温室效应是如今人类所面临的一个重大问题，而二氧化碳对温度效应的贡献最大，因此发展研究捕集（Capture）CO2的新型高效节能技术及相关理论，对避免温室效应，保护环境具有极其重要的意义。本文提出了将膜分离法和水合物法结合起来即水合物膜法，并利用自行组建的水合物膜法分离二氧化碳实验系统初步探索了多孔陶瓷管的孔径，体系的压力、温度、气体组成等条件对水合物膜形成的影响。结果表明，采用380nm孔径的α-Al2O3陶瓷管组装成膜分离器，CO2/N2原料混合气中CO2含量越高，压力越高，温度越低，保持的静态时间越长，越有利于完整无缺陷的水合物膜的形成。

 Greenhouse gases have become a serious world problem. CO2 is known to be the most prevalent greenhouse gas and has the potential to cause severe changes in the global climate. New energy-saving and effective technology to capture CO2 should be developed in present factory for CO2 Emission Reduction. It has scientific significance and broad application prospects in reducing the greenhouse effect and environmental protection. Hydrate membrane separation which combined hydrate with membrane separation has been proposed. Influencing factors of forming hydrate membrane such as the pore size of ceramic tube, gas composition, pressure and temperature were investigated using the self-established experimental apparatus of hydrate membrane separation for CO2 capture. The results demonstrate that α-Al2O3 ceramic tube with average pore diameter of 380nm is better than the others for forming hydrate membrane. The CO2/N2 mixture gas with more CO2 will be more easy to form flawless hydrate membrane under condition of higher pressure , lower temperature and longer static time.

[1]  陈红萍，梁英华，王奔．二氧化碳的化学利用及催化体系的研究进展．[J]．化工进展，2009，28 (增刊) ：271-278
[2]  Keeling C D，Whorf T P. Atmospheric CO2 records from sits in the SiO2 air sampling network, in: Trends: A compendium of data on global change[R]//Carbon Dioxide Information Analysis Center,Oak Ridge National Laboratory ,U S Department of Energy,Oak Ridge,TN,USA,2005.
[3]  Stewart C, Hessami M, A study of methods of carbon dioxide capture and sequestration–the Sustainability of a photosynthetic bioreactor approach．[J]．Energy Conversion and Management，2005，46：403–420.
[4]  曾宪忠，陈昌和，高保成. 烟气脱碳技术进展.[J]. 化工环保，2000，20：12-17.
[5]  Peter E，Separation of CO2 from CO2/N2 and CO2/H2 mixtures [C].International Symposium on the Practical Applications of Gas Hydrates，Busan，Korea.October 17-18，2006
[6]  Hideo T，Akihio Y，Fumio K. Energy consumption estimation for greenhouse gas separation processes by clathrate hydrate formation．[J]．Energy，2004，29：1713-1729.
[7]  Schiojiri K，Okano T，Yanagisawa Y，et al. A new type separation process of condensable greenhouse gases by the formation of clathrate hydrates．[J]．Studies in Surface Science and Catalysis，2004，153：507-512.
[8]  Imen C，Anthony D，Laurence F，et al. Benefits and drawbacks of clathrate hydrates：A review of their areas of interest．[J]．Energy Conversion and Management，2005，46：1333-1343.
[9]  Cha S B, Ouar H, Wildeman T R, Sloan E D. A third-surface effect on hydrate formation．[J]．J Phys Chem, 1988, 92(23)：6492－6494
[10]  Wilson P W, Daniel Lester, Haymet A D J. Heterogeneous nucleation of clathrates from supercooled tetrahydrofuran (THF)/water mixtures,and the effect of an added catalyst．[J]．Chem Eng Sci, 2005, 60：2937－2941
[11]  Sun Y，Wang YＸ，Zhang Y，et al．CO2 sorption in activated carbon in the presence of water．[J]．Chemical Physics Letters.，2007，437：14-16.
[12]  Taekseo Y. Efficient Recovery of CO2 from Flue Gas by Clathrate Hydrate Formation in Porous Silica Gels．[J]．Environmental Science & Technology， 2005，39：2315-2319.
[13]  Tsutomu U，Takao E，Satoshi T，et al. Effects of pore sizes on dissociation temperature and pressures of methane，carbon dioxide，and propane hydrates in porous media[J]. The Journal of Physical and Chemical B，2002，106：820-826.
[14]  朱玲，王金渠，樊栓狮，水合物膜法捕集烟道气中CO2新技术．[J]．化工进展，2009，28：279-283
[15]　Kang S P， Lee H， Lee C.-S，et al．Hydrate phase equilibria of the guest mixtures containing CO2, N2 and tetrahydrofuran．[J]．Fluid Phase Equilibria，2001，185：101–109
[16]  Wang Y, Zhou YPg, Liu CM，et al．Comparative studies of CO2 and CH4 sorption on activated carbon in presence of water．[J]．Colloids and Surfaces A: Physicochem. Eng. Aspects，2008，322：14–18
[17]  Uchida T, Ebinuma T, Takeya S，et al．Effects of Pore Sizes on Dissociation Temperatures and Pressures of Methane, Carbon Dioxide, and Propane Hydrates in Porous Media．[J]．J. Phys. Chem. B 2002, 106：820-826
[18]  Linga P, Kumar R, Englezos P．Gas hydrate formation from hydrogen/carbon dioxide and nitrogen/car bon dioxide gas mixtures．[J]．Chemical Engineering Scienc，2007，62：4268 – 4276
[19]  Englezos P, Kalogerakis N, Dholabhai P，et al．Kinetics of formation of methane and ethane gas hydrates．[J]．Chem. Eng. Sci，1987，42：2647-2658
[20]  Zhong Y，Raogers RE，Surfactant effects on gas hydrate formation．[J]．Chem. Eng. Sci，2000，55：4175-4187
[21]  Uchida T，Ebinuma T，Kawabata J．Microscopic observations of formation processes of clathrate-hydrate films at an interface between water and carbon dioxide．[J]．J. Crystal Growth，1999，204：348－356
[22]  Uchida T， Ikeda IY， Takeya S，et al．CO2 hydrate film formation at the boundary betweenCO2 and water：effects of temperature, pressure and additiveson the formation rate．[J]．Journal of Crystal Growth 237–239 (2002) 383–387
[23]  Katsuki D, Ohmura R, Ebinuma T，et al．Formation, growth and ageing of clathrate hydrate crystals in a porous medium．[J]．Philosophical Magazine,Vol. 86, No. 12, 21 April 2006, 1753–1761