020212.
3. Mike Lilga. Perspectives on Biobased Products & Production of Oxidized and Reduced
Derivatives of 5-Hydroxymethylfurfural (HMF). Northwest Bioenergy Research Symposium Seattle.
WA. November 13. 2012.
4. Onofre Casanova Navarro, Avelino Corma Canoґs, Sara Iborra Chornet. Chemicals from
Biomass: Aerobic Oxidation of 5-Hydroxymethyl-2-Furaldehyde into Diformylfurane Catalyzed by
Immobilized Vanadyl-Pyridine Complexes on Polymeric and Organofunctionalized Mesoporous
Supports // Top Catal. 2009. No 52. P. 304?314. DOI 10.1007/s11244-008-9153-5.
5. Feringa Ben L., Hulst, Ron, Rikers, Ruud, Brandsma, Lambert. Dimetalation of Furans and
Thiophenes. One-Pot Procedures for Furan-2,5- and Thiophene-2,5-dicarboxaldehyde // Synthesis.
1988. No4. P. 316-318.
6. Tengfei Xiang. Synthesis and characterization of polymeric schiff bases from 2,5-diformylfuran.
2012. Master of Science, University of Akron, Chemistr. http://rave.ohiolink.edu/etdc/view?acc_
num=akron1353710697.
7. Gandini, A., Belgacem, M. N. Furans in polymer chemistry. Prog. Polym. Sci. 1997. 22. P. 12031379.
8. William Francis Cooper, B.A. and Walter Harold Nuttall, F.I.C.CXII. ? Furan-2:5-dialdehyde //
J. Chem. Soc., Trans.1912. No 101. P. 1074-1081. DOI: 10.1039/CT9120101074.
9. George Gonis , E.D. Amstutz. The Preparation of Furan-2,5-dicarboxylic Acid // J. Org.
Chem.1962. 27 (8). P. 2946?2947. DOI: 10.1021/jo01055a524.
# 571 #
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Andrey A. Morozov, Mikhail Y. Chernyak ? Preparative 5-Hydroxymethylfurfural Oxydation?
10. United States Patent 7411078. Method for producing furan-2,5-dicarboxylic acid.
11. Michиle Besson, Pierre Gallezot, and Catherine Pinel. Conversion of Biomass into Chemicals
over Metal Catalysts // Chem. Rev. dx.doi.org/10.1021/cr4002269.
12. Hicham Ait Rass, Nadine Essayema and Michиle Besson. Selective aqueous phase oxidation
of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acidover Pt/Ccatalysts: influence of the base and
effect of bismuth promotion // Green Chem. 2013. 15. P. 2240-2251. DOI: 10.1039/C3GC40727F.
13. Basudeb Saha, Saikat Dutta and Mahdi M. Abu-Omar. Aerobic oxidation of
5-hydroxylmethylfurfural with homogeneous and nanoparticulate catalysts // Catal. Sci. Technol.
2012. 2. P. 79-81.
14. Onofre Casanova, Sara Iborra, and Avelino Corma, Biomass into Chemicals: Aerobic
Oxidation of 5-Hydroxymethyl-2-furfural into 2,5-Furandicarboxylic Acid with Gold Nanoparticle
Catalysts // ChemSusChem. 2009. 2. P. 1138 ? 1144.
15. Thomas Pasini, Marco Piccinini, Magda Blosi, Rosa Bonelli, Stefania Albonetti, Nikolaos
Dimitratos, Jose A. Lopez-Sanchez, Meenakshisundaram Sankar, Qian He, Christopher J. Kiely,
Graham J. Hutchings and Fabrizio Cavani. Selective oxidation of 5-hydroxymethyl-2-furfural using
supported gold?copper nanoparticles // Green Chem. 2011. 13. P. 2091.
16. Yimei Wang, Bing Liu, Kecheng Huang, Zehui Zhang. Aerobic Oxidation of Biomass-Derived
5-(Hydroxymethyl)furfural into 2,5-Diformylfuran Catalyzed by the Trimetallic Mixed Oxide
(Co?Ce?Ru) // Ind. Eng. Chem. Res.dx.doi.org/10.1021/ie4034363.
17. Atsushi Takagaki, Miho Takahashi, Shun Nishimura, and Kohki Ebitani. One-Pot Synthesis
of 2,5-Diformylfuran from Carbohydrate Derivatives by Sulfonated Resin and Hydrotalcite-Supported
Ruthenium Catalysts // ACS Catal. 2011. 1. P. 1562?1565.
18. United States Patent2012/0059178 A1. Oxidation of furfural compounds. 2012.
19. United States Patent3326944. Method of producing dehydromucicacid. 1967.
20. Gary A. Halliday, Robert J. Young, Jr., and Vladimir V. Grushin. One-Pot, Two-Step, Practical
Catalytic Synthesis of 2,5-Diformylfuran from Fructose // Organic Letters. 2003. Vol. 5. No. 11.
P. 2003 ? 2005. DOI:10.1021/ol034572a.
21. Lewkowski J. Synthesis, chemistry and applications of 5-hydroxymethylfurfural and its
derivatives // Arkivoc. 2001. Vol. 25. No 1. P. 17-54.
22. N. V. Svetlakov, V. G. Nikitin, and E. A. Nikolaeva. Oxidation with Nitric Acid of Aliphatic
Alcohols and Diols to Carboxylic Acids // Russian Journal of Organic Chemistry. 2007. Vol. 43. No. 5.
P. 773?774. DOI: 10.1134/S1070428007050235.
23. ?????????? ?.?., ?????? ?.?., ???????? ?.?., ??????? ?.?. ??????????????????
?????? 5-?????????????????????? // ????? ????????????? ?????. 2011. ? 1. C. 87-92.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 573-581
~~~
??? 539.26:519.65:519.68
Multipopulation Genetic Algorithm for Simulation
of the Crystal Structure from X-Ray Diffraction Data
Alexander N. Zaloga*, Sergey V. Burakov,
Eugeniy S. Semenkin and Igor S. Yakimov
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
Received 12.10.2014, received in revised form 18.11.2014, accepted 06.12.2014
A multipopulation genetic algorithm for a crystal structure solution from the X-ray powder diffraction
data is proposed. Individual genetic algorithms are executed on different units of the computing
cluster. The local optimization is performed periodically by the full-profile structure analysis (Rietveld
method). The best trial structures are accumulated on the control unit for migration back to the routine
compute units. The work of multi-population algorithm is discussed on 3 example of test structures with
9-10 independent atoms. The reliability of the structure search increases in a half order of magnitude
more due to migration.
Keywords: X-ray powder diffraction, crystal structure analysis, Rietveld method, genetics algorithm.
??????????????????? ???????????? ????????
????????????? ??????????????? ?????????
?? ????????????????????? ??????
?.?. ??????, C.?. ???????,
?.?. ????????, ?.?. ??????
????????? ??????????? ???????????
??????, 660041, ??????????, ??. ?????????, 79
????????? ??????????????????? ???????????? ???????????? ???????? ??? ?????????????
??????? ??????????????? ????????? ?????????? ?????????? ?? ?????? ?????????????
?????????? ?????????. ?????????????? ???????????? ????????? ??????????? ?? ??????
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: zaloga@yandex.ru
# 573 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander N. Zaloga, Sergey V. Burakov? Multipopulation Genetic Algorithm for Simulation of the Crystal Structure?
????? ??????????????? ????????. ?????? ??????????? ?????? ?? ???? ????? ????????????
????????? ??????????? ?? ?????? ???????????????? ???????????? ??????? ? ?????????????
?? ??????????? ????. ?? ????????? ?? ?????????? ????????? ??????? ? ????????? ??
?????????????? ?????. ?????? ???????????????????? ????????? ??????????? ?? ????????
?????????? ? 9-10 ???????????? ???????.
???????? ?????: ??????????????? ?????????, ????????????? ?????????? ?????????,
???????????? ???????????? ?????????, ??????????????? ??????????? ??????, ?????
?????????.
????????
?????????? ?? ??????? ??????????????? ????????? ?????????? ?????????? ????????
?????????? ?????? ? ???????????? ??????????????? ?????? ? ????????? ?? ???????? ????????? ? ????????????? ? ??????????? ????? ?????? [1, 2]. ???????? ??????? ??? ????????
????????? ????? ???????, ?????????? ? ??????????????????? ?????, ?????? ?????????????
?????????? ????????? [3]. ? ??????????? ???????????? ?????? ??????????? ????????????
?????? ??????? ??????????????? ????????? ? ?? ???????????. ???????? ?????? ??? ??????????? ?????? ????????? ? ?????????? ???????, ????????? ???? a, b, c ???????????????
??????, ???????????????? ?????? ????????? ? ??????????????? ?????????? ?????????????? ????????, ??????? ????? ???? ?????????? ?? ??????? ??????????????? ????????? [3].
??????????? ?????? ??????????????? ????????? ?????????????? ? ??????? ?????? ???????????????? ??????? ????????????? ????????? [4]. ???????? ????????? ?????? ???????
??????????? R-??????? ? ??????? ????? ????????? ? ????????????????? ????????????????,
?????????? ? ????????????? ?????????. ???????? ????????? ?????????????? ????????????
??????? ???????? ????? ?????? ??????????????? ?????????.
? ?????? ???????? ??????????? ???????????? ??? ???? ???? ?????????? ?????????????
????? ?????? ?????? ??????????? ??????? ? ?????? ???????????? [5, 6], ??????????, ???????
?????? ?????????, ?? ???????????????? ????????????? ????????????????? ??????????????. ????????? ????????? ???????? ?????? ???????? ?????? [7] ? ???????????? ???????????? ?????????? [8]. ????????? ????????? ????????????? ????????, ?.?. ????????????
????????? ?????????????? ?????????? ??????????? ????? ?????? ????????? (?????????)
??????????? ??????? ????? ???????????, ??????? ? ???????? ??????? ? ????? ?????????
????????? ?? ???????? ???????? R-???????. ???????????? ???? ??????? ? ??????? ???????
????????????? ? ????????????? ????????, ??? ????????? ????????? ??????????? ?????? ??????????????? ? ??? ?????????? ??? ?????????????????? ????????????, ??? ???? ????????????? ????????. ???????? ??????????? ???????? ?????? ??????????????? ????????? ????????
?????? ? ????????? ????????? R-??????? ? ?? ?????????? ????? ?? ??????????? ??????? ?
???????? ????????? ????????.
? [9] ???? ????????? ???????????? ????????? ????????????? ???????????? ????????
(??) ??? ??????????? ??????????????? ???????? ? ?????? ????????????. ? ?????? ?????? ?????????? ? ?????????? ?? ???? ?? ?????????????????? ???????????????????? ?????????????
# 574 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander N. Zaloga, Sergey V. Burakov? Multipopulation Genetic Algorithm for Simulation of the Crystal Structure?
????????????? ????????? (????), ???????????????? ??? ?????? ?? ???????????? ?? ? ?????????????? ???????? ???, ? ??????????? ?????????? ???????????? ?? ??????????????
????????? ? ????????? ?????????? ?? ???? ?????? ???????????? ???????? ????? ???????
???????????.
????? ???? ? ????????????????? ?????? ??? ?????????????
????? ???? ?????????? ?? ???. 1. ?????????????? ?? ??????????? ? ???? ?????? [10]
??????????? ???????????? ?????????????? ? ???????????? ?????????? ??????????, ?????
??? ????? ? ?????? ????????????? ????? ? ?.?., ??????? ????? ???????????. ????? ????
????????? ????????? ????????? n ????????? ????????? ??????????? ??????? ???????? ?
?? ?????? ?? n ?????????????? ???? ?? ??? ???????? ????????? ?????????????? ????????????????? ??. ??? ???????? ????????? ?????????? ?? ???? ????? ???? ????????, ??? ????????? ??????????? ??????? ????????????? ???????????? ????????? ????????? ?????? ? ???????? ??????? ? ????????? ? ?????????? R-??????? ? ???????? ?????? ???????? ?????????
??????????. ??????? ?????? ? ?????? R-??????? ??????????? ?????? ? ??????? ????????????? ????? ?? ?????????? ? ??????? ?????? ???????????????? ??????? ? ??????????? ? ????????? ??????? ?????????? ?????????. ????????? ????????, ??? ??? ????????? ? ????????????? ???????????????? ???????? ????? ???????? ?????? ????????????????? ????, ??
????????????? ????? 2-? ??????? ??, ?????????????? ????? ?????? ?????????? ??????????? ?????????? ??? ???????????????? ???????. ?????? ???? ??????? ????? ??????????? ???
??, ?? ????? ??????? ???????? ?? ????????? ?????????? ???????????????????? ????????
?????????? ??????? [11], ???????????? ????? ??? ???????????????? ????????? ???????????
?????? ????? ?? ???? ??????????. ??? ????????? ???????? ?????????? ??????????????????
?? ?? ???????.
???????? ????????? ???? ???????? ????????? ???????? ??????????? ??????? ?????
???????????, ????????????????? ?? ?????? ?????????????? ?????. ??? ???? ???? ???????????? ?????????? ??????????? ??????? ? ???????????? ?????? R-????????, ?????????? ??
?????? ???? ????? ?????????? ?????? ????????, ?????????? ? ????????????? ?? ??????????? ???? (??). ???????????? ?? ?????????? ???????? ?????????? ? ???????????? ???????????
? ?? ??????? ? ????????? ?? ?????????????? ????? ??? ?? ?? ????, ??? ??????????? ????
???????? R-???????.
??? ?????????? ????? ?? ??????????? ??????? ?? ?? ???????? ???????? R-???????
(????????????? ? ?????????? ???????????? ??????????????) ???? ????????? ??????, ? ?????? ???????????? ??????????????? ???????????????? ????????? ?? ???? ?????????? ?
??????????? ??????????. ????? ????? ????????????? ????? ???????? ???????????????????
??????????? ????????? ?????????, ?????????? ?????? ???????????? ?????????? ??????????, ????????? ????? ? ?.?.
??????? ???????????????? ?????? ??????????????? ?????? ???????????? ??????? ???????? ???????? ? ?????????? ?????????? ? ????????? ???????????? ????????. ??????????
???????? ???? ???????? ?????? ?????????, ? ????????? ? ?????????? ?????????? ???????????? ??????????? ?????????? (???????? ??????? ?????????). ??? ?????????????? ??????
???? ????????????? ??? ???????? ???????????? ????? ?? ???? ?????? ????????? ????????
# 575 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander N. Zaloga, Sergey V. Burakov? Multipopulation Genetic Algorithm for Simulation of the Crystal Structure?
??????????????,
????????? ???????,
?????? ??????
????????? ?????????
????????? P1?Pn
??????????? ???????
???.
????
1
???.
????
n
???.
????
k
Mk ?????? ????????
Pk ?? ??
??????????? ??????
??????? ??????? ???
???????? ? ???????
S1k ??????? ?? ??
???.
????
???????? ? ???????
S2k ??????? ? Pk
???. 1. ????? ???????????????????? ????????????? ????????????? ?????????
???????? ???? ?????????? ?????????? ????????? ??????? ?????????, ????????? ? ????. 1.
?????????? ????? ????????? ?????? ? ????? ????????, ????????????? ??????? ???? ??????
???????, ??? ??? ?? ???????? ??? ????? ???? ????? ?? ????????? ??????? ?? ??????? ? ???????????????? ???????? ????????.
??? ????????? ?????????? ??????????? ????????????? ?? ?????????? ? ???????? ?????????? ???? ??? ?????? ?????? ?? ???????? ???? ????????? ?? 100 ??????????? ??????
????????????????? ????????? ???? ?? 4-??????? ??. ??? ????????????? ?????? ?????????? ???? ? ?????????????????? ?? ? ????????? ????????? ????? ????????? ???????????
??????? ? ?? ?? ?????????????? ???? ? ????????? ?? 20 ?????? ?????? ?????? ?? ????????.
??? ???? ? ?????? ????? ????????? ?? ???? ?????????????? ????? ?????????? ???????????
????????????????? ??, ??? ??? ? 20 ?????? ???? ???????? ?? 60 ??????????? ???????????.
??????? ?????? ?????????? ? ??????? ????????? ?????????? ????????? ????????. ????? ??????????? ???????, ?????????? ??? ????????, ?????????? 2 % ?? ??????? ?????????. ????????? ???????????? ???????? ? ?????????? ??????? ???????????, ??????? ??????? ?????????
? ???????? ??????????? ??????? ? ????????? ????????? ???????? ?? R-??????? ? ???? ?????????. ????? ????, ?????????????? ???????? ?????????? ???????? ? ?????????? ? ?????????
# 576 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander N. Zaloga, Sergey V. Burakov? Multipopulation Genetic Algorithm for Simulation of the Crystal Structure?
??????? 1. ?????? ???????? ??????????????? ???????? ??? ????
??????????
???????
??????????
K4SnO4
K2PbO2
Ca2Al3O6F
????????? ???????;
????? ?????? ????? ????????
??????. ?????? ?????????;
? ??????????? ??????? ???????
????? ?????????? ?????? Z ? ??????
????? ??????
?????????
a=6,48Е, b=6,51Е, c=9,70Е, ?=71,82°, ?=99,89°,
9
27
?=113,13°; ? -1; Z=2
a=10,9Е, b=7,6Е, c=7,32Е, ?=119,3°, ?=88,4°, ?=117,7°;
10
30
? -1; Z=2
a=7,3205Е, c=6,9988Е; R -3; Z=12
9
25
??????? 2. ??????????? ?????????????? ?????? ???????? ?? ???? ? ??
????????
?????????
?????? ?????????;
??????????
?????????
????????
K4SnO4
50; 200
1
K2PbO2
100; 200
2
Ca2Al3O6F
100; 300
2
???????
??????????
??????, %
??????? ?????
??????????,
???
???????
R-??????
? ?(R)???
??????????
1
76
1,72
5,53 (0,01)
2
64
2,77
7,76 (0,03)
2
27
4,21
7,09 (0,01)
5,53 (0,001)
????????? ????????
S1
S2
????
????????????????? ??
K4SnO4
50; 200
1
0
50
3,08
K2PbO2
100; 200
2
0
27
5,20
7,75 (0,001)
Ca2Al3O6F
100; 300
2
0
6,7
4,50
7,09 (0,006)
?????? ????????? ?? ?????????? ???? ?????????. ??????????? ?????????????? ???????????
?????? ???????? ??????? ? ????. 2.
??? ?????? ???????? ?? ???? ?? ????????????????? ???????? ??? ? ??????????????
24 ?????????????? ????? ????????? K4SnO4 ???????????? ?? 100%-??? ???????????, ? ?????
??????? ???????? ????????? Er10W2O21 (??. ??. P b c n) ? 54 ????????? ??????? ??????? ????????? ???? ?????????? ? 3 ??????? ?? 5 (23 ????????? ??????? 500, ????? ????????? ????????
500).
?????????? ???????????
??????? ???? ? ????????? ??????????? ??????? ????? ??????????? ??? ???????
????????? ? [12]. ???????????? ????? ???????? ????? ???????? ???? ?? ???? ??????? ???????????? ?????????????????? ?? [13], ???????????? ?????????? ?????????? ?????? ???????????? ???????? ??????????????? ????? ??????? ???????????. ??????????? ?????? ???
???????? ???????? ? ????????????, ??????? ???????????????? ?? R-???????. ?? ???????
????????????? ??????????? ???????? ????????? ????????????? ?????????? [14], ???????????
????? 13 ??????????? ?????????, ????????, ??? 4-????????????? ???? ? ???????? ????????? ?? 100 ??????????? ??????? ????????? ?????????? 42 % (? 10 ??????? ?? 24 ??????), ?
????????????????? ?? ? 18 % (? 3 ??????? ?? 17 ??????) ??? ?????????? ?????????????? ??# 577 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander N. Zaloga, Sergey V. Burakov? Multipopulation Genetic Algorithm for Simulation of the Crystal Structure?
?????? (?? 20-??????? ?????????????? ????????). ??????? ???????, ???? ???????? ?????????
?????????? ? ~ 2,4 ???? ???????????? ?????????????????? ??, ??? ???????? ?????????????
???????????????? ????????. ?????? ?????? ?????? ?? ??????? ???????????? ????????, ????????, ??????, ??? ??? ????????? ? 13 ????????? ??????? ?????????? ???????????? ? ???????
???????? ?????? ???????????? ??????? ???????? ??????, ???????? ??? ?? ?????? ?? ????????????????? ???????? [15]. ??? ?? ????? ?? ?????? ??????? [5-7, 16] ?????????? ??????????????? ???????? ?????? ???????????? ?????????? ??? ???????????? ???????.
?? ?????? ????. 2 ?????, ??? ??? ??????? ???? ?? 4-??????? ?? ??? ?????? ???????? ?
25?30 ????????? ??????? ??????????? ?????????? ????????????? ??????? ?????????? 56 %
??? ????????? ?????????? ???? ???????????? ?????????????????? ?? ? 1,5?4 ???? (???
?????????? ?????????????? ????????). ??????? ???????????? ?????? ??????? ???????? ?????????? ?????????? ?? ??????????? ???? ???? ?????? (? ?????? R-???????) ???????????
??????? ?? ???? ????????? ? ???????? ???????? ???????, ???????? ?????????? ??? ?????
????? ?????? ???????? ??????? ??. ????? ???????? ???????? ???????????? ?????????? ??????????? ?? ???? ?????????? ??????????? ??????? ? R-???????? ???? ????????. ??? ?????????????? ???????????????? ?????????? ?????? ???????, ????????????? ? ?? ??? ???????????, ?????????? ????????? ??????? ??? ??????????? ???????????? ???????? ??????????
???????? (?? 3-4 ?????????). ?????? ? ??? ??? ?????????????? ??????????? ???????????????
????? ?? ??? ? ?????????? ? ??????????? ???????????? ??????????? ??????? ??????????
????????? ????????? ??????????? ???????? ? ?? (S2 ~ 1-2 % ?? ??????? ?????????). ??????? ????????? ??????? ?? ????????? ??????? ????????? ? ?????? ????????? ?????????? ???????? ??????? ??????????? ?????????? ? ????????? ???. ????? ???????? ????????? ????????
?????? ???? ???? ??????? ?????????.
?? ???. 2 ???????????? ??????? ?????????? ???? ?? ?? ??? ?????? ????????? Ca2Al3O6F.
?? ??? ??????? ?????? ????? ????????? ???????? (??????? ????? ? ????????? ????????? ????????? ???? ?????????), ?? ??? ??????? ? ??????????????? ??? ???????? R-???????.
??? ????????? ???????? ?????????? ??????? ???????????? ???????????? ????????
R-??????? (??????? ?????), ? ????? ?????? (?????? ?????) ??? ?????? ?? ??????????? ???????, ???????? ?? ?? ? ??????? ????????? ????????. ????????? ??????????? ???????????
????? ????? ??????? ???????? ??????????? ?????????? ?? ?? ????????? ?????? ???????????
???????, ??????????? ? ?????????? ?? ?????????????? ?????. ?????????? ????? ?????????? ?????? ??????, ??????????? ?? R-?????? ?? ?????????? (?? ????????) ????????? ?????? ? ?????? ?????? ??? ????, ????? ??? ?? ???????? ????????? ?? ?????????. ????? ?????
?????????? ??????? ???????? R-??????? ??? ?????? ???????? ??????????? ??????? ?? ??.
?? ????????? ? ?????? ?? ?????????? ????????? ???????? ???????? R-??????? ?????? ??????????? ????????? ???????? ????????. ?????? ?????????? ???? ? ???????? ????????
R-???????, ? ??????????????? ??????????? ?????? ? ? ???????? ????????? ??????? ????????
(?? 89-? ?????????). ??????? ????? ?????????? ?????? ???????? R-??????? ??? ???? ??????
??????? ?? ???? ?????????????? ????? ?? ?????? ?????????. ?? ?????? ????? ????????????
?????????? ?????? ?????? ? ?????-???? ?? ?????????, ? ?????? ???? ? ????????? ????? ??
?????? ??????? ?? ??? ?????????. ??-?? ?????????? ????????? ???????? ????????? ???????
????? ? ?????? ????? ?????? ???????????, ? ?????????? ????? ???? ????????????? ????????
# 578 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
???. 2. ??????? ?????????? ???? ??? ?????? ????????? Ca2Al3O6F; ??? ??????? ? ????? ?????????
????????, ??? ??????? ? ???????? R-???????
???. 3. ????????? (???????) ? ????????????????? (???????) ?????????????? ? ?? ???????? (?????) ???
????????? ?? ???? ????????? Ca2Al3O6F; Rwp-?????? 7,09 % ???.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander N. Zaloga, Sergey V. Burakov? Multipopulation Genetic Algorithm for Simulation of the Crystal Structure?
??????????????? ?????? ??????????? ??????? ? ?? ?? ?????????? (????? ??????????????
?????????????? ???????? S1 ? S2). ????? ???????, ?????? ???????? ????????? ???? ???????? ????????? ?????????????? ??????? ?????????? ????. ?? ?????????? ?????? ???? ???
?????? ??????????? ?????? ???????? ?????? (???. 3), ???????????? ???????????? ?????????
? ????????????????? ?????????????.
??????????
???????????? ????????? ???????????? ab initio ????? ??????? ??????????????? ????????? ?????????? ?????????? ?? ?????????? ??????????????, ?????? ????????????????
? ????? ???????????? ????????? ????????, ? ????????? ?? ???? ???????????? ???????????
??? ?????? ?? ???????????? ?? ? ????????????????? ?????????. ????????? ????????????? ?????? ???????? ?? ???? ???????? ? ??????????????????? ?????????? ????? ?????????
?????????. ?????????????? ???????? ?? ?? ?????? ????? ???????? ? ?????? ????????? ???????? ?? ???????????????? R-???????. ????????????? ? ????????? «???????????» ?????
?????????? ????????? ??????? ???????????? ???????? ?? ?????? ????????? ???????? ?
«??????????? ????????? ?????????». ??? ???????????? ?????? ?? ??? ? ???????? ?????
?????????? ????????????? ???????? ? ?????????? ???????. ???? ??????????? ??????????
???????? ????? ??????? ??? ??????????? ????? ??????? ??????????????? ????????.
?????? ????????? ??? ????????? ?????? ??-3 ? ?????? ???????????????? ???????
??? ?? ?????????? ???????????? ???????????? ?? 2014 ?.
?????? ??????????
1. Inorganic Crystal Structure Database. FIZ Karlsruhe. http://www.fiz-karlsruhe.de/icsd.html
2. Cambridge Structural Database. Cambridge Crystallographic Data Centre. http://www.ccdc.
cam.ac.uk/products/csd/
3. Powder Diffraction Theory and Practice, ed. R.E. Dinnebier and S.J.L. Billinge / Royal Society
of Chemistry, 2008. 507P.
4. Young R.A. The Rietveld Method / Oxford University Press. 1995. 298P.
5. David W. I. F., Shankland K.. Structure determination from powder diffraction data // Acta
Cryst. (2008). A64, 52?64.
6. Harris K. D. M. Powder Diffraction Crystallography of Molecular Solids // Top. Curr.
Chem. 2012,315, 133?177.
7. Radovan Cerny, Vincent Favre-Nicolin. Direct space methods of structure determination from
powder diffraction: principles, guidelines, perspectives // Z. Kristallogr. 222 (2007) 105-113.
8. Kenneth D.M. Harris. Fundamentals and applications of genetic algorithms for structure solution
from powder X-ray diffraction data // Computational Materials Science. V. 45. Issue 1. 2009. P. 16?20.
9. Yakimov Y. I., Semenkin E. S., Yakimov I. S. Two-level genetic algorithm for a fullprofile
fitting of X-ray powder patterns // Z. Kristallogr. Suppl. 30 (2009) 21-26.
10. A. Le Bail. The profile of a Bragg reflection for extracting intensities / Chapter 5 in: Powder
Diffraction: Theory and Practice, Ed. R.E. Dinnebier & S.J.L. Billinge, Royal Society of Chemistry,
Cambridge (2008) 134-165.
# 580 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Alexander N. Zaloga, Sergey V. Burakov? Multipopulation Genetic Algorithm for Simulation of the Crystal Structure?
11. Favre-Nicolin V., Cerny R. FOX, free objects for crystallography: a modular approach to ab
initio structure determination from powder diffraction // J. Appl. Cryst. (2002). 35, pp.734?743.
12. Habershon, S.; Harris, K. D. M.; Johnston, R. L. Development of a Multipopulation Parallel
Genetic Algorithm for Structure Solution from Powder Diffraction Data. // J. Comput. Chem. 2003,
V.24, No.14, pp. 1766 - 1774.
13. Albesa-Jovй D.; Kariuki B. M.; Kitchin S. J.; Grice L.; Cheung E. Y.; Harris K. D. M. Challenges
in Direct-Space Structure Determination from Powder Diffraction Data: A Molecular Material with
Four Independent Molecules in the Asymmetric Unit. ChemPhysChem. 2004, 5, 414?418.
14. Cheung, E. Y.; McCabe, E. E.; Harris, K. D. M.; Johnston, R. L.; Tedesco, E.; Raja, K. M. P.;
Balaram, P. // Angewandte Chemie, Int. Ed. 2002, 41, 494.
15. Thomas A. N. Griffin, Kenneth Shankland, at al. GDASH: a grid-enabled program for structure
solution from powder diffraction data. // J. Appl. Cryst. (2009). 42, 356?359.
16. Bryce Meredig, C. Wolverton. A hybrid computational?experimental approach for automated
crystal structure solution // Nature Materials, 12, 123?127 (2013).
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 582-589
~~~
??? 541: 661.183
Adsorption of the Volatile Aliphatic Acids
from Aqueous Solutions by Active Carbons
Anna O. Eremina, Valentina V. Golovina,
Nikolai V. Chesnokov* and Anatoly A. Sobolev
Institute of Chemistry and Chemical Technology SB RAS
50-24 Akademgorodok, Krasnoyarsk, 660036, Russia
Received 21.10.2010, received in revised form 20.11.2014, accepted 00.09.2014
Active carbons from brown coal, mixed birch wood and aspen wood wastes have been produced by
pyrolysis and air-steam activation. Results of study of formic and acetic acids adsorption by obtained
active carbons are presented. The principal technological scheme of waste water purification from
formic and acetic acids by active carbons is discussed.
Keywords: active carbon, adsorption, formic acid, acetic acid, water treatment.
????????? ??????? ????????????? ??????
?? ?????? ????????? ?? ???????? ?????
?.?. ???????, ?.?. ????????,
?.?. ????????, ?.?. ???????
???????? ????? ? ?????????? ?????????? ?? ???
??????, 660036, ??????????, ?????????????, 50-24
????????? ?????????? ???????????? ????????? ?????????? ? ???????? ?????? ?? ????????
?????, ?????????? ??????? ???????????? ? ??????????? ????????? ?? ????????? ???????
????????????? ????????? ? ???????? ?????????, ? ????? ?? ?????? ????. ??????????
?????????????? ??????????????? ????? ????????????? ??????? ??????? ??? ?? ???????
????????????? ??????.
???????? ?????: ???????? ?????, ?????????, ?????????? ???????, ???????? ???????, ???????
??????? ???.
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: cnv@icct.ru
# 582 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Anna O. Eremina, Valentina V. Golovina? Adsorption of the Volatile Aliphatic Acids from Aqueous?
????????
??????? ???? ????????? ???????????? ?????????? ???????, ???????????? ????????
???????, ??????? ??????, ?????????????? ??????? ???????? ? ???????????? ???????????
??????? ??????? ?????????????? ???? (?????? ????? ?????????????? ????? CnH2n+1COOH ?
CnH2n?1COOH, ??????? 1-6 ?????? ???????? ? ????????), ? ????????? ?????????? ? ????????
???????. ??????? ??????? ?????????? ????? ? ??????? ????? ? ?????????? ???????? ????????
???????????? ???????. ????? ?? ???????? ?????????????? ????? ???????????? ???????
??? ????? ???? ????????????? ????? ?? ????????????????? ??????????? [1-7], ??????????? ?
??????? ?????????? ????? ????? ????.
? ?????? ?????????? ?????????????? ?????????? ?????????? ? ????????? ???????????
??-?? ????????????? ??????? ???????????? ???????????, ??????? ????????? ????????? ????? ? ??????? ??????? ????????? ?????????? ???????????, ???????? ?????? ?????????????
????????????? ????????????? ??????????, ???????????? ????????? ???????? ???? ???????????? ???????? ?????????????????? ????? (?????????? ?????, ??????? ????????????? ? ???????????????, ?????????????? ????????? ? ??.).
? ????????? ?????? ??????? ????????? ??????? ????????????? ?????? ?? ??????? ?????????? ? ???????? ?????? ?? ?????? ???? ?? ???????????????? ???????? ?????, ??????????
?? ????????? ??????? ????????????? ????????? ? ???????? ?????????, ? ????? ?? ?????? ????
???????? ???????????? ? ??????????? ?????????.
????????????????? ?????
??? ???????????? ???????? ????? ???????????? ????????? ?????-?????, ??????????
????????????? ????????? ??????? ????????????? ????????? ? ???????? ?????????. ???????????? ????????? ?? ????????? ???-5? ? ?????? ?. ?????? ????????????? ????. ????????
????????? ?????-????? ???? ????????? 5,0 %, ????????? (?d) ? 1,8 %, ???????? ?????????
223 ??/?3, ????????? ????? ??? ? 0,06 ??3/?, ??????????? ?????????? ?? ???? ? 6,5 %. ????????? ?????????? ????-????? ???????????? ? ???????? ???????? ???? ??? ???????????
850 °?, ???????????? ???? 36 % ??., ????????? ? 5,3 % ??., ????????????????? ????????? 30
??? [8].
??? ????????? ????????? ???? ???????????? ????? ????? ????? ?2, ?????????? ??????????? ???????? ??? «????». ??????? ???????? ??????????? ????????????? ??? ????? ????:
????????? (Wtr ) ? 32,8 %; ?????????? ???? (Ad) ? 9,4 %; ?????????? ???? (Std) ? 0,3 %; ?????????? ??????? ??????? (Vdaf ) ? 47,4 %; ?????? ??????? ???????? (Qir) ? 3820 ????/??. ???????? ????? ?? ?????? ???? ???????? ? ???????? ???????? ???? ?? ????????????? ??????????
????????-????????? [9]: ??????????? ???????? 750 °?, ???????????? ???????? ???? 30 ??. %,
???????????? ????????? ? ??????????? ????? 4,5 ??. %, ????????????????? ?????????? ?????? ???? ? ???????? 15 ???.
??? ?????????? ??????????? ?????????????? ???????? ??????????? ??????????? ?????
???????? ????? ? ???????? ?????????????? ????????? ????????? ??????????? ????????
?????: ????????? 1 ? ??????? ???????? ? ??????????? ???????? ???????????????? ?????
? ?????? ??? 105 °?. ???????? ???????? ???????? ????? ????????? ? ????. 1. ???????????
??????-?????????? ? ????????????? ??????? ???????? ????? ????????? ?? ????????? ??# 583 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Anna O. Eremina, Valentina V. Golovina? Adsorption of the Volatile Aliphatic Acids from Aqueous?
??????? 1. ???????? ??????-?????????? ? ????????????? ???????? ???????? ?????
???????? ????
???????? ????
?? ?????????? ?????
?? ?????? ????
??????????????????????????????????
????????
???
???
7,4
6,1
9,6
8,4
??????????
?????????, ???. %
????????? (Ad), ???. %
2,6
0,4
12,3
2,3
193
215
655
688
1,56
1,49
0,49
0,52
????? ???????? (?? ???), ?? /?
0,24
0,21
0,13
0,14
???????? ???????????, ?2/?
536
513
560
600
??????????? ?????????? ?? ????, %
53,0
58,3
45,6
49,6
????????? ?? ?????????, %
59,0
55,0
67,0
63,0
???????? ?????????, ??/?
3
????????? ????? ???, ?? /?
3
3
??????? [10, 11]. ????? ???????? ? ???????? ??????????? ?????????? ??????? ???????? ????????? ????? ????? ?? ??????? ASAP.2400.VI.00. ?????? ?????? ?? ????????????? ????? ???????? ??????? ????????? ?? ???? [12].
?????????? ???????????????? ???????? ???? ????? ?????????? ???????? ????????
?????????. ???????? ?????, ?????????? ?? ?????????? ?????, ????? ????????? ????? ???
? 2,9 ???? ??????? (1,49 ??3/?), ??? ? ????????? ????, ??????????? ?? ?????? ???? (0,52 ??3/?).
?????? ??? ??????? ????????? ?????? ??? ???????? ?????, ?????????? ?? ?????? ????, ??
???? ???????? ? ????????? ?????? ??? (0,27) ??????????? ???????? ?????, ?????????? ??
?????????? ????? (0,11).
?? ???. 1 ???????????? ???????? ????????? ? ????????? ????? ?? ????????????????
???????? ?????. ??????? ????????? ??????? ??? ?????????? ??? ????????? ???? ?? ?????????
26 Е, ??? ????????? ???? ?? ?????? ???? ? 29 Е.
2
?
200
1
100
0
0
0,4
0,8 ?/?0
???. 1. ???????? ????????? (??????? ? ?????? ?????) ? (??3/?) ? ????????? (??????? ? ????? ?????)
????? ?? ???????? ?????, ?????????? ?? ?????????? ????? (1) ? ?????? ???? (2); P/P0 ? ?????????????
????????
# 584 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Anna O. Eremina, Valentina V. Golovina? Adsorption of the Volatile Aliphatic Acids from Aqueous?
????? ?????????? ???????? ???? ??????????? ??? ??????????? 105-110 °? ? ??????? 2 ?,
????????? ? ?????????? ??? ?????????? ? ?????????? ??????? ???????? ????? (?????? ?? 0,1
?? 10 ?) ? ????????? ?? 0,2 ??. ????????? ????????? ???????? ????? ?????? ????. ??? ?????
??????? ???????? ????? ???????? ? ??????? ? ?????????? ??????? 98-99 % (??? ??????????
????????? ????????? ??????) ??? ??????????? 40 °? ? ??????????? ??? ?????? ???????? ?
??????? 3 ?. ??????? ???????? ????? ???????? ? ????? ? ?????????? ???????? ?? 150 ?? ?????? ????????? ??????? ????????????? ??????, ??????????? ? ????? ?????????????? ? ??????? 48 ?. ?????? ??????? ???????? ??????????????????, ?????????? ?????????? ??????????
??????? ????????????? ??????.
? ???????? ??????????? ????????? ?????? ???????? ?????????? ? ???????? ?????? ????????? ???????????? ?? 6 ?? 100 ?????/?. ???????? ?? ??????????? ????????????? ?????? ?
??????????? ? ? ?????????? ????? ????????? ???????? ????? ???????????? ?? ????????????
????????? [13].
?????????? ? ??????????
?? ???. 2 ????????? ???????? ????????? ?????????? ? ???????? ?????? ?? ????????
????? (???????? ???????????? ?????? 12,5 ?????/?). ????? ??????? ??????? ??? ???????????, ?????????? ?????? ? ??????????? ???????????? ?????????? ????- ? ????????. ???????? ????? ???? ???????? ?? II ???? ?? ????????????? ??? [14]. ???????? ?????????
????? ?????????? ??? ??????????? ???????????? ????? 0,5-1,0 ?????/? ??? ????????? ???? ??
?????? ???? ? ??? ??????????? ???????????? ????? 8-10 ?????/? ??? ????????? ???? ?? ????????? ???????. ??? ??????????? ????????????? ????????????????? ?????????????? ????
??? ????????? ?? ????????????? ???????? (????????????) ?????????? ??????????????? ??
???????? ??????? [2].
????????? ??? ??????????, ??? ? ???????? ?????? ?????? ?? ???????? ????, ??????????
?? ?????? ????. ???, ??? ??????????? ????????????? ?????? 2-8 ?????/? ????????? ?????????? ? ???????? ?????? ?????? ?? ???????? ???? ?? ?????? ???? ?? ????????? ? ?????????? ??
???????? ???? ?? ????????? ??????? ? 2,6-2,8 ? 3,1-3,2 ???? ??????????????.
???????? ????????????? ??????? ??????????? ??????? ?? ??????? ?????????????? ???????? (?????????? ??? ???????? ???????), ? ????? ??????? ? ???, ??? ?????????? ??????? ?
????????? ????????????? ?? ?????????? ? ????????????? ????? (???. 2). ????????? ????????
??????? ????, ??? ??????????. ???????? ??? ???????? ??????????? ??? ????????? ???????
????????? ???? (6-10 ??/?3), ? ??????????? ??????? ????????? ???? ???????? ????? ?????????? ????????? ?????????? ? ???????? ?????? ???????????? (????. 2). ?????? ?????????? ???????? ???????????? ?????? ?? 50-100 ?????/? ???????? ? ????, ??? ???????? ? ?????????
????????? ?????????? ? ???????? ?????? ?????????? ?????????????? ? ???? ????????? ?????????? ??????? ????????????? ??????, ??? ????????. ???, ??-????????, ??????? ? ???, ???
? ????????? ? ?????????? ??????? ????????????? ?????? ????????????? ??????? ??????????? ??????????? ?????????? ?? ????????? ? ???????????? ??????????? ???????? (?????????
??????) ??????????, ? ?????????? ??????? ? ???????? ???????????.
?????????? ???????? ???????????? ??????? ? ???????? ?? ????????? ?????????????
??????? ?? ??? ?????????? ??????? ?????????, ? ???? ???????? ? ??????????? ????????
# 585 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Anna O. Eremina, Valentina V. Golovina? Adsorption of the Volatile Aliphatic Acids from Aqueous?
?
2
4
3
2
1
1
0
0
4
8
12 ??
???. 2. ???????? ????????? ? (?????/?) ?????????? (1, 3) ? ???????? (2, 4) ?????? ?? ???????? ?????,
?????????? ?? ?????????? ????? (1, 2) ? ?????? ???? (3, 4) ??? ???????? ???????????? ?????? 12,5 ?????/?;
?? ? ??????????? ????????????, ?????/?
??????? 2. ??????? ?????? ????????? ????????????? ?????? ?? ???????? ????, ?????????? ?? ??????
????
??????? ??????? ?????? ????????? ( %)
??? ??????? ????????? ????
?????????
6 ??/?3
10 ??/?3
20 ??/?3
???????? ???????????? 12,5 ?????/?
?????????? ???????
62,5
76,0
92,6
???????? ???????
79,3
90,9
94,1
???????? ???????????? 25 ?????/?
?????????? ???????
49,9
63,6
85,2
???????? ???????
54,2
72,1
90,9
???????? ???????????? 50 ?????/?
?????????? ???????
32,7
48,3
76,0
???????? ???????
27,3
43,0
69,8
???????? ???????????? 100 ?????/?
?????????? ???????
16,9
26,5
46,8
???????? ???????
15,8
26,1
46,1
????????????? ??????? ????????? ????. ??? ????????????? ?????????????? ?? ???. 3 ????????? ?????? ?? ????????? ???????? ??????? ?? ???????? ????, ?????????? ?? ?????? ????
??? ????????? ???????? ????????????? ???????? ???????.
????????? ??????????? ???????????? ???????? ????? ???????????? ??????? ? ??????? ???????? ??? ??????????? 300 °?. ???????? ???? ????????? ?????????? ??????? ??# 586 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Anna O. Eremina, Valentina V. Golovina? Adsorption of the Volatile Aliphatic Acids from Aqueous?
?
2,0
3
4
2
1,5
1
1,0
0,5
0,0
0
20
40
60
80 ??
???. 3. ????????? ? (?????/?) ???????? ??????? ?? ???????? ????, ?????????? ?? ?????? ???? (?? ?
??????????? ????????????, ?????/?) ??? ???????? ???????????? ???????? ??????? (?????/?): 1 ? 6,3;
2 ? 25; 3 ? 50; 4 ? 100
??????????? ???????????: ????? ???? ?????? ????????????????????? ????????? ?????????
?? 5?7 ???. %. ?????? ????? ????????? ????????? ??????????? ?? ?????????: ?? 45 %. ?????
?????????? ???????, ??????????? ?????? ??????, ???????????? ?????? ? ?????????? ?????????? 55?68 %.
?????????? ?????????????? ??????????????? ????? ????????????? ??????? ???????
???, ???????????? ???????? ????????? ?????????????? ????. ????? ???????? ?????????
??????: ????????? ??????? ??????? ??? ?? ?????????? ??????? ? ?????????? ?????????? ????????????? ????????; ?????????? ?????? ????????????? ??????? ?? ?????????????
??????; ?????? ??????????? ???????????? ???????? ?????. ?????? ????????????? ???????
??????????? ? ???? ??????????????? ????????????? ??????????, ???? ?? ??????? ???????????? ??????????? ?? ???????????. ?????? ??????????? ????????: 1) ???????? ? ???????????? ???????? ?????, ??????????? ? ???????????, ????? ??????? ? ???????? ????????? ??????????? ??????; 2) ?????????????, ??? ??????, ?????????? ?????? ??????, ???????????
?? ??????????? 20-25 °?; 3) ????????, ??? ?????????????? ????? ??????; 4) ???????????
??????, ??? ?????????? ??????? ??????????? ????? ????? ??????? ? ?????????. ????????????? ????? ???? ?????? ???????????? ???????? ???? ????????????? ????? ???????? ??
?????????????? ??????????.
? ???????????? ???????? (?????????? ??????? ????????? 2 ??, ?????? ???? ?????????
???? 20 ??, ???????? ???????? 10 ?-1) ????????? ??????? ??????? ??? ??????????? ?????????????? ?????????????? ?? ???????????? ???????? ???????. ???????? ??????? ???? ?????
???? ?????????? ????????? ????? ? ????????? 35 ?????/? ???????? ???????, 30 ??/? ???????
??????? ? 20 ??/? ????. ????? ?????? ??????? ?? ???????? ?????, ?????????? ?? ?????? ????,
????????? ???? ?? ????? ??????, ????????? 7 ?????/? ???????? ??????? ? 5 ??/? ???????
???????, ????? ?? ??????????. ????????????? ???? ???? ??????????? ?????? ?????????
?? ??? ?? ???????? ????. ? ?????????? ????? ?????????? ???????? ?????????? ??????????# 587 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Anna O. Eremina, Valentina V. Golovina? Adsorption of the Volatile Aliphatic Acids from Aqueous?
??? ????????: ???????? ??????? ?? 0,6 ?????/?, ??????? ??????? ? 0,5 ??/?. ????????????
???????????? ??????? ? ????????? ????? ???? ????????????? ?????????? ??? ?????? ? ???????? ???????, ?? ?????? ????????????? ?????????? ??? ?????? ??????? ??? ?????????
??????????? ? ??????? ????????? ??????????? ??? ??????????? ?????????.
??????
??????? ????????? ?????????? ? ???????? ?????? ?? ?????? ????????? (? ????????? ???????????? 6-100 ?????/?) ?? ???????? ?????, ?????????? ?? ????????? ??????? ????????????? ????????? ? ???????? ?????????, ? ????? ?? ?????? ????.
????????, ??? ????????? ?????? ?? ?????? ????????? ??? ??????????? ?????????????
?? 8 ?????/? ? 2,6-3,2 ???? ???? ?? ???????? ???? ?? ?????? ???? ?? ????????? ? ????????
????? ?? ????????? ???????. ??? ?????? ??????? ????????? ???? (6-10 ??/? 3) ?????????
???????? ??????? ?? ???????? ????? ? 1,2-1,3 ???? ????, ??? ?????????? ???????. ???
??????? ????????? ???? 20 ??/? 3 ? ???? ???????? ????????? ?????????? ? ???????? ?????? ?????????? ??????.
?????????? ?????????????? ??????????????? ????? ????????????? ??????? ??????? ???
?? ??????? ????????????? ??????, ??????? ?????????? ??????????????? ?????????, ?? ???????
?????????????? ?????????????? ???????????? ? ????????????? ??? ?????????? ?? ???????????? ??????????????, ?????????? ? ??????????????? ??????????????.
?????? ??????????
1. ??????? ?.?. ??????????? ??????? ????. ?.: ?????, 1982. 168 ?.
2. ??????????? ?.?., ???????? ?.?., ???????? ?.?.., ???? ?.?. ????????? ????????????
??????? ?? ????. ?.: ?????, 1990. 256 ?.
3. ?????? ?.?., ????? ?.?., ??????? ?.?. ?????????? ?????????? ?? ?????? ??????????
?????. ???????.: ?????, 2000. 243 ?.
4. ???????? ??????????? ????? ????? ? ?????????? ?????? ?????? ? ?????????? ?????????? / ?.?. ????????, ?.?. ???????, ?.?. ?????, ?.?. ????????, ?.?. ???????, ?.?. ??????;
???. ???. ??.-????. ??? ?.?. ??????. ???????????: ???-?? ?? ???, 2012. 211 ?.
5. ????????? ?.?. ??????????? ????????? ?? ?????? ?????????? ????? // ????? ???????? ???????. 2000. ?1. ?. 35-44.
6. ????????? ?.?., ??????? ?.?., ???????? ?.?. ??????? ?????????????? ???????????
?????????? // ????? ???????? ???????. 2009. ? 5. ?. 42-46.
7. ?????? ?.?., ??????? ?.?., ?????????? ?.?. ????????????? ??????????? ????????????? ????? ????????????? ???????? // ????? ???????? ???????. 2012. ? 3. ?. 56-64.
8. ??????? ?.?., ????? ?.?., ???????? ?.?. ? ??. ????????? ????????? ????? ? ?????????
???????? ???? // ????? ? ????????? ??????????? ????????. 1996. ?. 4. ? 3. ?. 193-199.
9. ????? ?.?., ??????? ?.?., ???????? ?.?. ?????? ????????? ??????????????? ???? //
?????? ? 2051096 ?? / ?.?. ?????, ?.?. ???????, ?.?. ????????. 1995.
10. ????? ?., ????? ?. ???????? ???? ? ?? ???????????? ??????????. ?.: ?????, 1984.
216 ?.
11. ???????? ?.?. ???????? ????: ??????????. ?.: ?????, 1985. 56 ?.
# 588 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Anna O. Eremina, Valentina V. Golovina? Adsorption of the Volatile Aliphatic Acids from Aqueous?
12. ????????? ?.?. ???????? ???????. ???????????,1995. 518 ?.
13. ????? ?.?., ????????? ?.?. ?????????? ?????? ???????????????? ??????? ???. 4-?
???., ???????. ? ???. ?.: ?????, 1974. 336 ?.
14. ??????? ?.?. ?????? ????????????? ???????. ?.: ?????, 1984. 592 ?.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 590-596
~~~
??? 615.322
Features of the Essential oil Accumulation
in the Angelica Decurrens (Ledeb.) B. Fedtsch. Roots
in Comparison with Angelica ?rchangelica L.
Olga S. Shchipitsyna and Alexander A. Efremov*
Siberian Federal University
79 Svobodny, Krasnoyarsk, 660041 Russia
Received 17.10.2014, received in revised form 20.11.2014, accepted 02.12.2014
Essential oil from the roots of the Siberian specie Angelica decurrens (Ledeb.) B. Fedtsch. was obtained
by hydro-steam-distillation method. Its component composition was studied in comparison with the
European Medicines specie Angelica archangelica L. The similarity of the essential oils compositions
was confirmed. The major components of both species are terpenes: ?-pinene and ?-phellandrene.
Essential oils in the A. decurrens and A. archangelica roots are accumulated in the secondary
secretory ducts. The identity of the essential structures of rhizomes of the Siberian A. decurrens and
the European A. archangelica was confirmed.
Keywords: Angelica decurrens (Ledeb.) B. Fedtsch., Angelica ?rchangelica L., essential oil, ?-pinene,
?-phellandrene, secretory ducts.
??????????? ?????????? ???????? ?????
? ?????? Angelica decurrens (Ledeb.) B. Fedtsch
? ????????? ? Angelica ?rchangelica L.
?.?. ????????, ?.?. ???????*
????????? ??????????? ???????????
??????, 660041, ??????????, ??. ?????????, 79
??????? ???????????????????? ???????? ??????? ????? ?? ?????? ???? Angelica decurrens
(Ledeb.) B. Fedtsch. ?????????? ??? ???????????? ?????? ? ????????? ? ?????????????
????? Angelica ?rchangelica L. ? ?????????? ???????? ????????????? ???????. ????????, ???
*
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: aefremov@sfu-kras.ru
# 590 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga S. Shchipitsyna and Alexander A. Efremov. Features of the Essential oil Accumulation in the Angelica Decurrens?
????????? ???????????? ????? ????? ???????? ???????????: ?-????? ? ?-??????????. ?????
?????????? ??????-????????? ????????? ???????? ???? Angelica decurrens ? ???????????
?????? ? ???????? ?? ???????????? ?????????? ???????? ? ?????? Angelica ?rchangelica.
???????? ?????: Angelica decurrens (Ledeb.) B. Fedtsch., Angelica ?rchangelica L., ??????? ?????,
?-?????, ?-??????????, ??????????? ??????.
????????
?? ???? ???? ????? ???????? ???? Angelica (??????) ???????? ? ???????? ??? ????? ???
????????? ???????? ????? ? ??????????? ????????? ??????? ? ???? ??????????? ????????????????, ??????????????????, ??????????????????????, ??????????? ? ????????????????? ?????????? [1, 2]. ??? ?????? ???????????? ? ???????, ??????????? ? ???????????????? ?????????????? [2, 3].
? ????????? ???????, ?????????? ????? ?? ????? ???????? ??????? ????????? ????????????? ????? ? ??????, ???????? ???????????? ??? ????????? ???????? ????? ? ???????????? ????????? Angelica decurrens (Ledeb.) B. Fedtsch (?????? ???????????) [4-6].
????????, ??? ?????? ??? ????????????????? ???????? ?????? ? ???? Angelica
archangelica L. (??????? ??????????????) ??? Angelica officinalis (Moench.) Hoffm. (?????? ??????????????) [7, 8]. ??? ?????? ????????? ????????????, ??? ??????? ????? ?? ?????? ????
????? ???????? ?????? ?????????? ???????? ? ??? ?????????????? ? ??????????? ??????????????? ??????????.
? ????? ? ???? ? ?????? ??????? ???????????????????? ?? ?????? ?????????? ????
Angelica decurrens ???????? ??????? ?????, ?????????? ??? ???????????? ?????? ? ??????????? ??????-????????? ???????? ? ????????? ? ??????????? ????????????? ????? Angelica
?rchangelica.
????????? ? ??????
????????????? ? ?????? ????? Angelica decurrens ?? ???????? ??????? ???? ????????????? ? 2012 ?. ? ????????? ??????? ?? ???-?????? ??????????? ??????? ????? ?? ??????????
??????? ? ????? ??????? ? ???????????? ? ???????????? ??????????? ? ??? ???????? ????? ?
???????????? ????????????? ?????????????????? ??????? [9, 10].
??? ???????? ?? ????? ? ?????? ???? ??? ???????, ??????????? ????????? ????? ????????? ? ???????????? ? ?????????????? ? ????????????????? ???????? ? ????? ????????????????????? ???????????? [10-13].
??????? ????? ?? ?????? Angelica decurrens ???????? ??? ?????? ?????? ???????????????????? ? ?????????????? ??????????? ???? ?? ??????????? ?????, ?????????????? ??
????????????? ??????. ? ???? ???????????? ???????? ??????????? ? ??????? ???????????,
? ??????? ???? ??????? ???????? ?????. ?????? ??????????? ???? ???????? ??????, ??????
? ??????? ? ??????? ???????? ? ??? ?? ??? ???????? ??????????? ?????. ?? ??? ???? ??
??????? ???????? ???????????????? ????. ? ??????? ????????? ???? ????????? ??????? ???
????? ???????? ????? ? ?? ??? ? ???????? ???????????. ??? ?????????? ?????????. ?????????
# 591 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga S. Shchipitsyna and Alexander A. Efremov. Features of the Essential oil Accumulation in the Angelica Decurrens?
???????? ????? ???????????? ? ??????? 16 ? ?? ??????? ??? ?????????, ??? ????????????????
????????????????. ????????????? ????????? ? ??????? ??????????? ??????? ????? ??????????, ?????????? ??? Na2SO4 [13, 14].
???????-????-?????????????????? ?????? ????????????? ??????? ???????? ????? ????????? ?? ??????? ???????-????-???????????? «Agilent Tecnologies» 7890? c ??????????? ????????????????? «Agilent Tecnologies» 5975? inert MSD ? ???????? ?????????. ??????? ?????????
??-5MS (????????? 5%-???????-95%-????????????????) ? ?????????? ????????? 0,25 ?? ?
???????? ?????? ??????????? ???? 0,25 ???. ???-???????? ? ????? (1,0 ??/???). ????????
?????????????? ????? ??? 50 ?? ? ??????? 3 ???, ????? ????????????????? ?????? ??????????? ?? ????????? 4 ??/??? ?? 280 ?? ? ????????? ??? ???????? ??????????? 3 ???. ??????????? ?????????? 280 ??, ??????????? ????????????? ?????? 170 ??, ??????? ?????????:
70 ??. ?????????? ??????????? ????????? ?? ???????? ?????, ????????????? ?????????
??????????? ????????? ?????????? ?????? ??????????? ? ?????? ????-???????? ? ???????????????? ??????? ??????????? ????????? ????? ? ?????? ?????????? ?????????? ??????
Wiley.7n ? NIST-08, ? ????? ? ?????????????? ???????? ???????? ??????????? ? ??????????
????-???????? [15]. ??? ?????? ?????????? ????-???????? ? ???????? ???????? ???????????
????????????? ????????? ?????????????.
??? ?????????? ???????????????? ??????? ?????????????? ?????????????? ????? ????????? ?????? Angelica decurrens. ??? ????????????? ?????????? ????????? ????????? ??????
????????? 1 ?? ??????????? ? ???????????????? ????, ????? ?????????? ?????? ??????????
????? ???????? ?? ????? 2 ??. ???????? ?? ?????????? ?????? ? ?????????? ????? ???????
??????????. ????????? ????????????? ??? ?????????? ? 100-200 ??? ?? ???????? ??????????
???-3 [11, 16].
?????????? ? ??????????
?????????? ? ???? ????????????????? ?????? ??????? ????? ?? ?????? Angelica decurrens
???????????? ????? ???????? ?????-?????? ????? ? ????? ???????? ??????. ??????? ?????
???????? ?????, ??????????? ??????? ????????????????????, ?? ??????????? ???? ??????? ???????? (0,38±0,04) %. ??????? ???????-????-????????????? ? ??? ???? ??????????? ????? 50
???????????, ???????? ?? ??????? ???????????? ? ????. 1. ?????????????? ???????????? ???????? ?????????????? ??????????: ?-????? (21,8 %) ? ?-?????????? (16,3 %), ??????? (4,0 %),
?-3-????? (3,3 %) ? ?-????? (3,7 %), ?? ???????????????? ??????????? ??????????? ??????????
??????????-D (6,8 %), ????????? ? ?? ????????? 3 %, ????????? ??????? ?????. ????????? ????
?????? ? ????? ??????????????? ?? ????????????? ??????? ???????? ????? ?? ?????? ?????????? Angelica ?rchangelica [17] ? ???????????? ???? [18], ??????????????? ????? ? ????. 1, ??????????, ??? ???????????? ?????? ??????? ????? ?????? ????? ????? ??????, ??? ????????????
????????? ???????????? ???????, ? ????? ??, ??? ? ??????? ????? ?? ?????? ?????? ??????
???????????? ????? ?????????????? ???????????? ???????? ?-?????, ?-?????????? ? ??????
?????????????? ??????????, ?????? ?????????? ??????????-D, ? ????????? ????????????????
????? ?????????? ??? ?? ???????, ??? ? ?? ??????????? ???????????.
? ?????????? ? ??????????? ??????? ??????????? ??????-?????????? ????????????? ????? ????? ????? ?????????? ?? ??????????? ??????-????????? ??????????. ??? ?????? ????
# 592 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
??????? 1. ???????????? ?????? ???????? ????? ?? ?????? Angelica decurrens (Ledeb.) B. Fedtsch. ?
?????????? ? ???????????? Angelica ?rchangelica L.
??????????, % ?? ???????? ?????
????????
??????
???????????
?????????
902
?????????
926
?-3-?????
1.7
-
1.1
932
?-?????
21.8
23.6
23.9
947
??????
1.9
0.9
1.3
952
????????
0.3
-
-
973
???????
4.0
-
0.3
975
?-?????
1.2
1.5
1.3
991
?-??????
0.6
4.7
2.1
A. decurrens
0.2
A. ?rchangelica
?????????
???????????
?????? [17]
?????? [18]
-
0.7
1003
????????
-
-
2.8
1004
?-??????????
1.3
1.9
0.7
1010
?-3-?????
3.3
0.3
3.4
1017
?-????????
1.5
-
-
1024
?-?????
3.7
-
1.1
1028
?-??????????
16.3
30.5
10.3
1028
???????
-
-
2.4
1033
?????????? ?????
0.6
-
-
1038
???-?-??????
0.4
1.3
0.2
1048
?????-?-??????
2.7
3.1
0.7
1058
?-????????
2.0
-
3.1
1066
?????-?????????????
-
-
1.2
1086
?-??????????
1.2
-
0.5
1177
????????-4-??
2.3
-
-
1191
?-?????????
0.7
-
-
1276
???????????
0.8
-
-
1277
????????????
2.9
-
1.3
1378
?-??????
-
0.3
0.8
1387
?-????????
0.7
0.9
-
1392
?-??????
-
3.4
-
1412
?-??????
-
0.7
-
1416
???-?-??????????
-
0.4
-
1421
?-??????
-
0.7
-
1428
???-?-??????
-
0.9
-
1440
????????????
0.8
-
-
1444
?-(Z)-????????
-
7.1
2.6
1450
?-???????
-
0.3
3.2
1484
????????? D
6.8
9.1
2.1
1494
????????????????
1.3
2.0
-
1502
? - ???????
1.0
-
-
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga S. Shchipitsyna and Alexander A. Efremov. Features of the Essential oil Accumulation in the Angelica Decurrens?
1508
? - ?????????
0.6
-
-
1510
(E,E)- ? -????????
-
2.6
-
1517
?-???????
2.1
0.5
-
1527
?-???????
1.3
1.4
-
1541
?- ???????
-
0.8
-
1580
??????????
1.1
-
-
1658
?-???????
-
0.9
-
1730
?????????
0.9
-
-
2140
?????
1.0
-
-
??? ???? ? ??. ?????? «-» ???????? ??????????, ?? ???????????? ? ?????? ??????? ?????.
1
???. 1. ?????????? ???? ?????????? ????? ?????????? ???? Angelica decurrens (Ledeb.) B. Fedtsch. (1 ??
? ????????, ??????? ????? ?? ????? 2 ??). ?????????? ??????-????????? ?????????: 1 ? ???????????
??????. ??????? 1 ??
Angelica ?rchangelica ??? ???? ?????????? ????????? ??????????? ??????, ????????????? ??
??????????? ????? ??????, ??? ????????? ? ?????????? ???? 21569-76? ?? ????? ?????? ?????????????? ? ? ??????????? ?????? ????? [9, 19, 20]. ? ???? ???????????????? ??????? ????
???????????, ??? ? ?????? Angelica decurrens ??????-?????????? ??????????? ?????????????
???????? ??????????? ?????? ???????????? ????????????? ?? ????????? ??????. ??????????? ?????? ???? ????? ?? ?????????? ????? ????????-????????, ???????? ?????????? ??????
(???. 1). ?????? ??????-????????? ????????? ? ?????? ???????????.
??????? ? ???????????? ??????-????????? ???????? ????????? Angelica decurrens, ????????? ????, ????????? ????????????? ?????????? ??????????-??????????? ????????????
? ?????? Angelica archangelica ? ??????? ?? ?????????? ????? ????? ? ??????? ????? ???????# 594 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga S. Shchipitsyna and Alexander A. Efremov. Features of the Essential oil Accumulation in the Angelica Decurrens?
?
1
?
1
???. 2. ?????????? ????? ????????????? ????????? ?????? ???????????? ???? Angelica archangelica
L. ?. ????? (0,5 ?? ? ????????). ?. ????? (1,5 ?? ? ????????), ?????????? ?????????? ???????? ?????,
?????????? ?????????, ?????????? ?????? ?????? ? ???????? ??????. 1 ? ??????????? ?????? ??
????????? ??????. ??????? 1 ??
??? ???? ??? ?????? ?????????????? ??????????? ??????? ? ????????????? ????????? [9].
????? ????, ??????-????????? ????????? ????????? ?????? ??????? ???? Angelica decurrens
? ???????? ?????????, ????????????? ? ???????? ?????, ?????? ???????????? ???? Angelica
archangelica ????? ????????? (???. 2) [18].
??????????
??????????? ?????????? ?????????? ? ???????????? ?????? ???????? ????? ?? ??????
?????????? Angelica decurrens (Ledeb.) B. Fedtsch. (??????? ????????????), ??????????????
???????????? ???????? ???????? ??????????? ?-????? (21,8 %) ? ?-?????????? (16,3 %). ???
????????? ????????, ??? ? ??????? ????? ?? ?????? Angelica decurrens ? ???????????? ? ?????????? Angelica archangelica L. (??????? ??????????????) ??????????? ?????????? ?????? ????
?????????????? ??????????, ? ????? ????, ??? ????? ????? ?????? ?? ????????????? ???????
? ??????????? ?? ?????????? ? ?????? ???????? ?????: 0,3-0,6 % ? ????????? ? ???????????
?????.
?????????? ???????? ??????-????????? ????????? ?????? Angelica decurrens ? ??????????? ?????? ? ? ???????? ?? ???????????? ?????????? ???????????? ???? Angelica archangelica,
??? ?????? ?????????????? ?????????????? ??????????? ????????????? ?????.
????? ???????, ??? ????????????? ?????????? ? ?????? ????, ??? ??? Angelica decurrens
?????? ???????????? ?? ???? ?????????? ?????????? ??????? ? ????????????? ?????? ???
????????? ????? ????????????? ???????, ? ???? ??????????????? ?????? ?????????? ?????? ?
# 595 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Olga S. Shchipitsyna and Alexander A. Efremov. Features of the Essential oil Accumulation in the Angelica Decurrens?
???????????, ?????? ??? ????? ???? ???????????? ? ???????? ????????? ???????? ???????????? Angelica archangelica ??? ????????? ????????? ???????? ?????.
?????? ??????????
1. ????????? ?.?., ????????? ?.?., ??????????? ?.?. ???????? ???? ??????: ??????????
?????? ? ????????????????? ???????? // ????????. 2004. T. 4. ?. 46-48.
2. Bisset N. G., Wichtl M. Herbal Drugs and Phytopharmaceuticals. N.-Y., 2001. 708 ?.
3. ????????? ?.?. ??????? ????? ??? ?????????? ? ????????????. ?., 1999. 284 ?.
4. ??????? ?.?., ??????? ?.?., ?????? ?.?. ???????? ???????? ???????. ??????? ? ???????????. ???????????, 1989. 271 ?.
5. ?????? ?.?., ???????? ?.?., ???????? ?.?. ??????? ?????? ????????. ????????, 1989. 334 ?.
6. ??????? ?.?. ????????????? ???????? ??????. ???????????, 1991. 431 ?.
7. Lee S.-B., Rasmussen S.K. Molecular markers in some medicinal plants of the Apiaceae family
// Euphytica. 2000. V.114. ?. 87-91.
8. Weinert E. Die Taxonomische Stellung und das Areal von Angelica archangelica L. und A.
lucida L. // Feddes Repert. 1973. V. 84. P. 303-314.
9. ???? 21569-76?. ????????? ? ????? ?????? ??????????????. ?., 1976. 3 ?.
10. ????????????? ???????????? ?????. ????????????? / ??? ???. ?.?. ????????, ?.?. ????????. ???., 2004. 765 ?.
11. ??????????????? ?????????? ????: ????? ?????? ???????. ????????????? ???????????? ?????. ?. 1. ?., 1989. 400 ?.
12. ???? 24027.0-80. ????? ????????????? ????????????. ??????? ?????? ? ?????? ????.
?., 1999. 5 ?.
13. ???? 24027.2-80. ????? ????????????? ????????????. ?????? ??????????? ?????????, ?????????? ????, ????????????? ? ????????? ???????, ???????? ?????. ?., 1980. 12 ?.
14. ???????? ?. ?. ?????????? ?????? ????????????? ????????. ?., 1983. 176 ?.
15. ?????? ?.?. ???????????? ??????? ??????? ????????. ???????????, 2008. 969 ?.
16. ????? ?.?. ?????? ???????-???????????????? ???????????? ???????????? ??????: ?????. ???????. ?., 1979. 115 ?.
17. Shchipitsyna O.S., Efremov A.A. Composition of etheral oil isolated from various vegetative
parts of Angelica from the Siberian region // Russ. J. of Bioorg. ?hem. 2011. V. 37. ? 7. ?. 888-892.
18. Pasqua G. Monacelli B., Silvestrini A. In vitro root differenciation and essential-oil
accumulation in Angelica archangelica // In Vitro Cell. Dev. Biol. 2001. V. 37. ?. 763-766.
19. Upton R., Graff E., Jolliffe G. American Herbal pharmacopoeia. B.-R.: CRS Press, 2011. 800 p.
20. European Pharmacopoeia 6.0. Vol. 2. Strassbourg: Council of Europe, 2007. 2240 p.
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Journal of Siberian Federal University. Chemistry 4 (2014 7) 597-609
~~~
??? 544.472.2; 547.458.8
Development of Solid Acid Catalysts Based
on Sibunit Carbon Material for Cellulose Transformation
into 5-hydroxymethilfurfural
Nikolai V. Gromova,b,c, Artem B. Ayupova, Cyril Aymonierb,
Vladimir ?. Agabekovd and Oxana P. Tarana,e*
a
Boreskov Institute of Catalysis SB RAS
5 pr. Lavrentieva, Novosibirsk, 630090, Russia
b
Institut de Chimie de la Matiиre Condensйe de Bordeaux, CNRS
ICMCB, UPR 9048, 87, av. du Dr Schweitzer, Pessac, 33608, France
c
Universite Bordeaux
1, ICMCB UPR 9048, Pessac, 33600, France
d
Institute of Chemistry of New Materials NAS of Belarus
36 F. Skorina str., Minsk, 220141, Belarus
e
Novosibirsk State Technical University
20 pr. K. Marx, Novosibirsk, 630092, Russia
Received 04.11.2014, received in revised form 14.11.2014, accepted 24.12.2014
Solid acid catalysts based on graphite-like carbon material ?Sibunit-4? have been developed to be
utilized in the one-pot process of 5-hydroxymethylfurfural production from cellulose using oxidation
and subsequent oxidation-sulfonation methods. The samples of oxidized carbon have been produced
via oxidation of the carbon?s surface by water solutions of nitric acid or by wet air mixture; for oxidizedsulfonated samples to be produced oxidized carbons have been additionally sulfonated in fuming
sulfuric acid at 200 °?. The catalysts developed have been investigated by methods of low-temperature
nitrogen absorption and titration with NaOH and also tasted in the one-pot hydrolysis-dehydration
of mechanically activated cellulose under hydrothermal conditions of 180 °?. The total amount of
acidic groups (sulfo, carboxyl, lactone, and phenolic) for oxidized samples is comparable and for
the oxidized-sulfonated is 1.5-2 times higher than the amount of acid groups in the sibunit sulfonated
at 200 ° C. The activity of the catalysts with respect to sulfonated samples at 150 ° C and 200 ° C is
comparable. The yields of 5-HMF and glucose ranges of 17-20% and 38-42%, respectively.
Keywords: catalysis, cellulose,
5-hydroximethylfurfural.
*
sibunit,
oxidation,
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: oxanap@catalysis.ru
# 597 #
sulfonation,
hydrolysis,
glucose,
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
?????????? ??????? ????????? ?????????????
?? ?????? ??????????? ????????? ???????
??? ????????? 5-??????????????????????
?? ?????????
?.?. ???????,?,?, ?.?. ??????, ?. ??????,
?.?. ?????????, ?.?. ??????,?
?
???????? ???????? ??. ?.?. ????????? ?? ???
??????, 630090, ???????????, ??. ????. ???????????, 5
?
???????? ????? ???????????????? ???????
????? ????????????? ?????? ??????? ???????????? (????? ????),
UPR 9048, ???????? ??????? ????????, 87, ??????, 33608, ???????
?
??????????? ?????, ?????,
UPR 9048, ??????, 33600, ???????
?
???????? ????? ????? ?????????? ??? ????????
????????, 220141, ?????, ??. ?. ???????, 36
?
????????????? ??????????????? ??????????? ???????????
??????, 630092, ???????????, ??. ????? ??????, 20
??????? ????????? ???????????? ??? ?????????????? ???????? ?????????
5-?????????????????????? (5-???) ?? ????????? ???????????? ?? ?????? ????????????????
??????????? ????????? «???????-4» ???????? ????????? ? ????????????????? ?????????
? ?????????????. ??????? ??????????? ???????? ???????? ????? ????????? ???????
?????????? ??????? ??????? ??? ??????? ????????? ??????. ??? ????????? ???????????????????????? ???????? ?????????? ???? ???????????? ? ????????? ?????? ??????? ???
200 °?. ???????????? ??????????? ???????? ?????????????????? ????????? ?????, ????????????????? ?????????? NaOH ? ?????????? ? ????????????? ???????? ?????????-????????????
????????????????? ????????? ? ??????????????? ???????? ??? 180 °?. ????? ??????????
????????? ????? (??????-, ?????????????, ????????? ? ?????????) ??? ?????????? ????????
???????????, ? ??? ??????????-?????????????? ????????? ? 1,5-2 ???? ?????????? ?????????
????? ????????, ??????????????? ??? 200 °?. ?????????? ????????????? ???????????
? ?????????, ??????????????? ??? 150 ? 200 °?. ?????? 5-??? ? ??????? ??????????? ?
???????? 17-20 ? 38-42 % ??????????????.
???????? ?????: ???????, ?????????, ???????, ?????????, ?????????????, ????????, ???????,
5-?????????????????????.
????????
5-????????????????????? (5-???) ?????? ? ????? ???????? ????????????? ??????????
??????????, ??? ?????????? ???????-???????? (platform molecules), ?????????? ?? ????????# 598 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
?????? ???????? [1-4], ??? ??? ????? ???? ??????????? ? ???????? ????????? ????? ? ?????
???? ???????? ??????????????: ? ???????????? ??????? ???????, ?????????? ??????????,
?????????, ???????????? ? ???????????? ????????? [5, 6]. 5-??? ? ????????? ????? ??????????? ????? ???????????? ????????? (?????????? ????? ?????? ????????) ?????????????
[6-8], ? ???????? ??????? ? ????????, ??????????, ? ???? ???????, ?? ???????? ? ????????. ?
???????? ????????????? ????????? ????????? ???????? ? ???????? ???????????? ???? ???????? ??????? ??????????? ??????, ???? ?????????????? ???????????? [9-13]. ????????????
????????????? ? 5-??? ???????? ????? ? ??????????? ??????? ??????????? ??????, ???????????? ? ???????? ????????????? ? ?????????? ????????, ?????????? ???????????? ????????????, ??? ? ?????? ????????? ? ??????????? ???????? ????????? ???????? ??? ????????????? [14]. ????????????? ? ???????? ????????? ????? ?????????, ??????? ?????? ??????? ?
???????? ????????, ?????????? ?????????????? ?????????, ? ????? ???????????-????????
????????? ??? ????????????? ?????????????? ????????????? ????? ? ????????????? ?????????? ???????? ????????. ???, ? ????????? ????? ????????? 5-???, ? ??????????? ?? ???????, ?????????? ?? 100 ?? 1000 ???????? ??? ?? ?????????. ??????? ????? ????? ????????
??? ????????? ?? ?????????? ????? ???????? ?????? ???????.
????????? ??????????? ????????? (??????? ???????) ???????? ????? ?? ???????? ??????????? (?? 60 %) ?????????????? ??????????????? ????????????????? ????? [15, 16] ? ????? ???? ??????????? ? ???????? ??????????????? ????????? ????????? 5-???. ??????????
????????????? one-pot-?????????, ? ????? ????????????? ????????????? ??????? ?????????
?????????????, ??????????? ????????? ?????? ????????? ???????? ???????? ?? ????????????
? ????????? ?????????? ??????? ???, ????? ??????????? ?????????? ?????????? ???????????? ??????? ????????? 5-???.
????? ???????? ???? ??????? ????????? ?????????????? ?????? ???????????? ?? ?????? ?????????? ?????????? ?????????????? ???????? ??????????????, ????????? ?????????
???????? ?? ????????? ??????? ? ?????????? ???????? ???????? (?? 60 %) ? ??????? ?????????????? [17-26]. ? ?????????, ?????? ????????? ????? ?? ??????? ???????? ????????
??????????? ????????? 5-??? ?? ????????? ? ??????????? ?????????? ?????????????, ????
??? ?????? ???????? ??????????? ????????? ? 5-??? ? ???????? ????????? ? ???????, ??????????????? ??????? ?? ???????? ? ???????????? ???????? ? 5-??? ? ?????????? ??? ????????? ????????? ?????????????, ??? ??????????????? ? ???????????????? ?????????? ??????? ????????? ? ????????????? one-pot-???????? ??? ????????? ????????????? ?????????.
?????? ?????????? ????????? ???????? ?????? ????????????, ??????? ?? ??????????
????????? ???????????? ??? ??????????? ?? ??????????? ??????? ????????? ?????. ???????
????????? ????? (???????????, ????? ???????? ? ???????????? ??????????) ????????? ???????????? ??????? ?? ???????? ?????????? ?????????????. ????????, ?????????? ???????????
????????? ?????? ???????? ?????, ? ????? ???????, ? ????? ?????????? ??????????? ?, ???
?????????, ? ????? ?????????? ?????????????. ? ?????? ???????, ??? ????? ??????? ???????????? ?????????? ?????????? ???????? ?????????????? ?????, ????????????? ??????????
????????? ????????? ???????? [25]. ?????????????, ??? ??????? ??????????? ???? ???????????
????????? ?????????? ????????? ??????????? ?????? ? ??????? ?????????. ? ????? ??????
??????? ????????????? ???? ???????????? ?? ?????? ???????????????? ??????????? ????# 599 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
????? «???????-4», ??????????? ?????????? ???????? ????????????, ??????????? ????????????? ? ??????? ???????????? ?????????? [27, 28].
????? ?????? ?????? ???????? ?????????? ?? ?????? ???????? ??????????, ?????????????? ??????? ????????? ????????????? ????????? 5-??? ?? ?????????. ??? ????? ????
????????? ????????????? ???????????? ??????? ????????? ??????? ????????? ???????????
???????? (????????? ??????? ????????, ??????? ????????? ??????, ?????? ????????) ?? ?????????? ? ????????????? ?????????? ????????????? ? ??????????? ????????????? ????????
? ??????????????? ????????.
????????? ? ??????
? ?????? ?????? ??? ??????????????? ??????? ? ???????? ?????????? ???? ??????? ?????????????? ????????? ?????????? ???????? ????? «???»: H2SO4 (???????), NaOH
(Panreac), ????????? (??????? < 0,10 ??, ??? ??????, ?????-?????????), 5-?????????????????????, D-???????? (Sigma-Aldrich), D-??????? (Sigma-Aldrich), D-??????? (??????, ??????), D-?????????? (Alfa Aesar), ??????????? ??????? (Acros Organics). ????? (99,998 %, ????
10157-70, OAO «?????????», ???????????, ??????) ???? ? ???????? ????????? ???? ? ????????.
????, ????????? ?? ????????? Milli-Q (Millipore, ???????), ????????? ??? ?????????????
???? ????????????? ? ?????????.
?? ???? ?????? ???????????? ??????????? ?????????????? ????????? (?????? ??????
5±4 ??? ? ?? ?????? ?????????? ???????????, ??????? ??????????????? 30 % ? ?? ??????
???), ?????????? ????? ???????????? ????????? ???????????? ????????????????????
????????? (??????? < 0,10 ??, ??? «??????», ?????-?????????) ? ??????????? ????????
«?????????-4?», (??? «?????????» ?. ???????????, ??????) ?? ????????, ????????? ? ?????
?????????? ?????? [29].
??? ????????????? ???? ?????????? ????????????? ???????????? ???????????? ??????????????? ?????????? ???????? «???????-4» (???????? ??????? ??????????? ?????????????, ?. ????), ?????????????? ????????? ???????? ??????? ???????????????? ????? ???
???????? ????????? ???????? ???????? ? ?????????? ? ???? ?????? ??? 150 °?. ???????
?????????? ? ?????????? ?????? ? ???????? ??????? ? ???????? ?????????? ?????? 250?
500 ???.
??? ????????????? ?????????? ???????? c?????? ???????? ??????? ???????? ??? ??????? ????????? ??????.
??????? c???????, ?????????? ??????? ????????, ?????????? ?? ????????, ????????????? ?? ?????????? ?????? [30]. ??????? c??????? 25 ? ???????? ? ????? ? ???????? ?????????????, ????????? 75 ?? ??????? ???????? ??????? ??????? (23 ??.% ??? 35 ??.% HNO3). ?????
????????? ?? ??????? ???? ??? ??????????? 90 °? ? ??????? 2 ?. ?????????? ??????? ????????????? ????????? ??? ????????? ??????? ?????????????? ????? ?? ?????????? ? ?????????
????? ?????? ??????-?????, ??????? ??????? ?????????? ? ??????? ? ??????????????????
?????? ?? ???????? ???? 23268.9-78.
??? ????????????? ???????, ??????????? ??????? ???????? 50 ? ??????????? ?????????
«???????-4» ???????? ? ????????? ??????, ??????? ???????? ? ????, ? ????????? ??????? ?
??????? 0,5 ?. ????? ? ?????? ???????? ????? ??????? ????? 20 ??.% ?2 ? N2, ??????? ????????
# 600 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
?????? ???? ????????? ?? ????? ?????????, ???????????????? ??? 90 °?. ???????? ??????
????. ????????? ????????? ? ??????? 4 ? ??? 450 °? [31].
??????? ???????? ????? ????????? ?????? ??? 160 °? ? ???? ??????.
????????????? ??????????-?????????????? ???????? ???????? ????????? ????? ?????????????? ????????? ?????????? ???????? ????????? ?????? ???????? ? ???????????
????????, ??????????? ? ????? ?????? [29], ??? 200 °? ? ??????? 10 ?. ?????????? ???????
???????? ?? ?????? ??????? ???????????, ????????? ??????? ????? ?? ??????????? ????????
?? ????????? ??? ? ?????? ?? ???????.
??? ???????? ????? ???????????? ????????????? ????? ??? ??????? ????????????? ???????????? ? ??????????????? ????? ??? 190 °? ? ??????????? ????????????? ? ??????? 3 ?,
????? ???? ????? ???????? ?? ??????????? pH, ?????? ??? 150 °?.
?????????? ?????????????? ???????? ??????????? ?? ????????? ????????? N2 ??? -204 °C
?? ????????? ASAP-2400 (Micrometritics, ???). ??? ??????? ?????????????? ???????????? ? ??????? ??? 130?150 °C. ??????? ??????????? ???????????? ?? ?????? ??? ? ????????? STSA, ?
????? ????????????? ??????? (? ???????? ????????? ???????????? ????? Cabot BP 280). ????????????? ??? ?? ??????? ????????? ?? ????????? ???????? ???????? QSDFT ? NLDFT.
????????? ???????????? ??????? ????????? ?????: ?????????, ?????????, ????????????? ? ??????????? ? ?? ??????????? ?????????? ????????-???????? ??????????? ??????????? ?????? [32, 33]. ??? ????? ??????? ???? (0,5 ?) ?????????????? ? 20 ?? 0,2 ? ???????? ?????????? ?????? ? ??????????? ? ??????? ????, ????? ???????????????. ?? ????????
???????? ???????? 5 ??, ??????? ????????? ? 25 ?? 0,1 ? HCl, ??? ????????????? ?????????????????? ??????. ?????????? ??????? ????????????? ??????????? 0,2 ? ????????? NaOH
?? ?????????????? ????????? ???-02 («???????», ??????). ????????? ??? ???????????? ?????????, ? ?????????? ?????????. ?????????? ????????? ????? ?? ??????????? ?????????? ??
??????? ????? ??????????? ??????, ??????????????? ?? ???????? ????????? ? ??????????
?????????? ????????.
???????? ????????? ????????? ??? ??????????? 180 °C ? ????????? a????? ? ?????????
???????? ???????? (Autoclave Engineers, USA) ??? ??????????? ????????????? (1500 ??/???).
?????????? ????????? ? ???????????? ?????????? 10 ?/?. ??????? ????????? ? ????????????
???????? ? ???????, ????????? 45 ?? ????, ??????? ?????????, ????????? ??????? ??? ???????? ??????? ? ???????? ?????? ??????????? ?????. ????? ?????????? ??????????? 180 є?
(????? ?????????? ???? ??????????? ?????????? ???????? 30 ???) ???????? ??????? ?????.
? ???? ??????? ?? ????????? ???????????? (????? 1, 2, 3, 5 ?) ???????? ????? ???????????
????? ??? ???????.
?????? ????????? ??????????? ????? ????????? ??????? ???? ?? ????????????
Shimadzu Prominence LC-20, ????????????? ??????????????????? ? ??????????????? ???????????. ?????? ?? ?????? ?????????? ?? ??????? Rezex RPM-Monosaccharide Pb2+ (Phenomenex,
300 ?? * 5,0 ??), ?????????????????? ??? 70 °C; ??? ??????? ?????? ???????????? ???????
Rezex ROA-Organic Acids (Phenomenex, 300 ?? * 5,0 ??), ?????????????????? ??? 40 °C. ?
???????? ???????? ????????? ?????????? ?? ????????? 0,6 ??/??? ???????????????? ????,
?????????????? ?? ????????? Milli-Q (Millipore, ???????), ??? 1,25 ?? ??????? ???????? ?????? ???????.
# 601 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
?????????? ? ??????????
??? ????????? ????????? ?????????? ????????????? ?????????? ?????????, ????????
?????????????? ??????? [17-19], ?????????????? ????? [23-25], ?????????? ?????????? [26].
?????? ????? ????????? ?????????? ?????????? ???????? ????????????? ??????????? ???????????, ??? ?????? ??????????? ?? ?????????? ??? ??????????????? ?????? ?????????
??????????? ????????????, ??? ?????????. ??????? ???? ????????????? ???????????? ? ????? ???????? ?? ??????????? ??????? ????????? ?????. ????? ?? ????? ????????????????
??????? ??????????? ???????? ????????????? ? ????????? ??????????? ????????? ? ????????????????? ??? ????????? ?????? ??????? [17, 18, 20, 23, 25]. ???????? ????????????? ?????? ??????? ????????? ??????????? ????? ??? ????????? ??????????? ????????????? ????????? ????????? ??????????? ??????. ???, ?????? ?????? [25] ????????? ??????? ??????? ???
????????? ???????????, ????? ????, ???? ?????????????? ???????? ????????????, ??????????????? ???????????? ??????? ? ?????? ?????????. ?????????? ????????, ??? ??????????????
?????????? ????????? ????? ????????? ?????????? ??????? ???????????? ?? ????????? ?
????????? ????????? ?????????? ??????????? ? ??????????? ?????. ? [24] ???? ??????????
?????????? ???? ? ??????????? ????? ????? ???????, ??????? ????????? ????? 0,03 ?????/?,
??? ????????????? ??????????????? ????????? -SO3H ? ??????????? ????? (????? 0,7 % ????????? ?????????? ???? ? ????????????).
? ????? ?????? ??? ???????????? ??????? ????????? ??????? ????????? ?? ???????? ?????????? ????????????? ??????? ??? ?????? ??????????? ????????: ????????? ??????? ????????, ????????? ??????? ????????? ??????, ????????????? ????????? ?????? ????????.
???????? ???????????? ??????? ??????? ????????????? ???????? ?????? ???????? ?? ???????? ?????????? ????????????? ??????? ? ????? ?????????? ?????? [29], ? ??????? ???????
??????????? ??????????? ?????????????, ???????????? 200 °?. ????????? ???????? ??????
???????? ??? ?????? ??????????? ????????? ??????? ?? ??????????? ?????????? ??????? ?????????? ????????? ????? ??? ????????????? ?????????? ????????? ??????????? ?????????,
?????? ?????????? ??????????? ??????? ???????? ??????? ?????????????? ??????????. ?????? ????????? ???????? ??????? ???????? ? ??????? ????????? ?????? ??????? ?? ??????
??????????? ????? ?????????? ???????????? [31, 34], ??????????, ??? ????? ????????? ????????? ??????? ?? ??????????? ???????? ??????? ?????????? ??????? ????????? ????? (?????????????, ????????? ? ?????????) ? ??????????? ??????????? ?????????? ?????????.
?????????? ?????????? ??????? ????????????? ?????????????? ??? 200 °? ??? ???????????
?? ??????????? ???????????.
????? ??????? ???? ???????????? ??? ????? ?????????????. ?????? ????? ? ??????????
??????? ????????: 23 ? 32 % ?????????? ??????? ??????? ? ??????? ???????? (C-N23, C-N32
? C-O ??????????????). ?????? ????? ? ?????????? ? ?????????????? ????????????, ?????????? ?????????????? ?????????????? ?????????? ???????? (C-N23-S200, C-N32?S200 ?
C-O-S200).
???????????? ?????????? ????????????? ??????? ?????????????????? ????????? ?????
????????, ??? ??? ?????? ????????? ? ???????????? ????????????? ????? ? ?????????? ?????????? ????????? ????????. ????????? ??????? ???????? ????????? ???????? ???????
??????? ?? ????????? ? ?????????? ????????? ????????? (????. 1). ? ????? ?????????? ??# 602 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
??????? 1. ?????????? ?????????????? ???????? ????????? «???????-4», ?? ?????? ??????????????????
????????? N2 ? ???????????? ????????? ????? ? ????????, ???????????? ??????? ????????-?????????
?????????? ??????????? ??????
???????1
SBET,
?2/?
V???????, ??3/?
?????.?????,
?????/?
?????.?????·10 -4,
?????/?2
C-O
348
0.33
0.28
8.0
C-N-32
320
0.27
0.36
11.2
C-N-23
306
0.22
0.33
10.8
C-O-S200
343
0.30
0.49
14.3
C-N-32-S200
290
0.27
0.51
17.6
C-N-23-S200
299
0.23
0.49
16.4·
C
379
0.21
0.042
1.0
[29]
?-S150
360
0.222
0.32
8.8
[29]
?-S200
400
0.240
0.40
10.0
[29]
?????? ?????????????:
C-? ? ????????-4?, ?????????? ??????? ????????? ?????? ??? 420 °?,
C-N32 ? «???????-4», ?????????? 32 % v/v ????????? ??????? ??????? ??? 90 °?,
C-N23 ? «???????-4», ?????????? 23 % v/v ????????? ??????? ??????? ??? 90 °?,
C-?-S200 ? «???????-4», ??????????????? ?????????? ??????? ????????? ?????? ??? 420 °? ? ??????????????
????????? ?????? ???????? ??? 200 °?,
C-N32-S200 ? «???????-4», ??????????????? ?????????? 32 % v/v ????????? ??????? ??????? ??? 90 °? ?
?????????????? ????????? ?????? ???????? ??? 200 °?,
C-N23-S200 ? «???????-4», ??????????????? ?????????? 23 % v/v ????????? ??????? ??????? ??? 90 °? ?
?????????????? ????????? ?????? ???????? ??? 200 °?,
? ? ?????? ???????????????? «???????-4»,
C-S150 ? «???????-4», ?????????????? ??? 150 °?,
C-S200 ? «???????-4», ?????????????? ??? 200 °?
1
????????? ? ?????? ??? ??????????? ? ???? ?-O > C-O-S200 > C-N32 > C-N23 > C-N23-S200>
C-N32-S200. ?? ???? ?????????????? ????????????? ???????? ? ????? ???????? ??????????
??????????? ????????? ?? ????????? ? ??????????? ??????????? ????????? ? ????????????? (????. 1 ? [29]).
?????????? ???????? ??????????? ?????? ????????, ??? ????? ????????? ????? ?????
????????? ??????????? ?? 8·10 -4 ?? 11,2·10 -4 ?????/?2, ? ????? ???????????? ?????????????
?????????? ?? 14,3·10 -4 ? 17,6·10 -4 ?????/?2. ? ????? ????? ?????????, ??? ????? ??????????
????????? ????? ? ?????????? ???????? ???????????, ? ? ??????????-?????????????? ? 1,5-2
???? ?? ????????? ? ?????????????? ???????? ???????? ?-S200 (????. 1).
??? ???????????? ?????????? ??????????????? ????????????? ? ???????? ????????? ????
???????????? ???????????????????? ?????????, ?????????????? ?????????? ??? ??????????
??????????????? ????????? ? ??????????? ???????? ? ??????? 10 ??? ?? ?????? ???????? 5±4
??? ?????????? ????? ?????????? ?????? [29]. ???????????? ??????????? ? ????????? ???
??????????? 180 °? ? ????????? ??????. ?????? ???? ??????????? ??????, ?????????? ? ????
??????? ? ????? ?? ??????????, ??????????? ??????? ????, ??????? ??????????? ??????
???? ??????????. ????????? ?????????? ???????? ????????? 5-??? ? ???????; ?????????????? ? ?????????? ? ????????; ???????? ? ???????. ????? ????, ?????????? ???????????
????????? ????????? ?????????? ? ??????????? ??????, ???????????? ? ?????????? ?????# 603 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
??????? 2. ?????? ????????? ??????? ??????????????? ????????? ? ??????????? ??????? ??????????
?????????????. ??????? ???????: ???????????? ????????? ? ???????????? 10 ?/?, ????? ???????????
????? 45 ??, T = 180 °C, ????????? Ar, ???????????? ????? ??????? 5 ?
???????????? ??????
???????? ????????? ? ?????
?? ??????????
17.8
5
3.1
C-N32
38.6
2
20.3
5
1.1
C-N23
40.0
2
18.0
5
0.6
???????????
???????
3
??????????
???????
40.7
C-O
5-???
t, ?
5-???
???????
?????,
%
???????
????????
t, ?
???????
???????
?????,
%
??????????
????? ????????? ?? ????????? ???????, %
27.4
1.1
8.4
17.8
1.6
1.1
22.3
0.1
2.8
20.3
1.2
0.0
23.7
0.4
7.7
18.0
1.7
0.0
C-O-S200
43.7
2
17.2
5
0.0
34.5
0.5
6.6
17.2
1.3
1.6
C-N32-S200
42.8
3
17.6
5
1.1
31.9
0.0
4.8
17.6
1.2
4.6
C-N23-S200
42.6
3
15.9
5
2.9
15.3
0.0
7.6
15.9
2.5
0.6
C
0.0
5
0.0
5
0.0
0.0
0.0
0.0
0.0
0.0
0.0
?-S150
33.5
2
17.0
5
1.2
23.5
3.6
4.0
17.0
0.0
0.0
?-S200
45.9
2
21.5
5
1.0
18.9
6.0
9.7
21.5
0.0
0.0
????? 5-??? ? ??????????? ?????, ? ????????????? ???????? ??????? 1-2,5 % ? ?? 4,5 %
?????????????? ?? ???? ?????? (????. 2).
??????????? ??????????????? ??????? ???? ?????????? ???????? ?? ????????, ?????????????? ?? ???????????? ????? ????? ??????????? ????????? ? ?????? ????? ? ??????????? ????????? ?????????????, ?????????? ?? ???. 1 [35, 36]. ??-??????, ?????????? ????????
????????? ? ???????????? ??????????????; ??-??????, ???????? ?????????????? ?? ???????; ?-???????, ???????????? ??????? ?? ???????? ? ??????? ?? ??????? ????? ?? ?????????????? ??? ??????????; ?-?????????, ???????????? ???????? ? ???????????? 5-??? ????
????????? ? ?????????????. ?, ???????, ? ??????????? ??? ?? ????????? ????????????? ???????? ?????????? 5-??? ? ???????????? ??????????? ? ?????????? ??????. ???????, ??? ?
??????????? ???????????? ????????? ????????????? ??????????? ??????? ???????? ????????
????????? ???????, ? 5-??? ?? ????????????? ? ??????? [29]. ?????????? ???? ??????????
??????? ?????? 5-??? ??? ??????????? ??????? ??????? ??????????? ??????? ????? ????????????????? ? ????????????? ???? ????????? ????????? ????????? ? ??????????? ???????
????????? ?????????? ????????????? ?? ????????? ? ???????????? ?????????. ?? ????????, ??? ?? ?????????? ????????????? ???????? ????????? ??????? ?/??? ??????????????.
????? ??????????? ?? ??????????? ?????????? ??? ?? ??????????? ????????????, ??? ???????? ? ???????????? 5-???, ??????????? ????? ??????????? ???????????, ??? ???????????
? ?????????? ???????.
??? ????????????? ???????????? ???????? ?????????? ??????? ?????????? ? ????????
??????????????? ?????????, ???????? ?? ????????? ? ?????????????? ?????????, ?????????? ??????? ??????????. ??? ???????? ????????, ?????????? ??????? ????????, ?????????# 604 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
?????????
HO
HO
OH
O HO
O
O
HO
OH
OH
O HO
O
O
O HO
O
O
OH
OH
n
OH
??????????? ????????????? ? ??????????
HO
HO
HO
HO
OH
O HO
O
O
O HO
OH
HO
OH
HO
??????????
???????
???????
HO
OH
O
OH
OH
OH
HO
O
HO
HO
OH
OH
OH
???????????
????????
O
O
O HO
OH
OH
HO
OH
O
HO
HO
OH
OH
O
OH
OH
OH
-3H2O
????????????
????????
O
-3H2O
O
O
H
5-?????????????????????
O
HO
H
H
?
O
H
???????????
??????
O
+2H2O
??????????
???????
O
OH
H
OH
O
???. 1. ????? ????? ??????????? ????????? ? 5-??? [35, 36]. (?????? ??? ???????? ????????, ???????????? ?? ???????????? ??????, ?? ??????????????? ? ?????????????, ??????????? ? ?????? ??????)
??? ??????? ??????? ???????? ???????? 5-??? ? ??????? ?? ???? ?????????????, ??? ?????
????????? ???????????? ??????????? ????????? ????? ?? ?? ??????????? (????. 1). ??????
?????????????? ????? ?? ?????? ??????? ? 5-??? ???? ????????????? ? ??? ???????????????????????? ????????, ???????? ?? ?? ??? ????? ?????????? ????????? ????? ?? ??????????? ? ?????? ???????? ? ??????? ? 1,5 ???? ??????, ??? ? ?????????? ?????????????. ?
??????? ???????? ??????? 5-??? ? ??????? ???????????????? ?????????? ? ????????? 17-20
? 38-42 % ?????????????? (????. 2).
????????? ?????????? ????????????? ?????????? ? ??????????-?????????????? ????????????? ? ????????? ????????, ??????????????? ??? ????????? ????????????, ????????,
??? ?????????? ?????????????, ?????????????? ? ?????? ??????, ????????? ? ????????? ?????
# 605 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
????????? ????????, ??????????????? ??? 150 ? 200 °? (????. 2). ?????????? ???? ?????????? ??????????? ? ????????????? ???????. ???, ? ?????? [25] ???? ???????? ??????????????
(1,6 %) ???????? ??????? ??????? ? ??????????? ???????? ????????? ????, ???????????????
??? 250 °?, ? ??????? ????, ??????????????? ??????????? ??????? ???????? ? ???????????????
??? ??? ?? ???????????.
???????????? ????? (20,3 %) 5-??? ??????? ? ??????????? ??????? C-N32, ???????????
32 %-??? ??????? ????????. ???????????? ????? ??????? (43,7 %) ? ? ??????????? ???????????? C-O-S200, ??????????? ??????? ???????? ? ???????????????. ?????? ??? ?????????? ??
????????? ???????????, ?????????? ??? ???????????? ?-S200, ??????????????? ??? 200 °?,
??????? ????????? 21,5 ? 45,9 % ??? 5-??? ? ??????? ??????????????.
????? ???????, ??????? ??????????? ????? ? ??????? ??????? ?????????? ?? ????????
?????????? ?????????? ????????????? ??? ?? ???????. ??? ?????????? ?????????? ???????
????????????? ?????????? ????????????? ?? ?? ??????????, ???????? ?? ???????? ??????????
?????????? ????????? ?????, ?????????? ?????????????? ????????????. ? ?????????, ????????? ????? ????????? ???????? ??????????? ??????? ?????????????? ????? ? ??????? ???????????? ? ??????????? ?? ??????? ?? ?????????????? ?????????? ? ????????????? ??????????
??????????. ????????? ? ????????? ???? ??????? one-pot-???????? ???????????? ??????????
????????? ???????, ?????????????? ?????????? ???????? ????????????, ?? ?????????? ????
??? ????? ?????? ? ?????????? ??????? ????? ???? ?????????. ????? ????, ???????? ???????????? ??????? ????????? ????????????? ?? ????????????? ??????? ?? ????????? ???????? ? ????????????? ????????. ???, ????????, ???????? ????? [20, 21] ???? ????????? ???????????? ???? ????????? ????? ????????? ???????: -SO3H, -COOH, -OH ? ???????? ?????????
????????? ? ???????????, ??? -OH ?????? ?????? ???????????? ???? ? ????????? ??????????? ?????????????? ????? ??????????? ?????????? ?????? ????? ????????????? ??????? ??
??????????? ???????? ? ?????????? ?-1,4-??????????? ?????. ? ????????, ??-????????, ?????????????? ?? ??????????? ???????????? ?????????? ???????? ??????????????? ???? -SO3H
? -COOH.
??????????
????????? ????????????, ???????????? ?? ???????? ?????????????? ? ???????????
??????? ????????? ????????????? ??????? ?? ????????? 5-???, ??????????? ?????? ?????????? ???????????. ???????????? ??????????????? ?? ?????? ????????????? ???????????????? ????????? «???????-4», ????????????? ??????? ??????????. ? ????? ???????????
???????????? ?????? ???????? ????????????? ????????? ????? ??????? ???????? ???????
???????? ??? ??????? ????????? ??????, ? ????? ????????????? ???????????? ?????????
?????? ????????. ?????????? ???????????? ??????????? ???????? ?????????????????? ????????? N2 ? ????????-????????? ?????????? ??????????? ??????, ? ?? ?????????????? ???????? ?????????????? ? ???????? ????????????? ??????????????? ??????????? ?????????????? ???????????????????? ?????????. ?????????? ?????????? ?????????? ? ????????????
???????????? ??????????????? ???????? [29].
??? ?????? ????????????? ????????? ??????????? ?????????, ?????????????? ? ??????
??????, ????? ? ??? ??????????, ? ?????????????? ????????????? ????????? ?????????? ??# 606 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
???????. ????? ?????????? ??????? ????????? ????? (??????-, ?????????????, ????????? ?
?????????) ??? ?????????? ???????? ???????????, ? ??? ??????????-?????????????? ????????? ? 1,5-2 ???? ?????????? ????????? ????? ???????? ?????????????? ???????????????
??? 200 °? ????????.
?????????? ???????????? ???????? ?????????? ?????????????, ???????????? ????? ????? ? ?? ????????? ? ????????, ?????????????? ??? 150 ? 200 °?. ???????? ??????? 5-???
? ??????? ??????????? ? ???????? 17-20 ? 38-42 % ??????????????. ??? ?????????? ??????????? ??????????? ?????????? ?????????? ?????????????? ????????????, ???????????? ??
????????? ????????? ???????????? ???????? ? ????????????? ? ??? ???? ????????? ?????
????????? ?????????? ???????.
?????????? ????????? ???????????? ???????? ?????????????? ?????????? ??????
??????????????? ???????????? (????? 12-03-93116-?????_?), ?????????????? ???????? ?? ???-??? ???????? ? 24, ??????? ?????????? ?? ??? ????????? ??????? ??????? ???? ??-1183.2014.3., ?????????-??????????? ??????? ???????????? «????????».
?.?. ?????? ???????? ????????? ????????????? ?????????? ??????? ? ?????? ?? ???????????? ?????????.
?????? ??????????
1. Werpy T., Peterson G. Top Value Added Chemicals From Biomass. Volume I: Results of
Screening for Potential Candidates from Sugars and Synthesis Gas. / ????? ?? ?????? ???????????? ?????????? ??? - 2004. ????? ???????: http://www.energy.gov/eere/bioenergy/downloads/
top-value-added-chemicals-biomass-volume-i-results-screening-potential
2. ???. 8772515 B2 ???, ??? C07D307/48. Method to convert biomass to 5-(hydroxymethyl)furfural (HMF) and furfural using lactones, furans, and pyrans as solvents / Dumesic J.A. et. al.;
????????? ? ???????????????? Wisconsin Alumni Research Foundation. - ?????. 08.07.2014.
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7. ???. 4339387 ???, ??? C07D307/46. Process For Manufacturing 5-Hydroxymethylfurfural
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hydrothermal treatments of sawdust and cellulose // Journal of Supercritical Fluids. 2009. V. 50. P. 121?127.
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Journal of Siberian Federal University. Chemistry 4 (2014 7) 597-609
~~~
??? 544.472.2; 547.458.8
Development of Solid Acid Catalysts Based
on Sibunit Carbon Material for Cellulose Transformation
into 5-hydroxymethilfurfural
Nikolai V. Gromova,b,c, Artem B. Ayupova, Cyril Aymonierb,
Vladimir ?. Agabekovd and Oxana P. Tarana,e*
a
Boreskov Institute of Catalysis SB RAS
5 pr. Lavrentieva, Novosibirsk, 630090, Russia
b
Institut de Chimie de la Matiиre Condensйe de Bordeaux, CNRS
ICMCB, UPR 9048, 87, av. du Dr Schweitzer, Pessac, 33608, France
c
Universite Bordeaux
1, ICMCB UPR 9048, Pessac, 33600, France
d
Institute of Chemistry of New Materials NAS of Belarus
36 F. Skorina str., Minsk, 220141, Belarus
e
Novosibirsk State Technical University
20 pr. K. Marx, Novosibirsk, 630092, Russia
Received 04.11.2014, received in revised form 14.11.2014, accepted 24.12.2014
Solid acid catalysts based on graphite-like carbon material ?Sibunit-4? have been developed to be
utilized in the one-pot process of 5-hydroxymethylfurfural production from cellulose using oxidation
and subsequent oxidation-sulfonation methods. The samples of oxidized carbon have been produced
via oxidation of the carbon?s surface by water solutions of nitric acid or by wet air mixture; for oxidizedsulfonated samples to be produced oxidized carbons have been additionally sulfonated in fuming
sulfuric acid at 200 °?. The catalysts developed have been investigated by methods of low-temperature
nitrogen absorption and titration with NaOH and also tasted in the one-pot hydrolysis-dehydration
of mechanically activated cellulose under hydrothermal conditions of 180 °?. The total amount of
acidic groups (sulfo, carboxyl, lactone, and phenolic) for oxidized samples is comparable and for
the oxidized-sulfonated is 1.5-2 times higher than the amount of acid groups in the sibunit sulfonated
at 200 ° C. The activity of the catalysts with respect to sulfonated samples at 150 ° C and 200 ° C is
comparable. The yields of 5-HMF and glucose ranges of 17-20% and 38-42%, respectively.
Keywords: catalysis, cellulose,
5-hydroximethylfurfural.
*
sibunit,
oxidation,
© Siberian Federal University. All rights reserved
Corresponding author E-mail address: oxanap@catalysis.ru
# 597 #
sulfonation,
hydrolysis,
glucose,
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
?????????? ??????? ????????? ?????????????
?? ?????? ??????????? ????????? ???????
??? ????????? 5-??????????????????????
?? ?????????
?.?. ???????,?,?, ?.?. ??????, ?. ??????,
?.?. ?????????, ?.?. ??????,?
?
???????? ???????? ??. ?.?. ????????? ?? ???
??????, 630090, ???????????, ??. ????. ???????????, 5
?
???????? ????? ???????????????? ???????
????? ????????????? ?????? ??????? ???????????? (????? ????),
UPR 9048, ???????? ??????? ????????, 87, ??????, 33608, ???????
?
??????????? ?????, ?????,
UPR 9048, ??????, 33600, ???????
?
???????? ????? ????? ?????????? ??? ????????
????????, 220141, ?????, ??. ?. ???????, 36
?
????????????? ??????????????? ??????????? ???????????
??????, 630092, ???????????, ??. ????? ??????, 20
??????? ????????? ???????????? ??? ?????????????? ???????? ?????????
5-?????????????????????? (5-???) ?? ????????? ???????????? ?? ?????? ????????????????
??????????? ????????? «???????-4» ???????? ????????? ? ????????????????? ?????????
? ?????????????. ??????? ??????????? ???????? ???????? ????? ????????? ???????
?????????? ??????? ??????? ??? ??????? ????????? ??????. ??? ????????? ???????????????????????? ???????? ?????????? ???? ???????????? ? ????????? ?????? ??????? ???
200 °?. ???????????? ??????????? ???????? ?????????????????? ????????? ?????, ????????????????? ?????????? NaOH ? ?????????? ? ????????????? ???????? ?????????-????????????
????????????????? ????????? ? ??????????????? ???????? ??? 180 °?. ????? ??????????
????????? ????? (??????-, ?????????????, ????????? ? ?????????) ??? ?????????? ????????
???????????, ? ??? ??????????-?????????????? ????????? ? 1,5-2 ???? ?????????? ?????????
????? ????????, ??????????????? ??? 200 °?. ?????????? ????????????? ???????????
? ?????????, ??????????????? ??? 150 ? 200 °?. ?????? 5-??? ? ??????? ??????????? ?
???????? 17-20 ? 38-42 % ??????????????.
???????? ?????: ???????, ?????????, ???????, ?????????, ?????????????, ????????, ???????,
5-?????????????????????.
????????
5-????????????????????? (5-???) ?????? ? ????? ???????? ????????????? ??????????
??????????, ??? ?????????? ???????-???????? (platform molecules), ?????????? ?? ????????# 598 #
Copyright ??? «??? «??????» & ??? «A???????? K????-C?????»
Nikolai V. Gromov, Artem B. Ayupov? Development of Solid Acid Catalysts Based on Sibunit Carbon Material?
?????? ???????? [1-4], ??? ??? ????? ???? ??????????? ? ???????? ????????? ????? ? ?????
???? ???????? ??????????????: ? ???????????? ??????? ???????, ?????????? ??????????,
?????????, ???????????? ? ???????????? ????????? [5, 6]. 5-??? ? ????????? ????? ??????????? ????? ???????????? ????????? (?????????? ????? ?????? ????????) ?????????????
[6-8], ? ???????? ??????? ? ????????, ??????????, ? ???? ???????, ?? ???????? ? ????????. ?
???????? ????????????? ????????? ????????? ???????? ? ???????? ???????????? ???? ???????? ??????? ??????????? ??????, ???? ?????????????? ???????????? [9-13]. ????????????
?????????
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