对膜法烯烃/烷烃分离技术的现状进行了总结，论述了膜法促进传递分离烯烃/烷烃的机理、研究进展及存在的问题。分析了固体聚合物电解质膜对烯烃/烷烃分离性能的影响因素，探讨了固体聚合物电解质中高分子材料和烯烃载体对膜性能的影响，阐述了烯烃载体Ag+的中毒及再生过程和烯烃渗透的时间依赖性。

The research status of solid polymer electrolyte membranes for olefin/paraffin separation is reviewed. The olefin/paraffin separation mechanism, research progress and current problems of facilitated transport membrane are described clearly. The influence of solid polymer electrolyte membrane on the performance of olefin/paraffin separation is analyzed, the polymeric membrane materials and olefin carriers for solid polymer electrolyte membranes are also discussed. Finally, the poisoning/regeneration mechanisms of carrier sliver salt and the olefin time-dependent permeation are also discussed.

[1] Semenova S I. Polymer membranes for hydrogencarbon separation and removal. [J]. J membr Sci, 2004,231:189-207.
[2] Burns R L, Koros W J. Defining the challenges for C3H6/C3H8 separation using polymeric membranes. [J]. J Membr Sci, 2003,211:299-309.
[3] Sridhar S, Khan A A. Simulation studies for the separation of propylene and propane by ethylcellulose membranes. [J]. J Membr Sci, 1999,159:209-219.
[4] Ilinitch O M, Semin G L, Chertova M V, et al. Novel polymeric membranes for separation of hydrocarbons. [J]  J Membr. Sci, 1992,66:1-8.
[5] Krol J J, Boerrigter M, Koops G H. Polyimide hollow fiber gas separation membranes: preparation and the suppression of plasticization in propane/propylene environments. [J]. J Membr Sci, 2001,184:275-286.
[6] Tanaka K, Taguchi A, Hao J Q, et al. Permeation and separation properties of polyimide membranes to olefins and paraffins. [J]. J Membr Sci, 1996,121:197-207.
[7] Yoshino M, Nakamura S, Kita H, et al. Olefin/paraffin separation performance of asymmetric hollow fiber membrane of 6FDA/BPDA-DDBT copolymide. [J]. J Membr Sci, 2003,212:13-27.
[8] Mulder M. Basic principles of membrane technology. 2nd ed. [M]. Dordrecht: Kluwer Academic Publishers. Inc, 1996.
[9] Dewar M J S. A review of the π-complex theory. [J]. Bull Soc Chim Fr, 1951,18:C71-79.
[10] Chatt J, Duncanson L A. Olefin coordination compounds. Part III. Infrared spectra and structure: Attempted preparation of acetylene complexes. [J]. J Chem Soc, 1953,2939-2947.
[11] Way J D, Noble R D, Flynn T M, et al. Liquid membrane transport: a survey. [J]. J Membr Sci, 1982,12:239-259.
[12] Teramoto M, Matsuyama H, Yamashiro T, et al. Separation of ethylene from ethane by a flowing liquid membrane using silver nitrate as a carrier. J Membr Sci., 1989 (45): 115-136.
[13] Teramoto M, Matsuyama H, Yamashiro T, et al. Separation of ethylene from ethane by supported liquid membranes containing silver nitrate as a carrier. [J]. J Chem Eng Jpn, 1986,19:419-424.
[14] Neves L A, Crespo J G, Coelhoso I M. Gas permeation studies in supported ionic liquid membranes. [J]. J Membr Sci, 2010,357:160-170.
[15] Won J, Kim D B, Kang Y S, et al. An ab initio study of ionic liquid silver complexes as carriers in facilitated olefin transport membranes. [J]. J Membr Sci, 2005,260:37-44.
[16] Gan Q, Rooney D, Zou Y. Supported ionic liquid membranes in nanopore structure for gas separation and transport studies. [J]. Desalination, 2006,199:535-537.
[17] Kim J H, Won J, Kang Y S. Olefin-induced dissolution of silver salts physically dispersed in inert polymers and their application to olefin/paraffin separation. [J]. J Membr Sci, 2004,241:403-407.
[18] Sungpet A, Way J D, Thoen P M, et al. Reactive polymer membranes for ethylene/ethane separation. [J]. J Membr Sci, 1997,136:111-120.
[19] 叶震, 刘丽, 陈勇, 等. 聚砜/磺化聚砜共混及离子交换膜C3H6/C3H8渗透性能的研究. [J]. 膜科学与技术, 2002,22:1-5.
[20] Park Y S, Won J, Kang Y S. Preparation of Poly(ethylene glycol) Brushes on Polysulfone Membranes for Olefin/Paraffin Separation. [J] Langmuir, 2000,16:9662-9665.
[21] Pinnau I, Toy L G. Solid polymer electrolyte composite membranes for olefin/ paraffin separation. [J]. J Membr Sci, 2001,184:39-48.
[22] Yoon Y, Won J, Kang Y S. Polymer electrolyte membranes containing silver ion for facilitated olefin transport. [J]. Macromolecules, 2000,33:3185-3186.
[23] Kim J H, Min B R, Won J, et al, Anomalous temperature dependence of facilitated propylene transport in silver polymer electrolyte membranes. [J]. J Membr Sci, 2003,227:197-206.
[24] Pinnau I, Toy L G, Casillas C. Olefin separation membrane and process. [P]. US patent 5670051. 1997.
[25] Noble R D. Analysis of facilitated transport with fixed site carrier membranes. [J]. J Membr Sci, 1990,50:207-214.
[26] Eriksen O I, Aksnes E, Dahl I M. Facilitated transport of ethene through Nafion membranes. Part II. Glycerine treated, water swollen membranes. [J]. J Membr Sci, 1993,85:99-106.
[27] Hsu W Y, Gierke T D. Ion transport and clustering in nafion perfluorinated membranes. [J]. J Membr Sci, 1983,13:307-326.
[28] Yang J, Hsiue G. Swollen polymeric complex membranes for olefin/paraffin separation. [J]. J Membr Sci, 1998,138:203-211.
[29] Yamaguchi T, Baertsch C, Koval C A, et al. Olefin separation using silver impregnated ion-exchange membranes and silver salt/polymer blend membranes. [J]. J Membr Sci, 1996,117:151-161.
[30] Hsiue G, Yang J. Novel methods in separation of olefin/paraffin mixtures by functional polymeric membranes. [J]. J Membr Sci, 1993,82:117-128.
[31] Hong S U, Kim J Y, Kang Y S. Effect of water on the facilitated transport of olefins through solid polymer electrolyte membranes. [J]. J Membr Sci, 2001,181:289-293.
[32] Ho W S, Dalrymple D C. Facilitated transport of olefins in Ag+-containing polymer membranes. [J]. J Membr Sci, 1994,91:13-25.
[33] Azhin M, Kaghazchi T, Rahmani M. A review on olefin/paraffin separation using reversible chemical complexation technology. [J]. J Ind Eng Chem, 2008,14:622- 638.
[34] Kim J H, Min B R, Kim C K, et al. New Insights into the Coordination Mode of Silver Ions Dissolved in Poly(2-ethyl-2-oxazoline) and Its Relation to Facilitated Olefin Transport. [J]. Macromolecules, 2002,35:5250-5255.
[35] Hong S U, Kim J Y, Kang Y S. Olefin Transport Through Solid Polymer Electrolyte Membranes. [J]. Polym Adv Technol, 2001,12:177-182.
[36] Kim J H, Min B R, Kim H S, et al. Facilitated transport of ethylene across polymer membranes containing silver salt: effect of HBF4 on the photoreduction of silver ions. [J]. J Membr Sci, 2003,212:283-288.
[37] Park Y S, Won J, Kang Y S, Facilitated transport of olefin through solid PAAm and PAAm-graft composite membranes with silver ions. [J]. J Membr Sci, 2001,183:163-170.
[38] Wang Y B, Ren J Z, Deng M C. Ultrathin solid polymer electrolyte PEI/Pebax2533/AgBF4 composite membrane for propylene/propane separation. [J]. Sep Purif Technol, 2011,77:46-52.
[39] Kang S W, Kim J H, Char K, et al. Nanocomposite silver polymer electrolytes as facilitated olefin transport membranes. [J]. J Membr Sci, 2006,285:102-107.
[40] Hess S, Staudt-Bickel C, Lichtenthaler R N. Propene/propane separation with copolyimide membranes containing silver ions. J Membr Sci., 2006.275:52-60.
[41] Kang S W, Lee D H, Park J H, et al. Effect of the polarity of silver nanoparticles induced by ionic liquids on facilitated transport for the separation of propylene/ propane mixtures. [J]. J Membr Sci, 2008,322:281-285.
[42] Kang S W, Hong J, Park J H, et al. Nanocomposite membranes containing positively polarized gold nanoparticles for facilitated olefin transport. [J]. J Membr Sci, 2008,321:90-93.
[43] Mun S H, Kang S W, Cho J, et al. Enhanced olefin carrier activity of clean surface silver nanoparticles for facilitated transport membranes. [J]. J Membr Sci, 2009,332:1-5.
[44] Kang S W, Kim J H, Oh K S, et al. Highly stabilized silver polymer electrolytes and their application to facilitated olefin transport membranes. [J]. J Membr Sci, 2004,236:163-169.
[45] Kim J H, Won J, Kang Y S. Silver polymer electrolytes by π-complexation of silver ions with polymer containing C=C bond and their application to facilitated olefin transport membranes. [J]. J Membr Sci, 2004,237:199-202.
[46] Yang J, Hsiue G. Selective olefin permeation through Ag(I) contained silicone rubber-graft-poly(acrylic acid) membranes. [J]. J Membr Sci, 1997,26:139-149.
[47] Sunderrajan S, Freeman BD, Hall C K, et al. Propane and propylene sorption in solid polymer electrolytes based on poly(ethylene oxide) and silver salts. [J]. J Membr Sci, 2001,182:1-12.
[48] Kim J H, Kim C K, Won J, et al. Role of anions for the reduction behavior of silver ions in polymer/silver salt complex membranes. [J]. J Membr Sci, 2005,250:207-214.
[49] Kim J H, Min B R, Kim C K, et al. Spectroscopic Interpretation of Silver Ion Complexation with Propylene in Silver Polymer Electrolytes. [J]. J Phys Chem B, 2002,106:2786-2790.
[50] Kim J H, Park S M, Won J, et al. Unusual separation property of propylene/propane mixtures through polymer/silver complex membranes containing mixed salts. [J]. J Membr Sci, 2005,248:171-176.
[51] Merkel T, Blanc R, Zeid J, et al, Separation of olefin/paraffin mixtures with carrier facilitated membrane. [R]. DE-FC36-04GO14151, Membrane Technology and Research Inc., 2007.
[52] Kim J H, Lee D H, Won J, et al. The structural transitions of π-complexes of poly(styrene-b-butadiene-b-styrene) block copolymers with silver salts and their relation to facilitated olefin transport. [J]. J Membr Sci, 2006,281:369-376.
[53] Müller J, Peinemann K. Development of facilitated transport membranes for the separation of olefins from gas streams. [J]. Desalination, 2002,145:339-345.
[54] Kim J H, Min B Y, Won J, et al. Role of Polymer Matrix in Polymer/Silver Complexes for Structure, Interactions, and Facilitated Olefin Transport. [J]. Macromolecules., 2003 (36): 6183-6188
[55] Bondar V I, Freeman B D, Pinnau I. Gas transport properties of poly(ether- b-amide) segmented block copolymers. [J]. J Polym Sci. Part B: Polym Phys, 2000,38:2051–2062.
[56] Bondar V I, Freeman B D, Pinnau I. Gas Sorption and Characterization of Poly(ether-b-amide) Segmented Block Copolymers. [J]. J Polym Sci. Part B: Polym Phys, 1999,37:2463-2475.
[57] Pozun Z D, Tran K, Shi A, et al. Why silver nanoparticles are effective for olefin/paraffin separations. [J]. J Phys Chem C, 2011,115:1811-1818.
[58] Chatt J, Venanzi L M. Olefin complex of rhodium. [J]. Nature, 1956,177:852-853.
[59] Wang W, Zhang L, Xu X B, et al. Formation of novel Olefin–Copper(I) coordination compound dependent on conformation of Olefin ligand. [J]. Inorg Chem Commun., 2011,14:626-631.
[60] Trebellas J C, Olechowski J R, Jonassen H B, et al. Metal-olefin complexes III. The rhodium(I) π-complex of cis,cis-1,6-cyclodecadiene by the metal-catalyzed isomerization of cis,trans-1,5-cyclodecadiene. [J]. J Org Chem, 1967,9):153-158.
[61] 许峥, 周荣琪, 段占庭. 络合吸收法分离烯烃/烷烃. [J]. 化工进展, 2000,19:14-17.
[62] Keller G E, Marcinkowsky A E, Verma S K, et al. Olefin recovery and purification via silver complexation. Separation and purification Technology. [M]. Li N N, Calo J M, Eds. Marcel Dekker, Inc, New York, 1992, Chapter 3.
[63] Steigelmann E F. Membrane process and product. [P]. US Patent. 4014665. 1977.
[64] Marcinkowsky A E, Keller G E, Verma S K. Olefin separation process. US Patent. 4174353. 1979.