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Russian- French Laboratory of Membranes and Technologies of Molecular

Selective Processes RFL Nikolai PLATÉ

TTTHHHEEE MMMEEEMMMBBBRRRAAANNNEEESSS AAANNNDDD MMMOOOLLLEEECCCUUULLLAAARRR---SSSEEELLLEEECCCTTTIIIVVVEEE SSSEEEPPPAAARRRAAATTTIIIOOONNN PPPRRROOOCCCEEESSSSSSEEESSS

organized by

A.V.Topchiev Institute of Petrochemical Synthesis, RAS

and

Ecole Nationale Supérieure des Industries Chimiques

Laboratoire des Sciences du Génie Chimique

Moscow, Russia

October 7th-10th, 2008

TIPS RAS

2

Content

Cooperation stages ………………………………………………………..3

Russian-French Laboratory (RFL Nikolai Platé)……………………….7

5th Russian-French seminar program……………………………………8

Abstracts of presentations………………………………………………13

3

COOPERATION STAGESof TIPS RAS (Moscow, Russia) and INPL (Nancy, France):

Cooperation projects:

1998-2002 - INCO grant «New membranes and integrated hybrid membranes systems forVOC’s recovery from industry », IC15-CT98-0140

2002-2004 - INTAS Grant Ref n°. 2000 – 00230 «Synthesis and study of the molecularproperties and the sub-molecular organisation of new high permeability polymeric materialsbased on unsaturated silyl hydrocarbons enhanced with selective transfer properties towardsorganic gases and vapours”

2005-2007 - RFBR-CNRS (France) №05-03-22000 «Smart separation processes withperspective polymeric materials».

2006-2009 - National French project ANR-06-CO2-002-05 «СО2 removing from gas mediaand the utilization”

2007-2010 - Russian–French laboratory of membranes and molecular-selectivetechnologies « RFL Nikolai PLATÉ »

French – Russian Seminars

SMART MEMBRANE PROCESSES AND ADVANCED MEMBRANE MATERIALS2005, 2005, 2006, 2007

Moscow State University

TIPS RAS

A.V. Topchiev Institute ofpetrochemical Synthesis RAS

Ecole Nationale Superieuredes Industries Chimiques

4

I Russian-French Seminar: Kliazma, Moscow, 8-9 October, 2004

II French-Russian Seminar: Nancy, 16-19 June 2005

5

April, 2006: Work meeting at Moscow State University

III French-Russian Seminar: Moscow, October 2006

6

IV French-Russian Seminar: Nancy, 15-17 October 2007

Laboratoire franco-russe des membranes et génie des procédés de séparation moléculaireLFR Nikolai PLATÉ, December, 2007

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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 leLaboratoire 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.

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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

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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.

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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

11

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

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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

13

ABSTRACTS OF PRESENTATIONS

14

ANALYSIS OF PUBLISHED DATA ON MASS-TRANSFER PROCESSESIN MEMBRANE CONTACTORS

R. YastrebovLaboratory of physical-chemistry of membrane processes,A.V.Topchiev Institute of Petrochemical Synthesis RAS,

29 Leninskii prospect, 119991 Moscow, Russia; Tel: +74959554222; email: yaroman@ips.ac.ru

IntroductionIn present time great attention is focused on ecological problem and on problem of biogasseparation. One of the ways for solution of this problem is extraction of CO2 from different gasmixtures 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 andmembrane methods of separation. Main problems that arising with development of such gas-liquid membrane systems are: creation of superpermeable non-porous membranes, selection ofeffective liquid absorbent and organization of mass transfer in gas-membrane-liquid system.

ResultsAnalysis of literature data on membrane contactors was carried out. Main attention in the work isfocused 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 ofgas and liquid flows on mass-transfer in membrane contactor. Almost all the studies of MCswere carried out using porous membranes in order to reduce mass transfer resistance.Unfortunately it was found that utilization of porous membrane often leads to significantreduction of overall mass transfer coefficient due to the wetting of membrane pores. Thisphenomenon may arise even if membrane material is highly hydrophobic. For example forpolypropylene membrane reduction of mass transfer reaches 20% if membrane pores wetting isequal to 5% [1]. Example 2: if pore wetting increase to 100%, reduction of mass transfer reachesis more than 60% [2]. Utilization of non-porous membrane can help to avoid this problem. At thesame time non-porous membrane introduce additional mass transfer resistance [3]. Analysis ofsuch data is very important and helpful for the development of new highly efficient membranecontactors and shows that search and utilization of highly permeable non-porous membranes forMCs should be priority task.

References1. 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 PurificationTechnology 46 (2005) 33-40.

2. M. Al-Marzouqi, M. El-Naas, S. Marzouk, N. Abdullatif, Modeling of chemical absorptionof 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-liquidmembrane contactors for gas separation, Chem. Eng. Res. Design 75 (1997) 685-692.

AcknowledgementsThis work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, Grant RFBRNo. 07-03-00752 and Goscontract No. 02.516.11.6043.

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Experimental study on hollow fiber membrane contactor:determination of permeabilityP.T. Nguyen1, D. Roizard1, E. Favre1

1 Laboratoire des Sciences du Génie Chimique (CNRS UPR 6811) ENSIC-INPL, 1 rueGrandville, 54 001 Nancy, France

email: Denis.Roizard@ensic.inpl-nancy.fr

AimIn order to reduce greenhouse gases emissions, different technologies for capture and removal ofCO2 are currently developed. One promises method is the use of hollow fiber membranecontactor. Numerous studies on this technology have been done and the mass transfer coefficientin the different parts have been calculated (kl on the liquid side, kg on the gas side and km in themembrane). The coefficients kl and kg are, most of the time, determined by correlation and km isthen deduced. However, the correlation in the liquid side depends strongly of the polydispersityand of the spatial arrangements [1] which leads to numerous correlations with a wide range ofvalues. This work aimed to test different methods and set up to determine the permeability ofmembrane in order to directly obtained km and avoid the use of correlation to calculate kl.

MethodsPermeability 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 andthen, gas is injected upstream; the evolution of the pressure downstream is recorded. The set upand 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 coulddirectly be deduced:- first method: pure CO2 is injected inside the fibers at high pressure and the pressure in the shellside 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 thefibers at 1 bar (figure 3). The evolution of CO2 flow rate is also recorded.

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Figure: set up for N2 sweeping experiments

These methods will be explained in more details and the drawbacks of each one will behighlighted.

ResultsThe 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 fibermembrane 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 (between1800 and 2600 barrer for PDMS) and are in the same order of magnitude than those obtainedwith flat sheets. However the experiments still need to be improved and more experiments arenecessary.

ConclusionExperiments on PDMS have been done for flat sheets and hollow fibers. The results are in thesame order of magnitude but are still different maybe because of a difference of the polymer. Forthe moment, it is not possible to extrapolate results of flat sheets for hollow fibers, more data arenecessary (for example with PTMSP hollow fibers). The set up for time lag method is validatedbut the experiments for hollow fibers permeability need improvements.

References[1] Jing-Liang Li, Bing-Hung Chen, Review of CO2 absorption using chemical solvents inhollow fiber membrane contactors, Separation and Purification Technology, 41 (2005) 109-122.

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MODELING OF RECYCLING MEMBRANE CONTACTOR SYSTEMWITH AQUEOUS POTASSIUM CARBONATE

FOR CO2 RECOVERY FROM GAS MIXTURESM.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:mshalygin@ips.ac.ru

The recovery of CO2 from gas mixtures is important problem nowadays. CO2 recovery from gasmixtures can be applied in such processes as biogas separation, enrichment of biohydrogen, postcombustion capture of CO2. High level of gas mixture purification and low losses of othercomponents are usually should be achieved in these cases. Therefore, separation process shouldbe highly selective. Another important requirement is low consumption of energy. Gas-liquidmembrane contactor (GLMC) is proposed as separation device which can satisfy bothrequirements. GLMC unites advantages of absorption methods of separation such as highselectivity and wide list of absorbents with advantages of membrane methods of separation suchas high, determined and constant exchange area. GLMC is a device where gas and liquid phasesare presented and separated by a membrane.Recycling system based on two GLMCs is suggested for separation of CO2-containing gasmixtures. First GLMC works as absorber and second one works as desorber. Gas mixture entersinto the absorber where CO2 is absorbed by a liquid (absorbent). Liquid constantly circulatesbetween absorber and desorber. Desorber serves for desorption of CO2 from liquid (regenerationof absorbent).A mathematical model of the system has been developed in order to investigate its separationproperties and potential. Separation properties of the system depend on a large number ofparameters such as concentration of components in gas mixture, type and concentration of liquidabsorbent, 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 ofcomponents can be achieved. Moreover, dependencies of system characteristics on liquid flowrate are non-linear or even extremal. Such behavior opens the possibility of optimization andadjustment of the system separation properties that is especially important for biogas andbiohydrogen purification because productivity of bioreactors and/or gas mixture composition canvary significantly during the time.

AcknowledgementsThis work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, GoscontractNo. 02.516.11.6043, Grant RFBR No. 07-03-00752.

18

NONISOTHERMAL ABSORPTION OF CARBON DIOXIDE INTOHOLLOW FIBER CONTACTOR

Noureddine BOUCIFa1, Denis ROIZARDa, and Eric FAVREa2

a Laboratoire des Sciences du Génie Chimique (UPR 6811-Nancy Université), ENSIC-BP 4511, rue Grandville, F-54001 Nancy Cedex- FRANCE

1 On sabbatical leave from the Département de Chimie Industrielle et LPQ3M, Université deMascara, Mascara 29000, Algérie.

2 Corresponding author phone: ++33 3 83 17 53 90, fax: ++33 3 83 32 29 75,Eric.Favre@ensic.inpl-nancy.fr

AbstractThe nonisothermal effects seriously influence the mass transfer rates in gas liquid absorptionfollowed by chemical reaction [1,2]. A mathematical model was developed for the absorptionof carbon dioxide in aqueous monoethanolamine solution in a hollow fiber membranecontactor considering diffusion and reaction of gas through an exothermic and reversiblesecond order reaction. The model consists of a set of coupled partial differential equations formass and heat transfer, which were solved using an orthogonal collocation scheme. Thenumerical simulation involves dimensionless parameters such as the Graetz for both species,the Sherwood, the Damköhler, and the Nusselt number of various module temperatureentrance. It has been found that the carbon dioxide and solvent depletion extents are stronglyaffected by the temperature increase. The substantial increase in absorption rate withtemperature is mainly due to the fact that physical properties and kinetics coefficients areincreasing 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 Reactionin Falling Films”, Chem. Eng. Sci., 41, (1986),1655-1671.

2. Akanksha, K. K. Pant, and Srivastava V. K., “Carbon Dioxide Absorption intoMonoethanoalmine in a Continuous Film Contactor”, Chem. Eng. Journal, 133, (2007),229-237.

19

CFD SIMULATION OF A PHOTOCATALYTIC REACTORG. Vincent, E. Schaer, O. Zahraa and P. M. Marquaire

Departement de Chimie-Physique des RéactionsCNRS, ENSIC - INPL

1, rue Grandville, BP 20451, 54001 NANCY Cedex, FRANCE, Tel: +33 3 83 17 53 04email: Eric.Schaer@ensic.inpl-nancy.fr

IntroductionPhotocatalytic degradation of organic compounds appears as a promising process for remediationof air polluted by VOCs. Photocatalytic processes use a semi-conductor photocatalyst, usuallyTiO2, as a slurry or deposited on a support, exposed to near UV light to induce the degradationreactions. Recent researches at ENSIC DCPR in Nancy have shown the interest of CFDsimulations for a better description of photocatalytic reactors and of degradation reactions.

MethodsAn annular reactor equipped with a fiberglass support impregnated of TiO2 Degussa P25 andirradiated by a commercial fluorescent tube placed at the center of the device is used for thedegradation of acetone, which is a typical pollutant of indoor air. A gas chromatograph is used tofollow acetone concentration variations during photocatalytic oxidation.CFD simulations of such a reactor have been performed using Comsol Multiphysics andcompared with experimental results such as RTD and acetone concentrations. The classicalNavier-Stokes equations describe the free zone (in the absence of support) whereas the Brinkmanequation was used to describe the flow in the porous photocatalytic support.

ResultsThe calculated upward velocity distributions in the cylindrical annulus are well compared withthe theoretical ones [1] and the simulated RTD are almost superimposed to the experimentalones, as can be seen in figure 1.The coupled simulation (hydrodynamics and chemical reaction) helps to ensure that no externaldiffusion effects affect the transfer. The pollutant concentration evolution inside the reactor canbe described, as can be seen in figure 2, and the Langmuir Hinshelwood kinetic parameters ofacetone degradation can be deduced of the comparison between theoretical and measured outletconcentrations [2].

ConclusionCFD simulations of photocatalytic reactor improve the accuracy of kinetic constantdetermination, when compared to those deduced of a theoretical plug flow and can thus addressthe 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.

20

Figure 1 : Simulated and measured RTD

Figure 2 : Acetone concentration variations inside the annular reactor, Cinit = 5. 10-4 kg.m-3

21

DRY METHANE REFORMING ON POROUS CATALYTICMEMBRANES

A.Fedotova, M.Tsodikova, V.Teplyakova, T.Zhdanovaa, O.Buhtenkoa , D.Roizardb, E.Favreb,V.Korchakc

aLab. of Catalytic Nanotechnology, Lab. of Physico-Chemistry of Membrane Processes,A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia

bLaboratoire des Sciences du Génie Chimique, Ecole Nationale Supérieure des IndustriesChimiques, Nancy, France

cLab. of Catalysis, N.N. Semenov Institute of Chemical Physics RAS, Moscow, RussiaLeninsky pr.29, Moscow, 119991, Moscow, Russia, +74959554222 alexey.fedotov@gmail.com

Two greenhouse gases, methane and carbon dioxide, are still general prospective non-oilresources for receiving carbonaceous products and hydrogen. Recently an attention is paying togas-core heterogeneous catalytic reactions of C1-substrats in microreactors for the purpose of anintensification of processes. In this case several general advantages of microreactors can benoted: small sizes of industrial installations, duplication possibility of membrane unit instead ofits scaling, good controllability of the process in the reactor. The most prospective directions inthis field are processes of methane conversion into syngas and light olefins.

In Laboratories of Catalytic Nanotechnologies and Physico-Chemistry of MembraneProcesses (TIPS RAS) were done catalytic experiments of oxidizing methane conversion and drymethane reforming using ceramic catalytic membranes [1]. It was found that in a membranereactor methane conversion is intensive already at 600oC, but in a traditional reactor with a bulklayer this temperature is up to 900oC. This difference is because of better heat and mass transferin 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 butpractical interest of all of them represented Ni-Al membrane modified by La-Ce and Pd-Mncatalysts. It was shown that La-Ce on Ni-Al has higher activity in dry methane reforming thanNi-Al/Pd-Mn (ρsyngas=6000 l/dm3

reactor∙h at tauresidence=1sec on Ni-Al/La-Ce achieves at 600oC, buton Ni-Al/Pd-Mn it is only at 650oC), but in the same time ratio of H2/CO is better on the secondsystem (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 islower than modified have [2-4]. With a purpose of ascertainment of the mechanism of thereaction the dynamics of methane and carbon dioxide conversion on catalytic membranes wasstudied. The peculiarity of the process is a high rate of the reaction between CO2 and carbonwhich is generated by dissociating methane.

In LSGC ENSIC (Nancy, France) and LMSPC ECPM (Strasbourg, France) were studiedstructures and physical properties of membrane materials which were used in experiments citedabove. It was shown that samples have high density and granular morphology, specific surfacearea is apr.0.5 m2/g, pores are very big (~5 mkm in a volume) and porosity is up to 40%. By X-Ray Diffraction were indentified structures of forming compounds.

References

Patent: [1] Porous ceramic catalytic module and possibility of syngas production in a presence ofit. 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 catalyticnanoreactors, Russian Nanotecnologies, 1 (2006), 142-152.

22

Abstract: [3] M.V. Tsodikov, V.V. Teplyakov, A.S. Fedotov, A.V. Chistyakov, Oxidativeconversion of methane on porous membrane catalytic systems, 3-rd Russian-French Seminar onSmart Membrane Processes and Advanced Membrane Materials, Moscow, 2006.

Abstract: [4] M.V. Tsodikov, V.V. Teplyakov, A.S. Fedotov, A.V. Chistyakov, Oxidativeconversion of methane on porous membrane catalytic systems, PERMEA 2007.

Acknowledgments

Author wants to thank V.Uvarov (ISMAN RAS), M.Vargaftik (IGIC RAS), N.Kozicina (IGICRAS) for given samples and palladium containing precursors.

Author is very grateful to research assistants of LMSPC ECPM and especially to A.Kiennemannand C.Courson for help and kindness.

23

Amino acids and peptides separation by a process coupling ion exchange,carbonic acid elution and electroregeneration

Lu W.1, Grévillot G.1, Muhr L.11Laboratoire des Sciences du Génie Chimique, Nancy-Université CNRS ENSIC LSGC,

1, rue Grandville 54001 Nancy France Tel: 00 33 (0)3 83 17 53 45Email : Wei.Lu@ensic.inpl-nancy.fr

AimFirst of all, the idea was to use as eluent a solution of carbon dioxide dissolved in water underpressure. 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 theamino acids which could be obtained pure and without pH buffers. In the present work, a processinvolved ion exchange, elution by carbonic acid and a step of electrochemical regeneration hasbeen designed and tested experimentally for recover the pure amino acids. This process respectsthe environment.Methods

An EDI cell (electrodeionization) used is made in laboratory (Fig. 1). The experimental set-up isshowed in Fig. 2. The amino acid reserved in present work is Glycyl-glycine (GLYGLY). Theprocess has three steps: dipeptide fixation, carbonic acid elution, electroregeneration. Thecarbonic acid for elution in the step 2 is obtained by the step 3-electroregeneration. The fractionsof GLYGLY are collected and analyzed to determine the concentration using thespectrophotometer.

Results

BM AEM BM

1 2 3 4

Fig.1 : Cellule EDI Fig.2 : Installation expérimentale

Figure 4. Elution curve of GLYGLY with thecarbonic acid solution recovered

Figure 3. Breakthrough curves of saturation withGLYGLY (initial form of the bed CO3)

24

Experiments performed show the feasibility of a cyclic process, with three steps, using no pHbuffers, no production of effluences for the purification of amino acids. The amino acids areobtained pure and not in the pH buffers. With a first approximation, the amino acids which cannot only be fixed but also eluted in this process should satisfy with a criterion:

1apK < acidpK < 2apK , i.e. between 6.35 and 10.35 (à 298K).

ConclusionTwo application cases exist: one of them can be fixed and the others can’t, the separation ofamino acid mixture is achieved; one of them can’t be fixed and the others can, the separation isachieved.

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 ofamino 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 ofcarbon dioxide under pressure as displacer, ChERD, 81(10): 1333-1342.

25

TRANSPORT OF AROMATIC AMINO ACIDS DURINGELECTRODIALYSIS

A.E. Bukhovets, T.V. EliseevaVoronezh State University, Russia

1 Universitetskaya sq., 394006 Voronezh (Russia). Tel: +7(4732)208932;email: bukhovets@inbox.ru

AimScientists’ interest to the chemistry of amino acids is explained by their important physiologicalcharacteristics. Electrodialysis is a green technology and has many advantages for the recoveryof amino acids. The aim of our study is to reveal the peculiarities of amino acids transportthrough the ion-exchange membranes during electrodialysis.MethodsThe experiments have been carried out in ordinary laboratory seven-compartment cell withalternating cation-exchange MК-40 and anion-exchange MA-41 and MA-40 membranes (UCCLtd. Shchekinoazot, Russia).ResultsTyrosine transport through the ion-exchange membranes MA-41 and MК-40 at wide initialsolution pH range has been considered. At the initial solution pH 5.6 tyrosine transport isconducted predominantly through the anion-exchange membrane, and flux has the form of curvewith maximum. Maximum conforms to limiting diffusion current density. After exceedinglimiting 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] isobserved. Amino acid flux through the cation-exchange membrane is only diffusive. At theincrease of initial solution pH up to value 11.93, the increase of tyrosine flux through the anion-exchange membrane can be found, but the flux through the cation-exchange membranepractically remains the same. It is explained by the fact that tyrosine is present mainly in theform of anion at the given initial pH solution, and anions are transferred correspondingly throughthe anion-exchange membrane.We have not found tyrosine transport increase through the cation-exchange membrane at initialsolution 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, aswell as the absence of tyrosine electromigration in cation form.This special tyrosine behaviour can be used for separation of amino acids mixtures containingtyrosine by providing electromigration of target amino acid from diluate compartment throughthe cation-exchange membrane.ConclusionStudy of amino acids transfer peculiarities through ion-exchange membranes can help us toimprove the process of these organic ampholytes purification and separation. The observedpeculiarities of aromatic amino acids transport are the basis of their recovery from variousmixtures 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

26

THE INFLUENCE OF MACROSTRUCTURE OF FOILS BASED ONEXFOLIATED GRAPHITE ON GAS PERMEANCE

D.Syrtsova1, O.Shornikova2

1Laboratory of Physical chemistry of Membrane Processes, TIPS RAS, Moscow, RussiaLeninski pr., 29, 119991, dasha@ips.ac.ru

2Departement of Chemical Technology and New Materials, MSU, Moscow, Russia

AimThe new perspectives of membrane gas separation processes development stimulates the searchof new membranes that provide better separation performance with high thermal and chemicalstability. Inorganic porous matrixes including carbon based materials, for example, molecularsieves [1] and adsorption selective membranes [2] demonstrate some advantages in comparisonwith most traditional organic membranes: the permeation properties of carbon membranes is nottime dependent, they have chemical stability and enough high gas selectivity. This paper presentsthe results of the gas permeability study of the foils based on exfoliated graphite, which wasdeveloped at Moscow State University. It was fond [3] that permeance of such materials stronglydepends of macrostructure of exfoliated graphite, particularly, density and structure anisotropy.In this work the influence of characteristic property of graphite macrostructure on permeance andselectivity for different gas flow directions through graphite foils at wide range density arepresented.MethodsThe permeability of H2, N2, O2, CO2 and some light hydrocarbons was measured by gaschromato- graphy technique (differential permeability method) at temperature 23-95oC.ResultsThe mechanisms of gas transport in graphite foils were studied. It was shown that contribution ofLengmure sorption to CO2 selective gas transport through the membrane is very important. Alsoparallel and normal mode of gas flow through graphite were investigated. The dependences ofgraphite density on gas permeance and selectivity at gas flow parallel to membrane surface werestudy. It was obtained that for parallel flow gas permeance is higher than for normal flow. Butthe difference is more at high density. The membrane tortuosity for both modes was estimatedand it was found that for parallel mode the tortuosity is lower for all gases. As result, themembrane permeability at parallel mode was higher. It is interesting to note that for parallelmode experiments the level of H2/CO2 selectivity is closed to Knudsen one and selectivitymaximum for normal flax was not achieved.The temperature dependences of gas permeance for both modes were studied It was shown thatcharacter of the curve is defined by as sample density as gas flux direction.ConclusionIn presented study it was shown that selective gas flow in exfoliated graphite matrix flow isdefined by gas-matrix sorption and membrane macrostructure including anisotropy effect.Obtained results can be effectively used for developing of new carbon based membranes forseparation 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 polymerscience, 2005, v. 50, pp. 93-179

27

SYNTHESIS OF DIBLOCK COPOLYMERS OF 1-TRIMETHYLSILYL-1-PROPYNE WITH 4-METHYL-2-PENTYNE THROUGH SEQUENTIAL

LIVING POLYMERIZATION BY NbCl5 BASED CATALYSTSE.Y. Sultanov, V.S. Khotimskiy

Laboratory of Synthesis of Permselective Polymers, Topchiev Institute of PetrochemicalSynthesis, Moscow, Russia

Leninskiy pr. 29, 119991. Tel: +74959554205; email: sultanov@ips.ac.ru

AimThe 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-1-propyne (PTMSP) and poly-4-methyl-2-pentyne (PMP) namely high gas permeabilityparameters of PTMSP [1] and resistance to most of hydrocarbons of PMP [2,3].Materials which combine these properties are challenging for membrane technology since theycan be used for separation of different gas mixtures containing hydrocarbons.MethodsSynthesis of block copolymers of TMSP with MP was performed by sequential livingpolymerization method. Gel permeation chromatography, IR-spectroscopy and viscosimetrywere used for characterization of obtained block copolymers and their solubility in differentsolvents was investigated. Polymer films from synthesized samples were prepared by castingmethod and permeability parameters of these films were measured by the volumetric method.ResultsTo determine ability of living polymerization of monomers TMSP and MP theirhomopolymerizations on NbCl5–based catalytic systems were investigated. Linear dependenceof number average molecular weight (Mn) versus conversion for the polymerization of TMSPand MP on catalytic systems NbCl5, NbCl5–Ph3SiH and NbCl5–Ph4Sn in cyclohexane andcontinuation 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 catalyticsystems 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.ConclusionConditions of living polymerization of TMSP and MP were found.The method for synthesis of block copolymers of TMSP with MP by sequential livingpolymerization of these acetylenes was developed.The ability to control resistance to solvents and permeability parameters in dependence oncomposition of block copolymers was established.References[1] K. Nagai, T. Masuda, T. Higashimura, B.D. Freeman, I. Pinnau, Poly(1-trimethylsilyl-1-propyne) 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 ofpoly(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 polymerizationof 4-methyl-2-pentyne and 1-trimethylsilyl-1-propyne by NbCl5-Ph4Sn catalyst, Polym. Sci. Ser.A, 2008 (in press)

28

BROMINATION AND CROSSLINKING OFPOLY(VINILTRIMETHYLSILANE)

A.A. Masalev, V.S. KhotimskiyLaboratory of Synthesis of Permselective Polymers, Topchiev Institute of Petrochemical

Synthesis, Moscow, RussiaLeninskiy pr. 29, 119991. Tel: +74959554205; email: masalev@ips.ac.ru

AimMembranes on the basis of polymers of Si-containing hydrocarbons possess high gaspermeability [1]. At the same time these polymers are soluble in various aliphatic and aromatichydrocarbons. Therefore, application of these polymers for separation of mixtures containinghydrocarbon admixtures is problematic. On the other side introducing of polar groups canimprove polymer resistance to hydrocarbons. Bromine can be one of such groups [2, 3]. Thisgroup may be used for further crosslinking of polymer membranes and that will provide polymerstability towards aliphatic and aromatic hydrocarbons.

Results of bromination of poly(vinyltrimethylsilane) (PVTMS) with N-bromosuccinimide andcrosslinking of brominated polymer samples with ethylenediamine are given in the presentation.

MethodsReaction of bromination was carried out with the use of N-bromosuccinimide in solution inCCl4. Ethylenediamine was used for performing of crosslinking of brominated polymer.Reaction of crosslinking was carried out in simulative conditions in solution as well as onprepared polymer films treated with ethylenediamine in methanol. Content of bromine inpolymer and molar fraction of crosslinking were estimated by elemental analysis and on thebasis of IR-spectra.

ResultsThe methods of bromination of PVTMS, which allows introducing bromine up to 50 wt.% inpolymer, and crosslinking of brominated polymers with different crosslinked fractions wereelaborated. Fraction of crosslinking was regulated by quantity of introduced bromine as well asratio bromine/ethylenediamine.

ConclusionsThe method of obtaining of crosslinked membrane on the basis of PVTMS stable towardsaliphatic and aromatic hydrocarbons was elaborated. Samples of polymer membranes withdifferent content of bromine and different content of crosslinked fraction were obtained andstudy of permeation parameters is planned.

References:[1] N.A.Plate, S.G.Durgaryan, V.S. Khotimsky, V.V.Teplyakov, Yu.P. Yampol’skii, Novelpolysiliconolefins for gas Separation, J. Membr. Sci.,52, 289 (1990).[2]Xu Tongwen, Yang Weihua, A novel positively charged composite membranes fornanofiltration prepared from poly(2,6-dimethyl-1,4-phenylene oxide) by in situ aminescrosslinking, J.Membr. Sci., 215 (2003) 25-32.[3] A. A. Masalev, V. S. Khotimskii, G. N. Bondarenko, and M. V. Chirkova, Bromination ofPoly[1-(trimethylsilyl)-1-propyne]with Different Microstructures and Properties of Bromine-Containing Polymers, Polym. Sci. Ser.A, 2008, Vol. 50, No. 1, pp. 47–53.

29

PREPARATION AND PROPERTIES OF NANOCOMPOSITE

MEMBRANES BASED ON RUBBERY POLY(ETHER IMIDE) AND SiO2

J. Grignard1, D. Roizard1, E. Favre1, J. Ghanbaja2

1Laboratoire 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:

Jacques.Grignard@ensic.inpl-nancy.fr2 Service commun de microscopies électroniques et microanalyses X, Faculté des Sciences

Université Henri Poincaré, BP 239, Bd des Aiguillettes, 54506 Vandoeuvre-Lès-Nancy, France

AimThe work's main objective is the synthesis of organic materials for novel uses in the area ofseparation of gas mixtures by dense membranes. The development of these materials is achievedthrough 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 canimprove the performance of permeation of polyimide. In this way, the preparation of originalmultiphase poly(ether imide) (PEI) materials was realized. The second method uses the previouscopolymers in which an inorganic phase is incorporated using either SiO2-fillers or organic silicaprecursors, i.e. TMOS and TEOS[1]. The objective was to understand to what extent thepresence of nano- or micro- sized silica particles may change the properties of the PEI matrix, inparticular the gas separation characteristics.

MethodsSeries of tribloc copolyimides were synthesized from commercial oligoalkoxy α,ω-diamines (Jeffamines), an aromatic diamine (ODA) used as chain extender, and an aromatique di-anhydride (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: eitherhydrophilic microparticles (16 µm), or nanoparticles (12 nm hydrophilic or 16 nm hydrophobicones). To form a more homogenous intermolecular three-dimensional silica network, in situ sol-gel approach was also carried out for the preparation of hybrid materials with the same amountsof silica using tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS). In order toestablish the relations between structures and properties of pure and mixed gases, thecharacterization of chemical structures, physical and physical-chemical properties thesematerials are carried out using adapted analytical methods: spectroscopy, thermogravimetry,calorimetry, microscopy, etc… In this paper, some FTIR, SEM, TEM, DSC and DMA analysiswill be exposed. The properties of PEI and PEI/SiO2 membranes were investigated in transientregime by time-lag experiment for several in gases (N2, CO2, O2, H2, CH4,…) at differenttemperatures, varying from 5 to 45 °C with a membrane thickness ranging from 60 to ≈200 µm.

Results & conclusionsPermeation tests show that the materials obtained are very permeable with CO2 and its selectivityhas interesting values(Table 1). Due to the rubbery structure of PEI the permeation properties forCO2 and N2 are very attractive because they are much higher than known aromatic polyimidesand composite polyimide/SiO2 membranes [2-4].

Table 1: Gas permeabilities (Barrers) forPEI & PEI/SiO2 films at 25 °C

Membrane CO2 N2 CH4

PEI (Jeff600-06) 98 1.58 4.60

PEI + 8%wt. SiO2 (16 nm) 123 2.09 5.49

PEI + 15%wt. SiO2 (16 nm) 63 1.33 -

30

Permeability increases and ideal selectivity decreases with the addition of low amounts ofhydrophobic silica particles. From SEM and TEM studies (Figure 1), it was exposed that silicananoparticles, powders or obtained by the sol-gel method, were distributed homogenously intothe PEI matrix.

References

[1] J. Lizhong, W. Wencai, W. Xiaowei, W. Dezhen, J. Riguang, Effects of Water on thePreparation, Morphology, and Properties of Polyimide/Silica Nanocomposite films Prepared bySol-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-silicacomposite 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 polyimide-organosilicate hybrid membranes, J. Membr. Sci. 211 (2003), p. 25

Figure 1: Cross-sectional SEM micrograph of PEI/SiO2 16nm (92:8) (A) and cross-sectionalTEM micrograph of PEI/SiO2 12nm (92:8) (B)

A B

31

FUNCTIONALIZED POLYMERS FOR CO2 SELECTIVEMEMBRANES. INVESTIGATION OF INTRODUCTION REACTIONS OFLOW-MOLECULAR POLYETHYLENEGLYCOL ETHERS AND «IONIC

LIQUIDS» GROUP IN Si-CONTAINING POLYMERSAuthor: Kiryukhina Y.V; Khotimsky V.S.

Laboratory of Synthesis of Selective Permeable Polymers, TIPS RAS, RussiaLeninsky prosp., 29, 119991 Moscow (Russia); +7(495)9554205;

e-mail: kiruhina@ips.ac.ru

AimThe 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 energycarriers methane and hydrogen from CO2 [1].

The method of membrane separation is one of the most advanced current methods forhydrogen purification. In a number of cases with low content of CO2 in mixture membranesselective 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 ofCO2 recovery from mixtures with H2 and CH4 are insufficiently high [2,3]. With the view ofincreasing of selectivity values the methods of synthesis of these polymers containing functionalgroups that are capable to raise CO2 solubility in polymer owing to reversible specific interactionhave been considered in the present work. This approach should provide high selectivities ofCO2 recovery. Ethylene oxide groups of low-molecular ethers of polyethylene glycol as well asgroups, modeling the structure of “ionic liquids”, have been chosen as groups which are capableto specific interaction. It is known that these groups possess good solubility and solubilityselectivity for CO2 [4,5].

MethodsThe introduction of functional groups in polymer were carried out in 2 steps:

- obtaining of Br-containing polymer by reaction of PTMSP and PVTMS with bromineand 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 N-

butyl-imidazole was considered.

Results and conclusionsThe examined reactions allow performing synthesis of polymers containing ethylene oxide

groups and fragments of “ionic liquids”. The investigation on optimization of content of thesegroups in order to get polymers with film-forming properties and study of permeation propertiesare in progress now.

ReferencesJournal: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)-1-propyne] 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, Novelpolysiliconolefins for gas Separation, J. Membr. Sci.,52, 289 (1990);

32

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 andTechnology, 40:525-541,2005;5. Haiqing Lin, Benny D. Freeman, Materials selection guidelines for membranes that removeCO2 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-ContainingPolymers, Polymer Science, Ser. A, 2008, Vol. 50, No. 1, pp. 37–42.

33

ASYMETRIC POLYIMIDES MEMBRANES FOR PERVAPORATIONSEPARATIONS

Ayman Elgendi, Denis Roizard , Favre EricLaboratoire des Sciences du Génie Chimique, CNRS

ENSIC1, rue Grandville, BP 20451, 54001 NANCY Cedex, FRANCE, Tel: +33 3 83 17 53 04

email: Ayman.El-gendi@ensic.inpl-nancy.fr

IntroductionThis work aimed at preparing polymeric nanofiltration membranes in order to get water selectivemembranes suitable for the retention of organic molecules from polluted water mixtures. Hencetwo objectives must be reached: first, the selection of water selective materials well resistant inalmost pure water, and secondly the preparation of high flux membranes having a thin dense toplayer for selective water permeation. Hence asymmetric membranes were prepared and theirseparation properties preliminary checked by pervaporation.

MethodsTo satisfy the first objective, a copolyimide (PEI) including alkyloxy- rubbery blocks wassynthesized by step polymerization; indeed, propyloxy- and more particularly ethyloxy- etherblocks are known to have high affinity with water. On the other hand, the imide block wasprepared from pyromellitic dianhydride (PMDA) and oxydianiline (ODA) to provide a waterresistant polymer structure after the formation of the imide cycle. Phase inversion method wasused to prepare high flux membranes from PEI organic solutions (15 to 30wt% in DMF). Theparameters of the inversion process were optimized to get highly permeable PEI membranes andto keep simultaneously the molecular separation properties of the related PEI dense films.

ResultsThe physico-chemical properties of PEI membranes were determined by swelling experiments inseveral 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 theseparation properties were respectively characterized by scanning electron microscope (SEM)and pervaporation. To control if the top layer was either tight or porous, pervaporationexperiments of pure liquids and mixtures were routinely carried out and compared with resultsobtained from homogenous dense membranes.

ConclusionThe best samples were found to exhibit molecular selectivity for Ethanol-Water and Toluene-Heptane mixtures. The obtained selectivities were close to the fully dense membranesselectivities with very high pervaporation flux. Hence these samples are promising candidates forthe nanofiltration of organic water mixtures.

Keywords: Polyetherimide, Phase inversion, Asymmetric membrane, Pervaporation

34

NEW ASPECTS OF GAS PERMEABILITY PARAMETERSCORRELATIONS FOR PREDICTION OF MEMBRANE PROPERTIES.

O. Malykh2, V.Teplyakov1,2

1A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences (TIPS RAS)119991, Leninsky pr. 29, Moscow, Russia

2M.V. Lomonosov Moscow State University (MSU), 119992, Leninskie Gory 1, Moscow,Russia

IntroductionAt present an active attention is directed on statistical treatment of experimental data andmethods of physical-chemical properties prediction based on available data. Main attention inpresent paper is focused on technique of statistical treatment of published gas permeability datafor different polymers with aim to fill “empty spaces” of permeability parameters data based onconsideration of possible correlations between them. This developed method allows us toestimate permeability of gases experimental data for which are absent. We used approximationfunctions for this estimation. Paper demonstrates the deviations for known parameters fromestimated values.

ResultsThe 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. Gasesinclude permanent gases, acid gases, lower hydrocarbons, some vapors and oxygen containingorganics presented in literature obtained from permeability experiments. Algorithm of polymerselection for definite separation processes with using desired region of parameters and requiredselectivity is developed. Regular function for permeability of gases was proposed and thisfunction was used for estimation of not known values. Graphic functions in 2D and 3D viewwere considered. Comparative dependences of gas permeability parameters are calculated andthe most linear dependences are accepted. Logarithmic and non-linear permeability function aresuggested. Gas permeability coefficients were calculated by using these functions and calculatedvalues were compared with known experimental (published) data. Deviation for theoreticalresults 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 coefficientswere 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 valuesfro this gases). The respective Database with selection of desired polymers (selectivity,permeability, class, chemical structure) was developed. Additionally, the software for calculationof separation productivity of membrane modules for multi-component gas mixture separationwas developed. The both parts of software have “bridge” for communication and can be inprospect used for education aims and practical applications.

Acknowledgements

This work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, Grant RFBRNo. 08-03-92495-НЦНИЛ_а and Goscontract No. 02.516.11.6043.

35

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, France2 G.E.V.S.M., Université Henry Poincaré, Nancy, France

3 Laboratoire des Sciences du Génie Chimique, ENSIC, 1 rue Grandville, 54000 Nancy, FranceTel: +33 (0)3 83 17 50 27; email: Danielle.Barth@ensic.inpl-nancy.fr

The phosphine imide strategy (1) was initially developed in organic solvents to achieve arapid and easy access to sophisticated cyclodextrines derivatives (urea, carbodiimides andisocyanates) (2). In this strategy, CO2 was used as reactant.

We have investigated the usability of supercritical CO2 (scCO2) as solvent and reactantfor a standard reaction. In our previous investigations on the reaction in scCO2, we havedeveloped a kinetic model for the standard reaction in a 100mL high pressure reactor (3). Itappears that the production of isocyanates in scCO2 was following a first order kinetic. Theproduction 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 resultsobtained in a 1L high pressure reactor. The comparison between calculated and experimentalresults was satisfactory with errors below 20%.

The scCO2 and phosphine imide strategy were also used to produce one compound ofpharmaceutical interest, which was previously produced in DMF (4):

The kinetic of this reaction was followed and the desired compound was obtained in lessthan 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, "PhosphineImide" Reaction on Peracetylated -Cyclodextrins: Comparison between Supercritical CO2 andOrganic Solvent Processes, Barcelona , ISASF Sympsonium 2008.

[4] Stéphane Menuel, Jean-Pierre Joly, Blandine Courcot, Josias Elysée, Nour-Eddine Ghermaniand Alain Marsura, Synthesis and inclusion ability of a bis-β-cyclodextrin pseudo-cryptandtowards Busulfan anticancer agent, 2007(63)1706

36

HIGH-PRESSURE MAGNETIC SUSPENSION BALANCE ANDSUPERCRITICAL CARBON DIOXIDE

S.Miccilino, D.BarthLaboratoire des Sciences du Génie Chimique, Nancy-Université, France

ENSIC, 1 rue Grandville BP20451-54001 NANCYtel : 33(0)3 83 17 50 27 ; danielle.barth@ensic.inpl-nancy.fr

Physical adsorption of fluids onto solids is of interest in the transportation and storage of fueland 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 extensivelystudied over a wide range of temperatures and pressures, the number of works related toadsorption at high pressures is limited. In order to study supercritical process such asadsorption/desorption of Volatile Organic Compounds, impregnation of polymers, diffusion ofSC-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-madeequipment. The balance working up to 35 MPa and 250°C, allows the determination of specificquantities without danger of pollution or destruction of the balance. We present in a first part abibliographic review about polymers[1] and adsorbents [2] and in a second part the laboratoryequipment.

Figure 1: Solubility of carbon dioxide Figure 2: SC-CO2 microbalancein poly(vinyl acetate)[1]

References

[1]Yoshiyuki Sato, Tadao Takikawa, Shigeki Takishima, Hirokatsu MasuokaSolubility and diffusion coefficients of carbon dioxide in poly(vinyl acetate) and polystyreneThe Journal of Supercritical Fluids, 19, 2 ( 2001) 187-198[2]A.Herbst,R.Staudt,P.HartingThe magnetic suspension balance in high pressure measurements of pure gasesJournal of thermal analysis and calorimetry 71(2003) 125-135

37

HYBRIDE MEMBRANE/PSA METHOD FOR HYDROGEN RECOVERYFROM MULTICOMPONENTS GAS MIXTURES OF BIOTECHNOLOGY

AND PEROCHEMISTRYO.L. Amosova1,2, O.V. Malykh2, V.V. Teplyakov1,2

1A.V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences (TIPS RAS)119991, Leninsky pr. 29, Moscow, Russia

2M.V. Lomonosov Moscow State University (MSU), 119992, Leninskie Gory 1, Moscow,Russia; e-mail: o.amosova@gmail.com

Traditional methods of separation and purification of gas mixture usually include cryogenic,absorption, adsorption and membrane technologies. The problems of recovery of hydrogen frommulticomponents gas mixture assume the development of safe technologies with low powerconsumption.

Our study presents a review of publications concerned with hydrogen recovery from the gasmixtures. Also the motivations for developing of integrated membrane/PSA method arediscussed. This method combines the using of membranes modules based on commerciallyaccessible membranes and well known pressure swing adsorption (PSA) processes for effectiverecovery of hydrogen from biogas. We also present the results of comparison of modules basedon commercially available membranes (GENERON hollow fibers membranes and flat sheetmembranes based on PVTMS) for hydrogen recovery from multicomponent gas mixturescontaining CO, CO2, N2, H2S. The estimation of H2S, CO, H2O permeability of membranes wascarried out by the correlation method. The comparative analysis of hollow fiber membranemodule and flat sheet membrane module for pre-concentration of H2 from multicomponents gasmixture include CO, CO2, N2, H2S has been made. Taking into account the principle of gasesseparation in condition of PSA we considered the basic classes of adsorbents for effectiverecovery of hydrogen from gas mixture. It is know that a special problem of hydrogen recoveryis the presence of aside gases. This problem can be solved by the combination of membrane andadsorption processes. Optimum parameters for PSA-separation (2 stage) are reached at the stageof 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 commerciallyaccessible 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 considerablyimproved by usage of new effective membrane materials and adsorbents.

This work is partially supported by FP6 IP n˚019825-(SES6) “HYVOLUTION”, Grant RFBRNo. 08-03-92495-НЦНИЛ_а and Goscontract No. 02.516.11.6043.