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Natural gas (NG) processing and membrane technology are two very important fields that are of great significance due to increasing demand for energy as well as gas mixtures separation. While NG is projected to be the number one primary source of energy by 2050, membrane separation is a commercially successful competitor to other separation techniques for energy efficient gas purification processes (Qiu et al., 2011). Most of the NG produced in the world is coproduced with acid gases such as CO2 which need to be removed to increase the caloric value of NG. A comprehensive review of research efforts in CO2 separation from natural gas is required to capture details of the current scientific and technological progresses on the development of new membrane materials with tailored gas transport properties, and the improvement of properties of the existing ones. This paper presents the progresses that have been achieved in the area of material science and engineering to eliminate the limitations that dominate the large scale application of membrane materials at the present time. Research efforts in material development in the context of the break through and challenges that exist for major industrial applications of membrane in CO2 removal from NG are reported.

Abstract

Challenges in Membrane Materials Development for Gas Separation

CO2-induced Plasticization and Conditioning

Figure 4. Permeability of CO2 as a function of Feed Pressure in Glassy PSF and Rubbery PEO (Data used were obtained from Scholes et al., (2010); and Lin and Freeman (2004)).

Membrane with Higher Plasticization Pressure

Figure 5. Separation Performance of Decarboxylation-induced Thermal Crosslinking of Hollow Fiber 6FDA-DAM:DABA (3:2) Membrane for Pure CO2 Gas (Data were obtained from Qiu et al., 2011)

References

Figure 6. (a) Separation Performance of Decarboxylation-induced Thermal Crosslinking of Hollow Fiber 6FDA-DAM:DABA (3:2) Membrane for 50%CO2 /50% CH4 Gas using data from Qiu et al. (2011) (b)Improved Plasticization Resistance via Crosslinking of 6FDA-DAM-DABA (2:1) using data from Staudt-Bickel & Koros (1999); and Kratochvil & Koros (2008)

The three important identified challenges are:

1.Better gas selectivity without sacrificing gas permeability

2.Problem of CO2-induced plasticization and conditioning

3.Maintaining the long-term gas separation performance by overcoming the problems of physical aging

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Bernardo, P., Drioli, E., & Golemme, G. (2009). Membrane Gas Separation: A Review/State of the Art. Ind. Eng. Chem. Res. , 48, 4638–4663.

Han, S. H., Lee, J. E., Lee, K.-J., Park, H. B., & Lee, Y. M. (2010). Highly gas permeable and microporous polybenzimidazole membrane by thermal rearrangement. Journal of Membrane Science , 357 , 143–151.

Kratochvil, A. M., & Koros, W. J. (2008). Decarboxylation-Induced Cross-Linking of a Polyimide for Enhanced CO2 Plasticization Resystance. Macromolecules , 41, 7920- 7927.

Lin, H., & Freeman, B. (2004 ). Gas solubility, diffusivity and permeability in poly(ethylene oxide). Journal of Membrane Science , 239 , 105–117.

Park, H. B., Han, S. H., Jung, C. H., Lee, Y. M., & Hill, A. J. (2010). Thermally rearranged (TR) polymer membranes for CO2 separation. Journal of Membrane Science , 359 , 11–24.

Qiu, W., Chen, C.-C., Xu, L., Cui, L., Paul, D. R., & Koros, W. (2011). Sub-Tg Cross-Linking of a Polyimide Membrane for Enhanced CO2 Plasticization Resistance for Natural Gas Separation. Macromolecules , 44, 6046–6056.

Scholes, C. A., Chen, G. Q., Stevens, G., & Kentish, S. E. (2010). Plasticization of ultra-thin polysulfone membranes by carbon dioxide. Journal of Membrane Science , 346 , 208–214.

Staudt-Bickel, C., & Koros, W. J. (1999). Improvement of CO2/CH4 separation characteristics of polyimides by chemical crosslinking. Journal of Membrane Science , 155, 145–154.

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Figure 3. Thermally Rearranged Polymer Membranes that Surpassed the 2008 Upper Bound [(a) Han et al., (2010) (b) Park et al. (2010)]

Figure 2. Robeson’s 1991 and 2008 Upper Bound Curves Representing a General Trade-Off for Membrane Gas Separation Performance

[(a) Wind et al., (2004); (b) Xiao et al., (2009)]

Figure 1. Permeability and Permselectivity of gases at feed pressure of 3.5 bar; membrane thickness of 20 μm (Bernardo et al., 2009)

180oC, 24hr 330oC, 20hr 350oC, 1hr

130

250 265

27 27 2655 69 69

Separation Performance of Decarboxylation-induced Thermal Crosslinking of Hollow Fiber 6FDA-DAM:DABA (3:2) Membrane for

50%CO2 /50% CH4Gas (Qiu et al., 2011)

Permeability PermSelectivity Plasticization Pressure(barrer) (bar)

Better Balance of Selectivity and Permeability

School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia

Jimoh K. Adewole and Abdul Latif Ahmad

Membrane Separation of CO2 from Natural Gas:

A State-of-the-Art Review on Material Development

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Cytop Hyflon AD 60

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Separation Performance of Decarboxylation-induced Thermal Crosslinking of Hollow Fiber 6FDA-DAM:DABA (3:2) Membrane for

Pure CO2 Gas (Qiu et al., 2011)

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Decarboxylation at high Temperature+220 oC, 23hr + rapid Quenching from above Tg

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Improved Antiplasticization Resistance via Crosslinking of 6FDA-DAM-DABA (2:1) (Staudt-Bickel & Koros ,1999; and

Kratochvil & Koros, 2008)

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Polysulfone (PSF) Polyethylene oxide (PEO)

Permeability of CO2 as a function of Feed Pressure in Glassy PSF and Rubbery PEO (Scholes et al., 2010; and Lin and Freeman, 2004)

Minimum Permeability

Plasticization Pressure

(b)

(a) (b)

Department of Chemical Engineering, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia DSL333