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Russian- French Laboratory of Membranes and Technologies of Molecular
Selective Processes RFL Nikolai PLATÉ
THE MEMBRANES AND MOLECULARSELECTIVE SEPARATION PROCESSES
organized by
A.V.Topchiev Institute of Petrochemical Synthesis, RAS
and
Ecole Nationale Supérieure des Industries Chimiques
Laboratoire des Sciences du Génie Chimique
TIPS RAS
Moscow, Russia
October 7th-10th, 2008
Content
Cooperation stages ………………………………………………………..3
Russian-French Laboratory (RFL Nikolai Platé)……………………….7
5th Russian-French seminar program……………………………………8
Abstracts of presentations………………………………………………13
2
COOPERATION STAGES
of TIPS RAS (Moscow, Russia) and INPL (Nancy, France):
Cooperation projects:
1998-2002 - INCO grant «New membranes and integrated hybrid membranes systems for
VOC’s recovery from industry », IC15-CT98-0140
2002-2004 - INTAS Grant Ref n°. 2000 – 00230 «Synthesis and study of the molecular
properties and the sub-molecular organisation of new high permeability polymeric materials
based on unsaturated silyl hydrocarbons enhanced with selective transfer properties towards
organic gases and vapours”
2005-2007 - RFBR-CNRS (France) №05-03-22000 «Smart separation processes with
perspective polymeric materials».
2006-2009 - National French project ANR-06-CO2-002-05 «СО2 removing from gas media
and the utilization”
2007-2010 - Russian–French laboratory of membranes and molecular-selective
technologies « RFL Nikolai PLATÉ »
French – Russian Seminars
SMART MEMBRANE PROCESSES AND ADVANCED MEMBRANE MATERIALS
2005, 2005, 2006, 2007
A.V. Topchiev Institute of
petrochemical Synthesis RAS
Moscow State University
Ecole Nationale Superieure
des Industries Chimiques
TIPS RAS
3
I Russian-French Seminar: Kliazma, Moscow, 8-9 October, 2004
II French-Russian Seminar: Nancy, 16-19 June 2005
4
April, 2006: Work meeting at Moscow State University
III French-Russian Seminar: Moscow, October 2006
5
IV French-Russian Seminar: Nancy, 15-17 October 2007
Laboratoire franco-russe des membranes et génie des procédés de séparation moléculaire
LFR Nikolai PLATÉ, December, 2007
6
Academician Nicolai Platé
(04/11/1934 – 16/03/2007)
International Associated Laboratory (IAL)
RUSSIAN –FRENCH LABORATORY OF MEMBRANES AND MOLECULAR-SELECTIVE
TECHNOLOGIES « RFL NIKOLAI PLATÉ »
established by A.V.Topchiev Institute of Petrochemical Synthesis (TIPS RAS) and le
Laboratoire des Sciences du Génie Chimique (LSGC - CNRS)
with support of: Russian Academy of Science (RAS), Russian Foundation of Basic Researches
(RFBR) and le Centre national de la recherche scientifique (SNRS)
SCIENTIFIC TOPICS
The following scientific themes were selected with regard to skills, common interests and
complementarities of the two Institutes in order to improve knowledge and get added-value for
each team:
I
Membranes and energy: highly permeable materials and highly selective for recovery
of energy vectors from various technological gas mixtures and purification of associated
gases.
II Membranes and environment: development of selective processes of air treatments for
the reduction of greenhouse gases effects and of organic vapor emissions.
III Membrane technologies in the chemical and petrochemical industry: functional
materials, membranes and catalyses membrane for chemical and petrochemical
processes.
7
PROGRAM OF 5TH RUSSIAN-FRENCH SEMINAR
Invited persons:
S.Khadzhiev, academician, Director of TIPS RAS
P-B. Ruffini, Conseiller pour la Science, la Technologie et l ’Espace
M.Tararine, Attaché pour la Science et la Technologie
V.Mayer, Head of CNRS Moscow office
C. Barrault, Chargee de mission pour la Science
G.Tereschenko, academician, Head of Membrane Centre at TIPS RAS
M.Sardin, Head of Chemical Engineering Laboratory, CNRS, Nancy-University
S. Turin, Department of Foreign Relations RAS
G. Shiriaeva, Deputy Director of International Relations of RFBR
List of French participants:
Laboratoire des Sciences du Génie Chimique (UPR 6811):
1. Prof. Michel Sardin, director
2. Prof. Eric Favre,
3. Dr. Denis Roizard,
4. Dr. Danielle Barth,
5. Dr. Eric Shaer,
6. Dr. Noureddine Boucif
Doctorants of LSGC:
7. Jacques Grignard, 3rd year PhD Student
8. Alexandre Scondo, 3rd year PhD Student
9. Wey Lu, 2nd year PhD Student
10. Ayman El-Gendi, 2nd year PhD Student
11. Fleur-Lise Nguyen, 2nd year PhD Student
List of Russian participants:
A.V.Topchiev Institute of Petrochemical Synthesis Institute, RAS:
Laboratory of Physical-chemistry of membrane processes:
1. Prof.Vladimir Teplyakov, Head of laboratory
2. Dr. Daria Syrtsova, Senior Researcher
3. Dr. Maxim Shalygin, Senior Researcher
4. Dr. Lyudmila Gasanova, Researcher
8
5. Anastasia Golub, Junior Reseacher
6. Vyacheslav Zhmakin, 1st year PhD student
7. Olga Amosova, 3rd year PhD student
8. Anastasia Rogacheva, 2nd year PhD student
9. Roman Yastrebov, 2nd year PhD student
10. Roman Grinberg, diploma student
Laboratory of Synthesis of selective-permeable polymers:
11. .Prof.Valeriy Khotimskiy, Head of laboratory
12. .Elena Litvinova, Senior Researcher
13. .Dr. Samira Matson, Researcher
14. Alexander Masalev, 3rd year PhD student
15. Yuliya Kiruhina, 2nd year PhD student
16. Eldar Sultanov, 3rd year PhD student
Laboratory of catalityc nanotechnologies :
17. Prof. Mark Tsodikov, Head of laboratory
18. Alexey Fedotov, 2rd year PhD student
M.V.Lomonosov Moscow State University:
19. Elmira Saddradinova, 3rd year PhD student
20. Oleg Malykh, 2st year PhD student
Voronezh State University:
21. Alexey Bukhovets, 1st year PhD student
R.E. Alekseev Nizhny Novgorod State Technical University:
22. Dr. Ilia Vorotyntsev
Acknowledgments
The financial supports of this seminar were provided by Russian Foundation of Basic
Researches (the Grant CNRS-RFBR 08-03-92550) and French Embassy in Moscow. Organize
committee of Seminar warmly acknowledged Vladimir Mayer (Moscow CNRS office), Michel
Tarrarrine and Presidium of RAS for their continuous help.
9
Program of Sessions
October 7th
Arrival of the Seminar participants to Moscow
October 8th
10.00 - Lab tour to TIPS RAS,
Discussion of LIA Program
14.00 - Bus to Foresta Tropicana Hotel (from TIPS)
17.00 – Registration of participants in Foresta Tropicana Hotel (near Moscow)
18.00 – 18.30 -Opening ceremony. Opening address.
S.Khadzhiev, academician, Director of TIPS RAS
M.Tararine, Attaché pour la Science et la Technologie
G.Tereschenko, academician, Head of Membrane Centre at TIPS RAS
M.Sardin, Head of Chemical Engineering Laboratory, CNRS, Nancy-University
Session I- Chairing person: prof. V.Teplyakov
18.40-19.20 - D. Roizard The Scientific research activity in the frames of Russian –French
laboratory RFL Nikolai PLATÉ
19.20-19.40 - Meeting of Scientific Council of Russian- French Laboratory of membranes and
technologies of molecular selective processes RFL Nikolai PLATÉ
19.40-21.00 - Welcome party
October 9th
Session II- Chairing person: Prof. M. Sardin
10.00-10.20 - E. Favre, The prospects of membrane gas separation technologies
10.20-10.30 – R. Yastrebov, Analysis of published data on mass-transfer processes in membrane
contactors
10.30-10.40 – P.-T. Nguyen, Experimental study on hollow fiber membrane contactor:
determination of permeability
10
10.40-11.00 - M. Shalygin, Modeling of recycling membrane contactor system with aqueous
potassium carbonate for CO2 recovery from gas mixtures
11.00-11.20 - N. Boucif, Nonisothermal absorption of carbon dioxide into hollow fiber contactor
11.20-11.40- coffe-breake
Session III - Chairing person : Prof. M.Tsodikov
11.40-12.00 - E. Schaer, CFD simulation of a photocatalytic reactor
12.00-12.10 - A. Fedotov, Dry methane reforming on porous catalytic membranes
12.10-12.40 - M. Sardin, Pollutant transfer and transport in natural porous media: a multi-scale
approach
12.40-12.50 - W. Lu, Amino acids and peptides separation by a process coupling ion exchange,
carbonic acid elution and electroregeneration.
12.50-13.00 - A. Buhovets, Transport of aromatic amino acids during electrodialysis
13.00-14.30- lunch
Session IV - Chairing person: Prof. D. Roizard
14.30-14.50 - V.Teplyakov, New membrane materials and methods of permeability prediction of
polymers
14.50-15.10 - D.Syrtsova, The influence of macrostructure of foils based on exfoliated graphite
on gas permeance
15.10-15.20 - E. Sultanov, Synthesis of diblock copolymers of 1-trimethylsilyl-1-propyne with
4-methyl-2-pentyne through sequential living polymerization by NbCl5 based
catalysts
15.20-15.30 - A. Masalev, Bromination and crosslinking of PVTMS
15.30-15.40 - J. Grignard, Preparation and properties of nanocomposite membranes based on
rubbery poly(ether imide) and SiO2
15.40-15.50 - Y. Kiryukhina, Functionalized polymers for CO2 selective membranes.
Investigation of introduction reactions of low-molecular polyethylenglycol ethers
and «ionic liquids» group in Si-containing polymers
15.40-15.50 - A. El-Gendi, Asymetric polyimides membranes for pervaporation separations
11
16.00-16.30- coffee –break
Session IV - Chairing person: Prof. E. Favre
16.30-16.50 - I. Vorotyntsev, High purification of fluorocarbons by membrane gas separation
16.50-17.00 - O. Malyh, New aspects of gas permeability parameters correlations for prediction
of membrane properties
17.00-17.10 - A. Scondo, Phosphine imide reaction in supercritical CO2: Modeling and
Applications Discussion of perspectives of membranes technologies, development
of new materials and molecular-selective chemical technologies
17.10-17.30 - D. Barth, High-pressure magnetic suspension balance and supercritical carbon
dioxide
17.30-17.40
-
O.Amosova,
membrane/PSA
method
for
hydrogen
recovery
from
multicomponents gas mixtures of biotechnology and petrochemistry
17.40-18.00 - Discussion of perspectives of membranes technologies, development of new
materials and molecular-selective chemical technologies. Closing Ceremony.
19.00- Seminar Dinner
October 10th
10.00-12.00 – Round table of young scientists: Discussion of Russian and French curses for
PhD; job opportunities and carriers for young Russian/ French scientists
13.00-15.00 - lunch
15.00 - departure from the hotel to Moscow
17.00- Lab tour to TIPS RAS
October 11th
10.00-12.00 - Visit of Seminar participants to Moscow State University, Department of
Chemical Technology and New Materials
12.00 - city tour, visit to Kremlin
October 12th
Departure from Moscow
12
ABSTRACTS OF PRESENTATIONS
13
ANALYSIS OF PUBLISHED DATA ON MASS-TRANSFER PROCESSES
IN MEMBRANE CONTACTORS
R. Yastrebov
Laboratory of physical-chemistry of membrane processes,
A.V.Topchiev Institute of Petrochemical Synthesis RAS,
29 Leninskii prospect, 119991 Moscow, Russia; Tel: +74959554222; email: [email protected]
Introduction
In present time great attention is focused on ecological problem and on problem of biogas
separation. One of the ways for solution of this problem is extraction of CO2 from different gas
mixtures and its further utilization. It is offered to use recycling gas-liquid membrane contactors
(MC) as separation devices for CO2 extraction. MCs combine advantages of absorptive and
membrane methods of separation. Main problems that arising with development of such gasliquid membrane systems are: creation of superpermeable non-porous membranes, selection of
effective liquid absorbent and organization of mass transfer in gas-membrane-liquid system.
Results
Analysis of literature data on membrane contactors was carried out. Main attention in the work is
focused on influence of different experimental parameters, such as wetting of porous membrane,
gas and liquid absorbent flow rates, temperature, co-current and counter-current orientation of
gas and liquid flows on mass-transfer in membrane contactor. Almost all the studies of MCs
were carried out using porous membranes in order to reduce mass transfer resistance.
Unfortunately it was found that utilization of porous membrane often leads to significant
reduction of overall mass transfer coefficient due to the wetting of membrane pores. This
phenomenon may arise even if membrane material is highly hydrophobic. For example for
polypropylene membrane reduction of mass transfer reaches 20% if membrane pores wetting is
equal to 5% [1]. Example 2: if pore wetting increase to 100%, reduction of mass transfer reaches
is more than 60% [2]. Utilization of non-porous membrane can help to avoid this problem. At the
same time non-porous membrane introduce additional mass transfer resistance [3]. Analysis of
such data is very important and helpful for the development of new highly efficient membrane
contactors and shows that search and utilization of highly permeable non-porous membranes for
MCs should be priority task.
References
1. Wang R., Zhang H.-Y., Feron P.H.M., Liang D.T., Influence of membrane wetting on CO2
capture in microporous hollow fiber membrane contactors, Separation and Purification
Technology 46 (2005) 33-40.
2. M. Al-Marzouqi, M. El-Naas, S. Marzouk, N. Abdullatif, Modeling of chemical absorption
of CO2 in membrane contactors, Separation and Purification Technology 62 (2008) 501-508.
3. Al-Safar H.B., Ozturk B., Hughes R., A comparison of porous and non-porous gas-liquid
membrane contactors for gas separation, Chem. Eng. Res. Design 75 (1997) 685-692.
Acknowledgements
This work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, Grant RFBR
No. 07-03-00752 and Goscontract No. 02.516.11.6043.
14
Experimental study on hollow fiber membrane contactor:
determination of permeability
P.T. Nguyen1, D. Roizard1, E. Favre1
1
Laboratoire des Sciences du Génie Chimique (CNRS UPR 6811) ENSIC-INPL, 1 rue
Grandville, 54 001 Nancy, France
email: [email protected]
Aim
In order to reduce greenhouse gases emissions, different technologies for capture and removal of
CO2 are currently developed. One promises method is the use of hollow fiber membrane
contactor. Numerous studies on this technology have been done and the mass transfer coefficient
in the different parts have been calculated (kl on the liquid side, kg on the gas side and km in the
membrane). The coefficients kl and kg are, most of the time, determined by correlation and km is
then deduced. However, the correlation in the liquid side depends strongly of the polydispersity
and of the spatial arrangements [1] which leads to numerous correlations with a wide range of
values. This work aimed to test different methods and set up to determine the permeability of
membrane in order to directly obtained km and avoid the use of correlation to calculate kl.
Methods
Permeability tests have been done on flat sheets of PTMSP and PDMS with the time lag method.
The set up for time lag experiments is shown in figure 1: vacuum is created in the whole cell and
then, gas is injected upstream; the evolution of the pressure downstream is recorded. The set up
and the method for the calculation of the permeability will be detailed.
Figure 1: set up for time lag experiments
Two different methods were tested to determine the permeability of hollow fibers and km could
directly be deduced:
- first method: pure CO2 is injected inside the fibers at high pressure and the pressure in the shell
side is 1 atm, the increase of CO2 flow rate in the shell side is measured (figure 2)
Figure 2:set up for difference of pressure experiments
- second method: a sweeping of N2 is sent in the shell side with injection of pure CO2 inside the
fibers at 1 bar (figure 3). The evolution of CO2 flow rate is also recorded.
15
Figure: set up for N2 sweeping experiments
These methods will be explained in more details and the drawbacks of each one will be
highlighted.
Results
The permeability measured for flat sheets of PTMSP (from 20 000 to 40 000 barrer) and PDMS
(4200 barrer) are in accordance with literature data which allowed us to validate our apparatus.
We would like to test a set up which could directly measure the permeability in hollow fiber
membrane contactor and see if the results for flat sheet could be extrapolated for hollow fibers.
The experiments on hollow fibers give a precise range of value for the permeability (between
1800 and 2600 barrer for PDMS) and are in the same order of magnitude than those obtained
with flat sheets. However the experiments still need to be improved and more experiments are
necessary.
Conclusion
Experiments on PDMS have been done for flat sheets and hollow fibers. The results are in the
same order of magnitude but are still different maybe because of a difference of the polymer. For
the moment, it is not possible to extrapolate results of flat sheets for hollow fibers, more data are
necessary (for example with PTMSP hollow fibers). The set up for time lag method is validated
but the experiments for hollow fibers permeability need improvements.
References
[1] Jing-Liang Li, Bing-Hung Chen, Review of CO2 absorption using chemical solvents in
hollow fiber membrane contactors, Separation and Purification Technology, 41 (2005) 109-122.
16
MODELING OF RECYCLING MEMBRANE CONTACTOR SYSTEM
WITH AQUEOUS POTASSIUM CARBONATE
FOR CO2 RECOVERY FROM GAS MIXTURES
M.Shalygin
Laboratory of Physical Chemistry of Membrane Processes,
A.V.TOPCHIEV Institute of Petrochemical Synthesis RAS, Russia
29 Leninskiy prospect, 119991 Moscow (Russia). Tel: +74959554229; email:
[email protected]
The recovery of CO2 from gas mixtures is important problem nowadays. CO2 recovery from gas
mixtures can be applied in such processes as biogas separation, enrichment of biohydrogen, post
combustion capture of CO2. High level of gas mixture purification and low losses of other
components are usually should be achieved in these cases. Therefore, separation process should
be highly selective. Another important requirement is low consumption of energy. Gas-liquid
membrane contactor (GLMC) is proposed as separation device which can satisfy both
requirements. GLMC unites advantages of absorption methods of separation such as high
selectivity and wide list of absorbents with advantages of membrane methods of separation such
as high, determined and constant exchange area. GLMC is a device where gas and liquid phases
are presented and separated by a membrane.
Recycling system based on two GLMCs is suggested for separation of CO2-containing gas
mixtures. First GLMC works as absorber and second one works as desorber. Gas mixture enters
into the absorber where CO2 is absorbed by a liquid (absorbent). Liquid constantly circulates
between absorber and desorber. Desorber serves for desorption of CO2 from liquid (regeneration
of absorbent).
A mathematical model of the system has been developed in order to investigate its separation
properties and potential. Separation properties of the system depend on a large number of
parameters such as concentration of components in gas mixture, type and concentration of liquid
absorbent, permeance of membrane, flow rates of gas and liquid, temperature, pressure, etc.
Therefore it was decided to fix some of them (type and concentration of liquid absorbent,
permeance of membrane, temperature and pressure) for the study of the system behavior.
Results of modeling show that high selectivity, purification level and recovery degree of
components can be achieved. Moreover, dependencies of system characteristics on liquid flow
rate are non-linear or even extremal. Such behavior opens the possibility of optimization and
adjustment of the system separation properties that is especially important for biogas and
biohydrogen purification because productivity of bioreactors and/or gas mixture composition can
vary significantly during the time.
Acknowledgements
This work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, Goscontract
No. 02.516.11.6043, Grant RFBR No. 07-03-00752.
17
NONISOTHERMAL ABSORPTION OF CARBON DIOXIDE INTO
HOLLOW FIBER CONTACTOR
Noureddine BOUCIFa1, Denis ROIZARDa, and Eric FAVREa2
a
Laboratoire des Sciences du Génie Chimique (UPR 6811-Nancy Université), ENSIC-BP 451
1, rue Grandville, F-54001 Nancy Cedex- FRANCE
1
On sabbatical leave from the Département de Chimie Industrielle et LPQ3M, Université de
Mascara, Mascara 29000, Algérie.
2
Corresponding author phone: ++33 3 83 17 53 90, fax: ++33 3 83 32 29 75,
[email protected]
Abstract
The nonisothermal effects seriously influence the mass transfer rates in gas liquid absorption
followed by chemical reaction [1,2]. A mathematical model was developed for the absorption
of carbon dioxide in aqueous monoethanolamine solution in a hollow fiber membrane
contactor considering diffusion and reaction of gas through an exothermic and reversible
second order reaction. The model consists of a set of coupled partial differential equations for
mass and heat transfer, which were solved using an orthogonal collocation scheme. The
numerical simulation involves dimensionless parameters such as the Graetz for both species,
the Sherwood, the Damköhler, and the Nusselt number of various module temperature
entrance. It has been found that the carbon dioxide and solvent depletion extents are strongly
affected by the temperature increase. The substantial increase in absorption rate with
temperature is mainly due to the fact that physical properties and kinetics coefficients are
increasing functions of temperature.
Keywords: Hollow fiber membrane, Gas-liquid absorption, Heat effects, Heat of reaction,
Orthogonal collocation.
References
1. Villadsen J. and P. H. Nielsen, “Models for Strongly Exothermic Absorption and Reaction
in Falling Films”, Chem. Eng. Sci., 41, (1986),1655-1671.
2. Akanksha, K. K. Pant, and Srivastava V. K., “Carbon Dioxide Absorption into
Monoethanoalmine in a Continuous Film Contactor”, Chem. Eng. Journal, 133, (2007),
229-237.
18
CFD SIMULATION OF A PHOTOCATALYTIC REACTOR
G. Vincent, E. Schaer, O. Zahraa and P. M. Marquaire
Departement de Chimie-Physique des Réactions
CNRS, ENSIC - INPL
1, rue Grandville, BP 20451, 54001 NANCY Cedex, FRANCE, Tel: +33 3 83 17 53 04
email: [email protected]
Introduction
Photocatalytic degradation of organic compounds appears as a promising process for remediation
of air polluted by VOCs. Photocatalytic processes use a semi-conductor photocatalyst, usually
TiO2, as a slurry or deposited on a support, exposed to near UV light to induce the degradation
reactions. Recent researches at ENSIC DCPR in Nancy have shown the interest of CFD
simulations for a better description of photocatalytic reactors and of degradation reactions.
Methods
An annular reactor equipped with a fiberglass support impregnated of TiO2 Degussa P25 and
irradiated by a commercial fluorescent tube placed at the center of the device is used for the
degradation of acetone, which is a typical pollutant of indoor air. A gas chromatograph is used to
follow acetone concentration variations during photocatalytic oxidation.
CFD simulations of such a reactor have been performed using Comsol Multiphysics and
compared with experimental results such as RTD and acetone concentrations. The classical
Navier-Stokes equations describe the free zone (in the absence of support) whereas the Brinkman
equation was used to describe the flow in the porous photocatalytic support.
Results
The calculated upward velocity distributions in the cylindrical annulus are well compared with
the theoretical ones [1] and the simulated RTD are almost superimposed to the experimental
ones, as can be seen in figure 1.
The coupled simulation (hydrodynamics and chemical reaction) helps to ensure that no external
diffusion effects affect the transfer. The pollutant concentration evolution inside the reactor can
be described, as can be seen in figure 2, and the Langmuir Hinshelwood kinetic parameters of
acetone degradation can be deduced of the comparison between theoretical and measured outlet
concentrations [2].
Conclusion
CFD simulations of photocatalytic reactor improve the accuracy of kinetic constant
determination, when compared to those deduced of a theoretical plug flow and can thus address
the design of such air treatment devices.
References
[1] R. B. Bird; W .E. Stewart and E. N. Lightfoot, Transport Phenomena, Second Edition, Wiley,
New York, 2002.
[2] G. Vincent, Procédé d’élimination de la pollution de l’air par traitement photocatalytique :
application aux COVs, Thèse INPL, 2008.
19
Figure 1 : Simulated and measured RTD
Figure 2 : Acetone concentration variations inside the annular reactor, Cinit = 5. 10-4 kg.m-3
20
DRY METHANE REFORMING ON POROUS CATALYTIC
MEMBRANES
A.Fedotova, M.Tsodikova, V.Teplyakova, T.Zhdanovaa, O.Buhtenkoa , D.Roizardb, E.Favreb,
V.Korchakc
a
Lab. of Catalytic Nanotechnology, Lab. of Physico-Chemistry of Membrane Processes,
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia
b
Laboratoire des Sciences du Génie Chimique, Ecole Nationale Supérieure des Industries
Chimiques, Nancy, France
c
Lab. of Catalysis, N.N. Semenov Institute of Chemical Physics RAS, Moscow, Russia
Leninsky pr.29, Moscow, 119991, Moscow, Russia, +74959554222 [email protected]
Two greenhouse gases, methane and carbon dioxide, are still general prospective non-oil
resources for receiving carbonaceous products and hydrogen. Recently an attention is paying to
gas-core heterogeneous catalytic reactions of C1-substrats in microreactors for the purpose of an
intensification of processes. In this case several general advantages of microreactors can be
noted: small sizes of industrial installations, duplication possibility of membrane unit instead of
its scaling, good controllability of the process in the reactor. The most prospective directions in
this field are processes of methane conversion into syngas and light olefins.
In Laboratories of Catalytic Nanotechnologies and Physico-Chemistry of Membrane
Processes (TIPS RAS) were done catalytic experiments of oxidizing methane conversion and dry
methane reforming using ceramic catalytic membranes [1]. It was found that in a membrane
reactor methane conversion is intensive already at 600oC, but in a traditional reactor with a bulk
layer this temperature is up to 900oC. This difference is because of better heat and mass transfer
in the membrane and also an amount of molecule collisions in membrane channels is higher.
Researches were done on several types of ceramic membranes modified by different catalysts.
All samples had different composition and activity in processes of methane conversion but
practical interest of all of them represented Ni-Al membrane modified by La-Ce and Pd-Mn
catalysts. It was shown that La-Ce on Ni-Al has higher activity in dry methane reforming than
Ni-Al/Pd-Mn (ρsyngas=6000 l/dm3reactor∙h at tauresidence=1sec on Ni-Al/La-Ce achieves at 600oC, but
on Ni-Al/Pd-Mn it is only at 650oC), but in the same time ratio of H2/CO is better on the second
system (at T=600oC this ratio is apr.1, but on Ni-Al/La-Ce at the same temperature it is 0.5).
Comparative experiments shown, that non-modified samples also have catalytic activity, but it is
lower than modified have [2-4]. With a purpose of ascertainment of the mechanism of the
reaction the dynamics of methane and carbon dioxide conversion on catalytic membranes was
studied. The peculiarity of the process is a high rate of the reaction between CO2 and carbon
which is generated by dissociating methane.
In LSGC ENSIC (Nancy, France) and LMSPC ECPM (Strasbourg, France) were studied
structures and physical properties of membrane materials which were used in experiments cited
above. It was shown that samples have high density and granular morphology, specific surface
area is apr.0.5 m2/g, pores are very big (~5 mkm in a volume) and porosity is up to 40%. By XRay Diffraction were indentified structures of forming compounds.
References
Patent: [1] Porous ceramic catalytic module and possibility of syngas production in a presence of
it. Patent RF № 2325219, 2006.
Journal: [2] M.I. Magsumov, A.S. Fedotov, M.V. Tsodikov, V.V. Teplyakov, O.A. Shkrebko,
V.I. Uvarov, L.I. Trusov, I.I. Moiseev, Peculiarities of C1-substrates reactions in catalytic
nanoreactors, Russian Nanotecnologies, 1 (2006), 142-152.
21
Abstract: [3] M.V. Tsodikov, V.V. Teplyakov, A.S. Fedotov, A.V. Chistyakov, Oxidative
conversion of methane on porous membrane catalytic systems, 3-rd Russian-French Seminar on
Smart Membrane Processes and Advanced Membrane Materials, Moscow, 2006.
Abstract: [4] M.V. Tsodikov, V.V. Teplyakov, A.S. Fedotov, A.V. Chistyakov, Oxidative
conversion of methane on porous membrane catalytic systems, PERMEA 2007.
Acknowledgments
Author wants to thank V.Uvarov (ISMAN RAS), M.Vargaftik (IGIC RAS), N.Kozicina (IGIC
RAS) for given samples and palladium containing precursors.
Author is very grateful to research assistants of LMSPC ECPM and especially to A.Kiennemann
and C.Courson for help and kindness.
22
Amino acids and peptides separation by a process coupling ion exchange,
carbonic acid elution and electroregeneration
Lu W.1, Grévillot G.1, Muhr L.1
1
Laboratoire des Sciences du Génie Chimique, Nancy-Université CNRS ENSIC LSGC,
1, rue Grandville 54001 Nancy France Tel: 00 33 (0)3 83 17 53 45
Email : [email protected]
Aim
First of all, the idea was to use as eluent a solution of carbon dioxide dissolved in water under
pressure. The works realised in laboratory [1-3] have demonstrated the feasibility of the elution,
the separation and in some cases of the concentration (by the effect of the displacement) of the
amino acids which could be obtained pure and without pH buffers. In the present work, a process
involved ion exchange, elution by carbonic acid and a step of electrochemical regeneration has
been designed and tested experimentally for recover the pure amino acids. This process respects
the environment.
Methods
BM
1
AEM
2
BM
3
4
Fig.1 : Cellule EDI
Fig.2 : Installation expérimentale
An EDI cell (electrodeionization) used is made in laboratory (Fig. 1). The experimental set-up is
showed in Fig. 2. The amino acid reserved in present work is Glycyl-glycine (GLYGLY). The
process has three steps: dipeptide fixation, carbonic acid elution, electroregeneration. The
carbonic acid for elution in the step 2 is obtained by the step 3-electroregeneration. The fractions
of GLYGLY are collected and analyzed to determine the concentration using the
spectrophotometer.
Results
Figure 3. Breakthrough curves of saturation with
GLYGLY (initial form of the bed CO3)
Figure 4. Elution curve of GLYGLY with the
carbonic acid solution recovered
23
Experiments performed show the feasibility of a cyclic process, with three steps, using no pH
buffers, no production of effluences for the purification of amino acids. The amino acids are
obtained pure and not in the pH buffers. With a first approximation, the amino acids which can
not only be fixed but also eluted in this process should satisfy with a criterion:
pK a1 < pK acid < pK a 2 , i.e. between 6.35 and 10.35 (à 298K).
Conclusion
Two application cases exist: one of them can be fixed and the others can’t, the separation of
amino acid mixture is achieved; one of them can’t be fixed and the others can, the separation is
achieved.
References
[1] Z. Pasztor, Comportement des acides aminés dans les colonnes d’échange d’ions : Fixation,
elution-séparation, Thèse INPL-ENSIC, Nancy. 1995.
[2] A. Zammouri, S. Chanel, L. Muhr, G. Grevillot, 1999, Displacement chromatography of
amino acids by carbon dioxide dissolved in water, Ind Eng Chem Res, 38(12) : 4860-4867.
[3] C. Harscoat, L. Muhr, G. Grevillot, 2003, Reactive ion exchange chromatography:
concentrations and separations of amino acids and peptides by means of an aqueous solution of
carbon dioxide under pressure as displacer, ChERD, 81(10): 1333-1342.
24
TRANSPORT OF AROMATIC AMINO ACIDS DURING
ELECTRODIALYSIS
A.E. Bukhovets, T.V. Eliseeva
Voronezh State University, Russia
1 Universitetskaya sq., 394006 Voronezh (Russia). Tel: +7(4732)208932;
email: [email protected]
Aim
Scientists’ interest to the chemistry of amino acids is explained by their important physiological
characteristics. Electrodialysis is a green technology and has many advantages for the recovery
of amino acids. The aim of our study is to reveal the peculiarities of amino acids transport
through the ion-exchange membranes during electrodialysis.
Methods
The experiments have been carried out in ordinary laboratory seven-compartment cell with
alternating cation-exchange MК-40 and anion-exchange MA-41 and MA-40 membranes (UCC
Ltd. Shchekinoazot, Russia).
Results
Tyrosine transport through the ion-exchange membranes MA-41 and MК-40 at wide initial
solution pH range has been considered. At the initial solution pH 5.6 tyrosine transport is
conducted predominantly through the anion-exchange membrane, and flux has the form of curve
with maximum. Maximum conforms to limiting diffusion current density. After exceeding
limiting diffusion current density the growth of amino acid flux through the membrane is ceased,
but at the same time, the decrease of the transfer that corresponds to the barrier effect [1] is
observed. Amino acid flux through the cation-exchange membrane is only diffusive. At the
increase of initial solution pH up to value 11.93, the increase of tyrosine flux through the anionexchange membrane can be found, but the flux through the cation-exchange membrane
practically remains the same. It is explained by the fact that tyrosine is present mainly in the
form of anion at the given initial pH solution, and anions are transferred correspondingly through
the anion-exchange membrane.
We have not found tyrosine transport increase through the cation-exchange membrane at initial
solution acidulation up to pH value 1.72, the amino acid distributional diagram suggests it.
Thus, we can speak about the absence of tyrosine conjugative transport with hydrogen ions, as
well as the absence of tyrosine electromigration in cation form.
This special tyrosine behaviour can be used for separation of amino acids mixtures containing
tyrosine by providing electromigration of target amino acid from diluate compartment through
the cation-exchange membrane.
Conclusion
Study of amino acids transfer peculiarities through ion-exchange membranes can help us to
improve the process of these organic ampholytes purification and separation. The observed
peculiarities of aromatic amino acids transport are the basis of their recovery from various
mixtures at final stages of synthesis in biotechnology.
References
[1] V.A. Shaposhnik, T.V. Eliseeva, Barrier effect during the electrodialysis, J. Membrane Sci.,
161(1999) 223
25
THE INFLUENCE OF MACROSTRUCTURE OF FOILS BASED ON
EXFOLIATED GRAPHITE ON GAS PERMEANCE
D.Syrtsova1, O.Shornikova2
1
Laboratory of Physical chemistry of Membrane Processes, TIPS RAS, Moscow, Russia
Leninski pr., 29, 119991, [email protected]
2
Departement of Chemical Technology and New Materials, MSU, Moscow, Russia
Aim
The new perspectives of membrane gas separation processes development stimulates the search
of new membranes that provide better separation performance with high thermal and chemical
stability. Inorganic porous matrixes including carbon based materials, for example, molecular
sieves [1] and adsorption selective membranes [2] demonstrate some advantages in comparison
with most traditional organic membranes: the permeation properties of carbon membranes is not
time dependent, they have chemical stability and enough high gas selectivity. This paper presents
the results of the gas permeability study of the foils based on exfoliated graphite, which was
developed at Moscow State University. It was fond [3] that permeance of such materials strongly
depends of macrostructure of exfoliated graphite, particularly, density and structure anisotropy.
In this work the influence of characteristic property of graphite macrostructure on permeance and
selectivity for different gas flow directions through graphite foils at wide range density are
presented.
Methods
The permeability of H2, N2, O2, CO2 and some light hydrocarbons was measured by gas
chromato- graphy technique (differential permeability method) at temperature 23-95oC.
Results
The mechanisms of gas transport in graphite foils were studied. It was shown that contribution of
Lengmure sorption to CO2 selective gas transport through the membrane is very important. Also
parallel and normal mode of gas flow through graphite were investigated. The dependences of
graphite density on gas permeance and selectivity at gas flow parallel to membrane surface were
study. It was obtained that for parallel flow gas permeance is higher than for normal flow. But
the difference is more at high density. The membrane tortuosity for both modes was estimated
and it was found that for parallel mode the tortuosity is lower for all gases. As result, the
membrane permeability at parallel mode was higher. It is interesting to note that for parallel
mode experiments the level of H2/CO2 selectivity is closed to Knudsen one and selectivity
maximum for normal flax was not achieved.
The temperature dependences of gas permeance for both modes were studied It was shown that
character of the curve is defined by as sample density as gas flux direction.
Conclusion
In presented study it was shown that selective gas flow in exfoliated graphite matrix flow is
defined by gas-matrix sorption and membrane macrostructure including anisotropy effect.
Obtained results can be effectively used for developing of new carbon based membranes for
separation H2/CO2 in fuel cells using and other gas separation process application.
References
[1] Material Science of Membranes for Gas and Vapor Separation Edited by Yu. Yampolski,
I.Pinnau and B.D.Freeman, 2006
[2] Fuertes A. B., Adsorption-selective carbon membrane for gas separation, Adsorption,
7(2001)117-129
[3] Celzard A., Marêche J.F., Furdin G. Modelling of exfoliated graphite, Progress in polymer
science, 2005, v. 50, pp. 93-179
26
SYNTHESIS OF DIBLOCK COPOLYMERS OF 1-TRIMETHYLSILYL-1PROPYNE WITH 4-METHYL-2-PENTYNE THROUGH SEQUENTIAL
LIVING POLYMERIZATION BY NbCl5 BASED CATALYSTS
E.Y. Sultanov, V.S. Khotimskiy
Laboratory of Synthesis of Permselective Polymers, Topchiev Institute of Petrochemical
Synthesis, Moscow, Russia
Leninskiy pr. 29, 119991. Tel: +74959554205; email: [email protected]
Aim
The aim of this work is the synthesis of block copolymers of 1-trimethylsilyl-1-propyne (TMSP)
with 4-methyl-2-pentyne (MP) as they may combine properties of poly-1-trimethylsilyl-1propyne (PTMSP) and poly-4-methyl-2-pentyne (PMP) namely high gas permeability
parameters of PTMSP [1] and resistance to most of hydrocarbons of PMP [2,3].
Materials which combine these properties are challenging for membrane technology since they
can be used for separation of different gas mixtures containing hydrocarbons.
Methods
Synthesis of block copolymers of TMSP with MP was performed by sequential living
polymerization method. Gel permeation chromatography, IR-spectroscopy and viscosimetry
were used for characterization of obtained block copolymers and their solubility in different
solvents was investigated. Polymer films from synthesized samples were prepared by casting
method and permeability parameters of these films were measured by the volumetric method.
Results
To determine ability of living polymerization of monomers TMSP and MP their
homopolymerizations on NbCl5–based catalytic systems were investigated. Linear dependence
of number average molecular weight (Mn) versus conversion for the polymerization of TMSP
and MP on catalytic systems NbCl5, NbCl5–Ph3SiH and NbCl5–Ph4Sn in cyclohexane and
continuation of polymer chain propagation after addition of new portion of monomer is observed
[4]. These are main evidences of living character of polymerization.
Block copolymers of TMSP with MP with various compositions were synthesized on catalytic
systems mentioned above. It is shown that solvent resistance and parameters of gas permeability
(O2 and N2) depend on the amount of TMSP and MP units in block copolymers.
Conclusion
Conditions of living polymerization of TMSP and MP were found.
The method for synthesis of block copolymers of TMSP with MP by sequential living
polymerization of these acetylenes was developed.
The ability to control resistance to solvents and permeability parameters in dependence on
composition of block copolymers was established.
References
[1] K. Nagai, T. Masuda, T. Higashimura, B.D. Freeman, I. Pinnau, Poly(1-trimethylsilyl-1propyne) and related polymers: synthesis, properties and functions, Prog. In Polym. Sci., 26
(2001), 721-798
[2] A. Morisato, I. Pinnau, Synthesis and gas permeation properties of poly(4-methyl-2-pentyne),
J. Membr. Sci., 121 (1996), 243-250
[3] V.S. Khotimsky, S.M. Matson, E.G. Litvinova, G.N. Bondarenko, A.I. Rebrov, Synthesis of
poly(4-methyl-2-pentyne) with various configurations of macromolecular chains, Polym. Sci.
Ser. A, 45 (2003), 740-746
[4] E.Y. Sultanov, M.Y. Gorshkova, E.N. Semenistaya, V.S. Khotimskiy, Living polymerization
of 4-methyl-2-pentyne and 1-trimethylsilyl-1-propyne by NbCl5-Ph4Sn catalyst, Polym. Sci. Ser.
A, 2008 (in press)
27
BROMINATION AND CROSSLINKING OF
POLY(VINILTRIMETHYLSILANE)
A.A. Masalev, V.S. Khotimskiy
Laboratory of Synthesis of Permselective Polymers, Topchiev Institute of Petrochemical
Synthesis, Moscow, Russia
Leninskiy pr. 29, 119991. Tel: +74959554205; email: [email protected]
Aim
Membranes on the basis of polymers of Si-containing hydrocarbons possess high gas
permeability [1]. At the same time these polymers are soluble in various aliphatic and aromatic
hydrocarbons. Therefore, application of these polymers for separation of mixtures containing
hydrocarbon admixtures is problematic. On the other side introducing of polar groups can
improve polymer resistance to hydrocarbons. Bromine can be one of such groups [2, 3]. This
group may be used for further crosslinking of polymer membranes and that will provide polymer
stability towards aliphatic and aromatic hydrocarbons.
Results of bromination of poly(vinyltrimethylsilane) (PVTMS) with N-bromosuccinimide and
crosslinking of brominated polymer samples with ethylenediamine are given in the presentation.
Methods
Reaction of bromination was carried out with the use of N-bromosuccinimide in solution in
CCl4. Ethylenediamine was used for performing of crosslinking of brominated polymer.
Reaction of crosslinking was carried out in simulative conditions in solution as well as on
prepared polymer films treated with ethylenediamine in methanol. Content of bromine in
polymer and molar fraction of crosslinking were estimated by elemental analysis and on the
basis of IR-spectra.
Results
The methods of bromination of PVTMS, which allows introducing bromine up to 50 wt.% in
polymer, and crosslinking of brominated polymers with different crosslinked fractions were
elaborated. Fraction of crosslinking was regulated by quantity of introduced bromine as well as
ratio bromine/ethylenediamine.
Conclusions
The method of obtaining of crosslinked membrane on the basis of PVTMS stable towards
aliphatic and aromatic hydrocarbons was elaborated. Samples of polymer membranes with
different content of bromine and different content of crosslinked fraction were obtained and
study of permeation parameters is planned.
References:
[1] N.A.Plate, S.G.Durgaryan, V.S. Khotimsky, V.V.Teplyakov, Yu.P. Yampol’skii, Novel
polysiliconolefins for gas Separation, J. Membr. Sci.,52, 289 (1990).
[2]Xu Tongwen, Yang Weihua, A novel positively charged composite membranes for
nanofiltration prepared from poly(2,6-dimethyl-1,4-phenylene oxide) by in situ amines
crosslinking, J.Membr. Sci., 215 (2003) 25-32.
[3] A. A. Masalev, V. S. Khotimskii, G. N. Bondarenko, and M. V. Chirkova, Bromination of
Poly[1-(trimethylsilyl)-1-propyne]with Different Microstructures and Properties of BromineContaining Polymers, Polym. Sci. Ser.A, 2008, Vol. 50, No. 1, pp. 47–53.
28
PREPARATION AND PROPERTIES OF NANOCOMPOSITE
MEMBRANES BASED ON RUBBERY POLY(ETHER IMIDE) AND SiO2
J. Grignard1, D. Roizard1, E. Favre1, J. Ghanbaja2
1
Laboratoire des Sciences du Génie Chimique (UPR 6811, Nancy Université), Groupe ENSIC –
BP 20451 1, rue Grandville, 54001 NANCY Cedex, France. Tel: +33(0)383175289; email:
[email protected]
2
Service commun de microscopies électroniques et microanalyses X, Faculté des Sciences
Université Henri Poincaré, BP 239, Bd des Aiguillettes, 54506 Vandoeuvre-Lès-Nancy, France
Aim
The work's main objective is the synthesis of organic materials for novel uses in the area of
separation of gas mixtures by dense membranes. The development of these materials is achieved
through two distinct methods. The first method involves the preparation of block copolymers
(flexible and rigid), each block constituting one of the phases of specific properties that can
improve the performance of permeation of polyimide. In this way, the preparation of original
multiphase poly(ether imide) (PEI) materials was realized. The second method uses the previous
copolymers in which an inorganic phase is incorporated using either SiO2-fillers or organic silica
precursors, i.e. TMOS and TEOS[1]. The objective was to understand to what extent the
presence of nano- or micro- sized silica particles may change the properties of the PEI matrix, in
particular the gas separation characteristics.
Methods
Series of tribloc copolyimides were synthesized from commercial oligoalkoxy α,ω-diamines
(Jeffamines), an aromatic diamine (ODA) used as chain extender, and an aromatique dianhydride (PMDA). To determine the influence of the characteristics of SiO2-fillers (i.e. origin,
amount, nature) on the properties of hybrid materials, two kinds of fumed silica were used: either
hydrophilic microparticles (16 µm), or nanoparticles (12 nm hydrophilic or 16 nm hydrophobic
ones). To form a more homogenous intermolecular three-dimensional silica network, in situ solgel approach was also carried out for the preparation of hybrid materials with the same amounts
of silica using tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS). In order to
establish the relations between structures and properties of pure and mixed gases, the
characterization of chemical structures, physical and physical-chemical properties these
materials are carried out using adapted analytical methods: spectroscopy, thermogravimetry,
calorimetry, microscopy, etc… In this paper, some FTIR, SEM, TEM, DSC and DMA analysis
will be exposed. The properties of PEI and PEI/SiO2 membranes were investigated in transient
regime by time-lag experiment for several in gases (N2, CO2, O2, H2, CH4,…) at different
temperatures, varying from 5 to 45 °C with a membrane thickness ranging from 60 to ≈200 µm.
Results & conclusions
Permeation tests show that the materials obtained are very permeable with CO2 and its selectivity
has interesting values(Table 1). Due to the rubbery structure of PEI the permeation properties for
CO2 and N2 are very attractive because they are much higher than known aromatic polyimides
and composite polyimide/SiO2 membranes [2-4].
Table 1: Gas permeabilities (Barrers) forPEI & PEI/SiO2 films at 25 °C
Membrane
CO2 N2 CH4
98 1.58 4.60
PEI (Jeff600-06)
PEI + 8%wt. SiO2 (16 nm)
123
2.09 5.49
PEI + 15%wt. SiO2 (16 nm)
63
1.33
29
Permeability increases and ideal selectivity decreases with the addition of low amounts of
hydrophobic silica particles. From SEM and TEM studies (Figure 1), it was exposed that silica
nanoparticles, powders or obtained by the sol-gel method, were distributed homogenously into
the PEI matrix.
A
B
Figure 1: Cross-sectional SEM micrograph of PEI/SiO2 16nm (92:8) (A) and cross-sectional
TEM micrograph of PEI/SiO2 12nm (92:8) (B)
References
[1] J. Lizhong, W. Wencai, W. Xiaowei, W. Dezhen, J. Riguang, Effects of Water on the
Preparation, Morphology, and Properties of Polyimide/Silica Nanocomposite films Prepared by
Sol-Gel Process, J. Appl. Polym. Sci. 104 (2007), p. 1579
[2] D. Ayala, A.E. Lozano, J. de Abajo, C. García-Perez, J.G. de la Campa, K.-V. Peinemann,
B.D. Freeman, R. Prabhakar, Gas separation properties of aromatic polyimides, J. Membr. Sci.
215 (2003), p. 61
[3] C. Joly, S. Goizet, J.C. Schrotter, J. Sanchez, M. Escoubes, Sol-gel polyimide-silica
composite membrane: gas transport properties, J. Membr. Sci. 130 (1997), p. 63
[4] C. Hibshman, C. J. Cornelius, E. Marand, The gas separation effects of annealing polyimideorganosilicate hybrid membranes, J. Membr. Sci. 211 (2003), p. 25
30
FUNCTIONALIZED POLYMERS FOR CO2 SELECTIVE
MEMBRANES. INVESTIGATION OF INTRODUCTION REACTIONS OF
LOW-MOLECULAR POLYETHYLENEGLYCOL ETHERS AND «IONIC
LIQUIDS» GROUP IN Si-CONTAINING POLYMERS
Author: Kiryukhina Y.V; Khotimsky V.S.
Laboratory of Synthesis of Selective Permeable Polymers, TIPS RAS, Russia
Leninsky prosp., 29, 119991 Moscow (Russia); +7(495)9554205;
e-mail: [email protected]
Aim
The problem of CO2 recovery from gas mixtures, containing CO2 admixtures, is
sufficiently of current interest to date. First of all this is a challenge of purification of energy
carriers methane and hydrogen from CO2 [1].
The method of membrane separation is one of the most advanced current methods for
hydrogen purification. In a number of cases with low content of CO2 in mixture membranes
selective for CO2 are more attractive.
It is known that Si-containing hydrocarbon polymers poly(1-trimethylsilyl-1-propyne)
[PTMSP] and poly(vinyltrimethylsilane) [PVTMS]have high CO2 permeability, but selectivity of
CO2 recovery from mixtures with H2 and CH4 are insufficiently high [2,3]. With the view of
increasing of selectivity values the methods of synthesis of these polymers containing functional
groups that are capable to raise CO2 solubility in polymer owing to reversible specific interaction
have been considered in the present work. This approach should provide high selectivities of
CO2 recovery. Ethylene oxide groups of low-molecular ethers of polyethylene glycol as well as
groups, modeling the structure of “ionic liquids”, have been chosen as groups which are capable
to specific interaction. It is known that these groups possess good solubility and solubility
selectivity for CO2 [4,5].
Methods
The introduction of functional groups in polymer were carried out in 2 steps:
- obtaining of Br-containing polymer by reaction of PTMSP and PVTMS with bromine
and N-bromosuccinimide [6],
- polymeranalogues reactions with the use of reactive Br-group in polymer.
To introduce ethylene oxide groups the reaction of Br-containing polymer with methyl
ether of polyethylene glycol in solution in THF in the presence of Na was considered.
To introduce moieties of “ionic liquids” the reaction of Br-containing polymer with Nbutyl-imidazole was considered.
Results and conclusions
The examined reactions allow performing synthesis of polymers containing ethylene oxide
groups and fragments of “ionic liquids”. The investigation on optimization of content of these
groups in order to get polymers with film-forming properties and study of permeation properties
are in progress now.
References
Journal:
1. Nathan W. Ockwig, Tina M. Nenoff, Membranes for Hydrogen Separation, Chem. Rev. 2007,
107, 4078-4110;
2. K.Nagai, T. Masuda, T. Nakagawa, Benny D. Freeman, I. Pinnau, Poly[1-(trimethylsilyl)-1propyne] and related polymers: syhthesis, properties and functions, Prog. Polym.Sci. 26 (2001)
721-798;
3. N.A.Plate, S.G.Durgaryan, V.S. Khotimsky, V.V.Teplyakov, Yu.P. Yampol’skii, Novel
polysiliconolefins for gas Separation, J. Membr. Sci.,52, 289 (1990);
31
4. Baltus, R.E., Culbertson, B.H., Counce, R.M., DePaoli, D.W, Luo, H., Dai, S., Duckworth,
D.C., Examination of Potential of ionic liquids for gas separation, Separation Science and
Technology, 40:525-541,2005;
5. Haiqing Lin, Benny D. Freeman, Materials selection guidelines for membranes that remove
CO2 from gas mixtures, Journal of Molecular Structure (2004) 1–18;
6. A. A. Masalev, V. S. Khotimskii, G. N. Bondarenko, M. V. Chirkova, Bromination of Poly[1(trimethylsilyl)-1-propyne]with Different Microstructures and Properties of Bromine-Containing
Polymers, Polymer Science, Ser. A, 2008, Vol. 50, No. 1, pp. 37–42.
32
ASYMETRIC POLYIMIDES MEMBRANES FOR PERVAPORATION
SEPARATIONS
Ayman Elgendi, Denis Roizard , Favre Eric
Laboratoire des Sciences du Génie Chimique, CNRS
ENSIC
1, rue Grandville, BP 20451, 54001 NANCY Cedex, FRANCE, Tel: +33 3 83 17 53 04
email: [email protected]
Introduction
This work aimed at preparing polymeric nanofiltration membranes in order to get water selective
membranes suitable for the retention of organic molecules from polluted water mixtures. Hence
two objectives must be reached: first, the selection of water selective materials well resistant in
almost pure water, and secondly the preparation of high flux membranes having a thin dense top
layer for selective water permeation. Hence asymmetric membranes were prepared and their
separation properties preliminary checked by pervaporation.
Methods
To satisfy the first objective, a copolyimide (PEI) including alkyloxy- rubbery blocks was
synthesized by step polymerization; indeed, propyloxy- and more particularly ethyloxy- ether
blocks are known to have high affinity with water. On the other hand, the imide block was
prepared from pyromellitic dianhydride (PMDA) and oxydianiline (ODA) to provide a water
resistant polymer structure after the formation of the imide cycle. Phase inversion method was
used to prepare high flux membranes from PEI organic solutions (15 to 30wt% in DMF). The
parameters of the inversion process were optimized to get highly permeable PEI membranes and
to keep simultaneously the molecular separation properties of the related PEI dense films.
Results
The physico-chemical properties of PEI membranes were determined by swelling experiments in
several pure liquids. They demonstrated the very good water resistance of PEI for water.
To get high fluxes membranes, asymmetric structures were prepared by phase inversion in water;
the influence of the experimental conditions on the membrane microstructure and on the
separation properties were respectively characterized by scanning electron microscope (SEM)
and pervaporation. To control if the top layer was either tight or porous, pervaporation
experiments of pure liquids and mixtures were routinely carried out and compared with results
obtained from homogenous dense membranes.
Conclusion
The best samples were found to exhibit molecular selectivity for Ethanol-Water and TolueneHeptane mixtures. The obtained selectivities were close to the fully dense membranes
selectivities with very high pervaporation flux. Hence these samples are promising candidates for
the nanofiltration of organic water mixtures.
Keywords: Polyetherimide, Phase inversion, Asymmetric membrane, Pervaporation
33
NEW ASPECTS OF GAS PERMEABILITY PARAMETERS
CORRELATIONS FOR PREDICTION OF MEMBRANE PROPERTIES.
O. Malykh2, V.Teplyakov1,2
1
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences (TIPS RAS)
119991, Leninsky pr. 29, Moscow, Russia
2
M.V. Lomonosov Moscow State University (MSU), 119992, Leninskie Gory 1, Moscow,
Russia
Introduction
At present an active attention is directed on statistical treatment of experimental data and
methods of physical-chemical properties prediction based on available data. Main attention in
present paper is focused on technique of statistical treatment of published gas permeability data
for different polymers with aim to fill “empty spaces” of permeability parameters data based on
consideration of possible correlations between them. This developed method allows us to
estimate permeability of gases experimental data for which are absent. We used approximation
functions for this estimation. Paper demonstrates the deviations for known parameters from
estimated values.
Results
The collection of database of gas permeability parameters for different polymers (rubber-like,
glassy, copolymers, etc) was carried out by using available sources of published data. Gases
include permanent gases, acid gases, lower hydrocarbons, some vapors and oxygen containing
organics presented in literature obtained from permeability experiments. Algorithm of polymer
selection for definite separation processes with using desired region of parameters and required
selectivity is developed. Regular function for permeability of gases was proposed and this
function was used for estimation of not known values. Graphic functions in 2D and 3D view
were considered. Comparative dependences of gas permeability parameters are calculated and
the most linear dependences are accepted. Logarithmic and non-linear permeability function are
suggested. Gas permeability coefficients were calculated by using these functions and calculated
values were compared with known experimental (published) data. Deviation for theoretical
results was estimated and dependence of its values from permeability value was determined.
Angle on linear graphics is compared with effective selectivity for gases pair. Linear coefficients
were presented as matrix and can be used further for calculation of gas permeability for H2, He,
O2, CO2, N2, CH4, Ar (because exists large number of polymers with known permeability values
fro this gases). The respective Database with selection of desired polymers (selectivity,
permeability, class, chemical structure) was developed. Additionally, the software for calculation
of separation productivity of membrane modules for multi-component gas mixture separation
was developed. The both parts of software have “bridge” for communication and can be in
prospect used for education aims and practical applications.
Acknowledgements
This work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, Grant RFBR
No. 08-03-92495-НЦНИЛ_а and Goscontract No. 02.516.11.6043.
34
PHOSPHINE IMIDE REACTION IN SUPERCRITICAL CO2:
MODELING AND APPLICATIONS
Alexandre SCONDO1, Florence Dumarcay2 , Alain Marsura2 and Danielle Barth3*
1
Laboratoire de Thermodynamique des Milieux Polyphasés, ENSIC, Nancy, France
2
G.E.V.S.M., Université Henry Poincaré, Nancy, France
3
Laboratoire des Sciences du Génie Chimique, ENSIC, 1 rue Grandville, 54000 Nancy, France
Tel: +33 (0)3 83 17 50 27; email: [email protected]
The phosphine imide strategy (1) was initially developed in organic solvents to achieve a
rapid and easy access to sophisticated cyclodextrines derivatives (urea, carbodiimides and
isocyanates) (2). In this strategy, CO2 was used as reactant.
We have investigated the usability of supercritical CO2 (scCO2) as solvent and reactant
for a standard reaction. In our previous investigations on the reaction in scCO2, we have
developed a kinetic model for the standard reaction in a 100mL high pressure reactor (3). It
appears that the production of isocyanates in scCO2 was following a first order kinetic. The
production of isocyanates was slower than their reaction with an electrophilic agent
(benzylamine) wich was very fast. These results were compared with those obtained in DMF,
and the use of scCO2 showed significant improvements in the kinetic of reaction.
In order to prove the efficiency of this model, we have used it to predict the results
obtained in a 1L high pressure reactor. The comparison between calculated and experimental
results was satisfactory with errors below 20%.
The scCO2 and phosphine imide strategy were also used to produce one compound of
pharmaceutical interest, which was previously produced in DMF (4):
The kinetic of this reaction was followed and the desired compound was obtained in less
than 3 hours with yeld over 92%.
References
[1] S. Porwanski, S. Menuel, X. Marsura, A. Marsura, The modified `phosphine imide' reaction:
a safe and soft alternative ureas synthesis, 45 (2004) 5027.
[2] S. Menuel, S. Porwanski, A. Marsura, New synthetic approach to per-O-acetyl-isocyanates,
isothiocyanates and thioureas in the disaccharide and cyclodextrin series, 30 (2006) 603
[3] Danielle Barth, Alexandre SCONDO, Florence Dumarcay and Alain Marsura, "Phosphine
Imide" Reaction on Peracetylated -Cyclodextrins: Comparison between Supercritical CO2 and
Organic Solvent Processes, Barcelona , ISASF Sympsonium 2008.
[4] Stéphane Menuel, Jean-Pierre Joly, Blandine Courcot, Josias Elysée, Nour-Eddine Ghermani
and Alain Marsura, Synthesis and inclusion ability of a bis-β-cyclodextrin pseudo-cryptand
towards Busulfan anticancer agent, 2007(63)1706
35
HIGH-PRESSURE MAGNETIC SUSPENSION BALANCE AND
SUPERCRITICAL CARBON DIOXIDE
S.Miccilino, D.Barth
Laboratoire des Sciences du Génie Chimique, Nancy-Université, France
ENSIC, 1 rue Grandville BP20451-54001 NANCY
tel : 33(0)3 83 17 50 27 ; [email protected]
Physical adsorption of fluids onto solids is of interest in the transportation and storage of fuel
and radioactive gases, the separation and cleaning of materials, solid-phase extractions,
adsorbent regenerations using supercritical fluids and supercritical fluid chromatography.
Although physical adsorption of pure gases on different porous solids has been extensively
studied over a wide range of temperatures and pressures, the number of works related to
adsorption at high pressures is limited. In order to study supercritical process such as
adsorption/desorption of Volatile Organic Compounds, impregnation of polymers, diffusion of
SC-CO2 we decided to buy a high-pressure magnetic suspension balance from Rubotherm
(Apollo Instruments, France) and to connect it to a supercritical carbon dioxide home-made
equipment. The balance working up to 35 MPa and 250°C, allows the determination of specific
quantities without danger of pollution or destruction of the balance. We present in a first part a
bibliographic review about polymers[1] and adsorbents [2] and in a second part the laboratory
equipment.
Figure 1: Solubility of carbon dioxide
in poly(vinyl acetate)[1]
Figure 2: SC-CO2 microbalance
References
[1]Yoshiyuki Sato, Tadao Takikawa, Shigeki Takishima, Hirokatsu Masuoka
Solubility and diffusion coefficients of carbon dioxide in poly(vinyl acetate) and polystyrene
The Journal of Supercritical Fluids, 19, 2 ( 2001) 187-198
[2]A.Herbst,R.Staudt,P.Harting
The magnetic suspension balance in high pressure measurements of pure gases
Journal of thermal analysis and calorimetry 71(2003) 125-135
36
HYBRIDE MEMBRANE/PSA METHOD FOR HYDROGEN RECOVERY
FROM MULTICOMPONENTS GAS MIXTURES OF BIOTECHNOLOGY
AND PEROCHEMISTRY
O.L. Amosova1,2, O.V. Malykh2, V.V. Teplyakov1,2
1
A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences (TIPS RAS)
119991, Leninsky pr. 29, Moscow, Russia
2
M.V. Lomonosov Moscow State University (MSU), 119992, Leninskie Gory 1, Moscow,
Russia; e-mail: [email protected]
Traditional methods of separation and purification of gas mixture usually include cryogenic,
absorption, adsorption and membrane technologies. The problems of recovery of hydrogen from
multicomponents gas mixture assume the development of safe technologies with low power
consumption.
Our study presents a review of publications concerned with hydrogen recovery from the gas
mixtures. Also the motivations for developing of integrated membrane/PSA method are
discussed. This method combines the using of membranes modules based on commercially
accessible membranes and well known pressure swing adsorption (PSA) processes for effective
recovery of hydrogen from biogas. We also present the results of comparison of modules based
on commercially available membranes (GENERON hollow fibers membranes and flat sheet
membranes based on PVTMS) for hydrogen recovery from multicomponent gas mixtures
containing CO, CO2, N2, H2S. The estimation of H2S, CO, H2O permeability of membranes was
carried out by the correlation method. The comparative analysis of hollow fiber membrane
module and flat sheet membrane module for pre-concentration of H2 from multicomponents gas
mixture include CO, CO2, N2, H2S has been made. Taking into account the principle of gases
separation in condition of PSA we considered the basic classes of adsorbents for effective
recovery of hydrogen from gas mixture. It is know that a special problem of hydrogen recovery
is the presence of aside gases. This problem can be solved by the combination of membrane and
adsorption processes. Optimum parameters for PSA-separation (2 stage) are reached at the stage
of membrane recovery (1 stage) of hydrogen from the mixture at low content (extraction ~ 80 97 % vol. of hydrogen with H2 permeate concentration is 70 % vol. with using of commercially
accessible membranes). At the PSA stage receiving of hydrogen with cleanliness of 99.9 %
(extraction degree ~ 90 %) is provided.
The received data are obtained known membranes and adsorbents and can be considerably
improved by usage of new effective membrane materials and adsorbents.
This work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, Grant RFBR
No. 08-03-92495-НЦНИЛ_а and Goscontract No. 02.516.11.6043.
37