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MEMBRANE TECHNOLOGY FOR CARBON DIOXIDE CAPTURE

Sandra Kentish CRC for Greenhouse Gas Technologies, Department of Chemical and Biomolecular Engineering, University of Melbourne, Victoria 3010 sandraek@unimelb.edu.au

INTRODUCTION
CO2 capture refers to the separation of carbon dioxide from other gases, and is a necessary precursor to geological sequestration. The cost of capture can be 70-90% of the total cost of sequestration and hence is the critical component in any economic analysis of this greenhouse gas technology. Fossil fuelled power generation represents the largest potential source of carbon dioxide. Carbon dioxide can be captured from this source by a number of mechanisms: by separation of oxygen from air prior to combustion. This leads to a flue gas rich in carbon dioxide that will require little or no treatment prior to separation. by gasification of the fuel source, reaction with water and subsequent separation of the carbon dioxide from product hydrogen. This water-shifted syngas is typically at relatively high pressure (20 atm) and in a reducing condition. CO2 concentrations are typically 35-40%1. by post-combustion capture of CO2 from the combustion flue gases. These flue gases are usually unpressurised, and in an oxidising condition. CO2 concentrations range from 3-5% v/v in gas plants to 13-15% v/v in coal plants2.

Solvent absorption technology is the only commercially proven method of flue gas CO2 capture. However, the use of membrane technology offers a viable alternative. Gas separation membranes are semi-permeable materials that permit the direct passage of carbon dioxide but retain other molecules. Membrane units are small in volume and occupy a small footprint. They are operationally simple and require little attention once commissioned. They will thus readily fill niche markets for carbon capture such as in offshore and remote locations. Polymeric Membrane Materials While gas separation membranes have not been proven in flue gas service, they have had commercial success in the separation of CO2 from natural gas at the well head. Initially cellulose acetate spiral wound membranes were used in this service, but the trend more recently has been towards hollow fibre polyimide membranes. Polyimides are glassy polymers with a high affinity for carbon dioxide. The inclusion of ring structures along the polymer backbone increases the polymer strength, while the inclusion of fluoride groups as side chains adds to the CO2 solubility.

The major technology barrier to more widespread use of such polymeric membrane technology is the currently short useful life span. After several years of operation in carbon dioxide service, the membranes fail in a process known variously as compaction, aging or plasticisation. This failure occurs by the chemical interaction of the carbon dioxide, or heavier hydrocarbons with the membrane material itself. To address this issue, RITE pursued the development of a novel cardo-type polyimide with UBE Industries and Sumitomo Electric for many years. However, this research program has now been substantially curtailed. Our work in this area attempts to strengthen the membrane structure through the introduction of an epoxy content3. Other workers are attempting to add strength to polyimide structures through the use of copolymers4, cross-linking agents5,6, and/or thermal annealing7. However, in most cases, the increase in strength is accompanied by a significant decrease in permeability. Many workers are considering alternate polymer backbones such as polysulfone, polyethersulfone, polyphenylene oxide, polyethylene oxide, polyetherketones and epichlorohydrin systems. The Los Alamos National Laboratory has been experimenting with a thin film polybenzimidazole membrane cast on a metallic substrate8. They claim that this structure is viable at temperatures between 150 and 370C and exhibits permselectivity towards CO2 that is an order of magnitude higher than current polymer membranes. Other workers have modified mesoporous silica membranes to attach amino groups to the surface9. This again results in a CO2 selective membrane that is selective and can operate at above ambient temperatures.

High Temperature Membrane Reactors Membranes are also showing promise for high temperature pre-combustion capture10. It is well known that both steam reforming and water gas shift reactions are equilibrium limited. One approach for overcoming this limit is to carry out the reaction in a reactor with walls that are selectively permeable to either CO2 or hydrogen (a membrane reactor). The removal of reaction products in this manner enhances the rate of reaction. This application requires a membrane that is viable at temperatures in excess of 600C. Membranes that are permeable towards hydrogen generally act as molecular sieves, with pore sizes small enough to permit passage only of this moiety (around 0.5 nm). These can be based on a zeolite matrix, carbon nanotubes or other inorganic substrates. Other workers utilise the high affinity of palladium and vanadium metals towards hydrogen as the basis for separation11,12. Membranes that are CO2 permeable rely on the affinity of this molecule for the membrane material itself. Ion-exchanged zeolites13, silica-zirconia14 and multiwalled carbon nanotubes15 have been considered for this purpose.

Membrane/Solvent Hybrid Technology Membrane and solvent technology can also be combined in a membrane contactor. In this instance, a system of inert membranes replaces the classical packed tower in a standard solvent absorption process. These semi-permeable membranes keep the gas and liquid phases separate but allow the passage of CO2 between the two. Kvaerner find Gore-tex ePTFE to be the most suitable for this purpose16. However, other workers are experimenting with polypropylene hollow fibres which are cheaper, but require the use of alternative solvent formulations17. This technology reduces the size of the absorber and stripper units by 65% and lowers the reboiler duty and solvent loss. By making the process equipment more tolerant to the solvent, the technology enables additional solvent optimization, which should further reduce energy requirements and associated costs.

CONCLUSION Gas separation membranes have the potential to capture carbon dioxide from both precombustion and post-combustion gas streams. The use of such technology currently represents a more costly and higher risk option than the commercially proven solvent absorption process. However, as the technology is immature, and there is an intensive research focus in this area, costs should fall quickly. It is envisaged that within five to ten years, membranes will be able to provide strong competition for solvent based systems.

REFERENCES
D.Wallace 'Capture and Storage of CO2: What Needs to be Done' in COP6 (Sixth Conference of the parties to the UN Framework Convention on Climate Change) (2000) The Hague 2 Herzog, H., Environmental Science and Technology, 35:7 (2001) 148 A153 A 3 Nagai, K., Booker, N., Mau, A., Hodgkin, J., Kentish, S., Stevens, G., Geertsema, A., Gas Permeation Properties of Polyimide/Epoxy Composite Materials, 222nd ACS Fall National Meeting, Chicago, 26-30 August 2001. 4 R.L. Burns, W.J. Koros, Macromolecules 36(7) (2003) 2374-2381 5 Y.Liu, T-S. Chung, R. Wang, D.F. Li, M.L. Chang, Ind. Eng. Chem. Res. 42(6) (2003) 1190-1195 6 J.D. Wind, C. Staudt-Bickel, D.R. Paul, W.J. Koros Ind.Eng. Chem. Res. 41(24) (2002) 6139-6148 7 A. Bos, I.G.M. Punt, M. Wessling H. Strathmann, Sep. Purif. Technol 14 (1998) 27-39 8 Pesiri D.R., Jorgnesen B., Dye R.C., J. Membrane Science 218 (2003) 11-18 9 S.Kim, V.V. Guliants, J. Ida, Y.S. Jerry, "Ordered Mesoporous Silica Membranes for Carbon Dioxide Separation from Flue Gas" 225th ACS National Meeting, New Orleans, 23-27 March 2003. 10 Klara S.M., Srivastava R.D.,Environmental Progress 21(4) (2002) 247-253 11 Damle A.S., Proceedings - Annual International Pittsburgh Coal Conference (2002) 1987-1998 12 Y. Gu, K. Kusakabe, S. Morooka, J. Chem. Eng. Japan 35(5) (2002) 421-427 13 Y. hasegawa, T. tanaka, K. Watanabe, B-H Jeong, K. Kusakabe, S. Morooka, Korean J. Chem. Eng. 19(2) (2002) 309-313 14 K. Osada, T. Kato, Kagaku Kogaku Ronbunshu 28(1) (2002) 67-72 15 R. Andrews, m. Jagtoyen E. Grulke, K-H Lee, Z. Mao, S.B. Sinnott, NASA Conference Publication (2001) 210948 701-706 16 O. Falk Pederson, H. Dannstrom, M. Gronvold, D. Stuksrud, O. Ronning, Gas Treatment Using Membrane Gas/Liquid Contactors 5th International Conference on Greenhouse Gas Control Technologies, Cairns, Australia, August 13-16 (2000) 17 P.S. Kumar, J.A. Hogenfoorn, P.H.M. Feron, G.F. Versteeg, Chemical Engineering Science 57 (2002) 1639-1651
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