On the limits of gas separation in CO2/CH4, N2/CH4 and CO2/N2 binary mixtures using polyimide membranes

Abstract The main purpose of this work is to establish the upper line boundary of permeability versus selectivity plots for gas separation of CO 2 , N 2 and CH 4 binary mixtures, by means of diffusion in polyimide membranes. Previous works reported the upper bound line for CO 2 /CH 4 mixtures, by choosing the best visual fit with respect to available data, which was theoretically justified by Freeman [1,2] . In the present case the theory was applied for molecular pairs formed between CO 2 , N 2 and CH 4 . The log–log plots of permeability ( P A/B ) versus selectivity ( α A/B ) for polyimide polymeric materials lead to a linear upper bound with a slope fitting well the molecular kinetic diameter difference between the constituents of the gas pair. The present work contributes to establish the position predicted by theory of the upper bound line for gas separation of CO 2 /CH 4 , N 2 /CH 4 and CO 2 /N 2 binary mixtures, by diffusion in polyimide membranes. The use of polyimide membranes gives a means for enriching the natural gas mixtures and their caloric potential, which is usually depleted by the presence of CO 2 and N 2 in the gas mixtures resulting from gas production, and secondary oil recovery operations.

[1]  Tai-Shung Chung,et al.  Gas permeability, diffusivity, solubility, and aging characteristics of 6FDA-durene polyimide membranes , 2001 .

[2]  B. Freeman,et al.  Gas separation properties of aromatic polyimides , 2003 .

[3]  Benny D. Freeman,et al.  Basis of Permeability/Selectivity Tradeoff Relations in Polymeric Gas Separation Membranes , 1999 .

[4]  W. Koros,et al.  Isomeric polyimides based on fluorinated dianhydrides and diamines for gas separation applications , 1990 .

[5]  W. Koros,et al.  Significance of entropic selectivity for advanced gas separation membranes , 1996 .

[6]  Yu. P. Yampolskii,et al.  Free volume model and tradeoff relations of gas permeability and selectivity in glassy polymers , 2000 .

[7]  W. Koros,et al.  Relationship between gas separation properties and chemical structure in a series of aromatic polyimides , 1988 .

[8]  William J. Koros,et al.  Improvement of CO2/CH4 separation characteristics of polyimides by chemical crosslinking , 1999 .

[9]  Benny D. Freeman,et al.  High‐Performance Polymer Membranes for Natural‐Gas Sweetening , 2006 .

[10]  Neil B. McKeown,et al.  Gas separation membranes from polymers of intrinsic microporosity , 2005 .

[11]  A. J. Hill,et al.  Ultrapermeable, Reverse-Selective Nanocomposite Membranes , 2002, Science.

[12]  B. Freeman,et al.  Gas and Vapor Sorption and Permeation in Poly(2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole-co-tetrafluoroethylene) , 2004 .

[13]  John E. Leffler,et al.  THE ENTHALPY-ENTROPY RELATIONSHIP AND ITS IMPLICATIONS FOR ORGANIC CHEMISTRY , 1955 .

[14]  Haruhiko Ohya,et al.  Polyimide Membranes: Applications, Fabrications and Properties , 1997 .

[15]  H. Strathmann,et al.  Membrane separation processes , 1981 .

[16]  H. Kita,et al.  Permeability and permselectivity of gases in fluorinated and non-fluorinated polyimides , 1992 .

[17]  Tai‐Shung Chung,et al.  Gas transport properties of poly(1,5-naphthalene-2,2′-bis(3,4-phthalic) hexafluoropropane) diimide (6FDA-1,5-NDA) dense membranes , 2002 .

[18]  Benny D. Freeman,et al.  Gas separation using polymer membranes: an overview , 1994 .

[19]  The Permeability of Different Rubbers to Gases and Its Relation to Diffusivity and Solubility , 1946 .

[20]  K. Haraya,et al.  The permeation of gases through a new type polyimide membrane. , 1986 .

[21]  W. Koros,et al.  Fluorinated polycarbonates for gas separation applications , 1989 .

[22]  W. Koros,et al.  Gas transport properties of polysulphones: 1. Role of symmetry of methyl group placement on bisphenol rings , 1991 .

[23]  Donald R Paul,et al.  Correlation and prediction of gas permeability in glassy polymer membrane materials via a modified free volume based group contribution method , 1997 .

[24]  Q. Xue,et al.  Separation of CO2 and CH4 through two types of polyimide membrane , 1999 .

[25]  Mark C. Porter,et al.  Handbook of Industrial Membrane Technology , 2007 .

[26]  H. Kita,et al.  Permeation and separation properties of polyimide membranes to olefins and paraffins , 1996 .

[27]  W. Koros,et al.  Gas transport in polymers based on bisphenol‐A , 1988 .

[28]  L. Robeson,et al.  Correlation of separation factor versus permeability for polymeric membranes , 1991 .

[29]  M. Kakimoto,et al.  Gas Permeability and Permselectivity of Polyimides Prepared from 4,4′-Diaminotriphenylamine , 1992 .

[30]  J. Petropoulos,et al.  DIFFUSION IN POLYMERS. , 1972 .

[31]  Y. Yampolskii.  Polymeric Gas Separation Membranes , 1993 .

[32]  W. Koros.  Gas separation membranes: needs for combined materials science and processing approaches , 2002 .

[33]  H. Kita,et al.  Gas Permeability and Permselectivity in Homo- and Copolyimides from 3,3′,4,4′-Biphenyltetracarboxylic Dianhydride and 3,3′- and 4,4′-Diaminodiphenylsulfones , 1990, Polymer Journal.

[34]  W. Koros,et al.  Thermally stable polyimide isomers for membrane‐based gas separations at elevated temperatures , 1995 .

[35]  William J. Koros,et al.  Olefin/paraffin gas separations with 6FDA-based polyimide membranes , 2000 .

[36]  William J. Koros,et al.  Defining the challenges for C3H6/C3H8 separation using polymeric membranes , 2003 .

[37]  William J. Koros,et al.  Polymeric membrane materials for solution-diffusion based permeation separations , 1988 .

[38]  B. Freeman,et al.  Plasticization-Enhanced Hydrogen Purification Using Polymeric Membranes , 2006, Science.

[39]  H. Kita,et al.  Gas permeability and permselectivity of polyimides with large aromatic rings , 1995 .

[40]  W. Koros,et al.  Polymeric membranes based on bisphenol-A for gas separations , 1989 .

[41]  H. Kita,et al.  Effect of methyl substituents on permeability and permselectivity of gases in polyimides prepared from methyl‐substituted phenylenediamines , 1992 .

[42]  W. Brandt,et al.  Diffusion of gases in fluorocarbon polymers , 1963 .

[43]  Y. Mi,et al.  Structure/permeability relationships of polyimide membranes. Applications to the separation of gas mixtures , 1989 .

[44]  John Howard Perry,et al.  Chemical Engineers' Handbook , 1934 .

[45]  Samuel Glasstone,et al.  The Theory Of Rate Processes , 1941 .

[46]  Robert E. Wilson,et al.  Fundamentals of momentum, heat, and mass transfer , 1969 .

[47]  D. V. Krevelen.  Properties of Polymers , 1990 .

[48]  R. M. Barrer.  Permeability in relation to viscosity and structure of rubber , 1942 .