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Determination of transport coefficients in microporous solids

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Abstract

Macroscopic transient methods are reviewed with respect to their applicability to the investigation of molecular transport in microporous sorption systems. Various levels of sophistication of data evaluation for nonequilibrium sorption results obtained by means of batch methods are identified and characterised. Special attention is paid to the characterisation ofFickian (intracrystalline) diffusion as well as to the identification and quantification of additional rate mechanisms that, in general, may simultaneously occur in molecular sieve systems. A state-of-art determination of transport coefficients is exemplified for the systems benzene/microporous gallosilicate of MFI-type, n-hexane/silicalite-I and p-ethyltoluene/ZSM-5. Their sorption rate behaviour can be understood either byFickian diffusion or byFickian diffusion and intracrystalline molecular immobilisation/mobilisation and surface barrier penetration, respectively. To analyse complex sorption rate patterns in microporous systems, the method oftotal curve fitting with full parameter region consideration becomes mandatory.

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References

  1. Barrer, R.M.,Appl. Mater. Res.,2, 129 (1963).

    Google Scholar 

  2. Barrer, R.M.,J. Chem. Soc. Faraday Trans.,86, 1123 (1990).

    Google Scholar 

  3. Barrer, R.M.,J. Chem. Soc. Faraday Trans.,88, 1463 (1992).

    Google Scholar 

  4. Barrer, R.M.,Langmuir,3, 309 (1987).

    Google Scholar 

  5. Barrer, R.M.,Philos. Mag.,28, 148 (1939).

    Google Scholar 

  6. Barrer, R.M.,Proc. Roy. Soc. London,A 167 and 406 (1938).

  7. Barrer, R.M.,Stud. Surf. Sci. Catal.,65, 257 (1991).

    Google Scholar 

  8. Barrer, R.M.,Zeolites and Clay Minerals as Sorbents and Molecular Sieves, Academic Press, London, 1978.

    Google Scholar 

  9. Barrer, R.M. and D.W. Brook,Trans. Faraday Soc.,49, 1049 (1953).

    Google Scholar 

  10. Barrer, R.M. and D.J. Clarke,J. Chem. Soc. Faraday Trans. I,70, 535 (1974).

    Google Scholar 

  11. Barrer, R.M. and T. Gabor,Proc. Roy. Soc. London,A 256, 267 (1960).

    Google Scholar 

  12. Barrer, R.M. and B.A. Ibbitson,Trans. Faraday Soc.,40, 206 (1944).

    Google Scholar 

  13. Barrer, R.M. and M.A. Rosemblat,Zeolites,2, 231 (1982).

    Google Scholar 

  14. Beschmann, K., G.T. Kokotailo, and L. Riekert,Chem. Eng. Process.,22, 223 (1987).

    Google Scholar 

  15. Betemps, M.,Chem. Eng. J.,20, 139 (1980).

    Google Scholar 

  16. Betemps, M., inProc. 5th Internat. Zeolite Conf. (Ed.: L.V.C. Rees), Heyden, London, p. 526, 1980.

    Google Scholar 

  17. Boniface, H.A. and D.M. Ruthven,Chem. Eng. Sci.,40, 2053 (1985).

    Google Scholar 

  18. Brandt, W.W. and W. Rudloff,J. Phys. Chem. Solids,26, 741 (1953).

    Google Scholar 

  19. Bull, M.L., N.J. Henson, A.K. Cheetham, J.M. Newsam, and S.J. Heyes,J. Phys. Chem.,97, 11776 (1993).

    Google Scholar 

  20. Bülow, M., P. Lorenz, W. Mietk, P. Struve, and N.N. Samulevic,J. Chem. Soc. Faraday Trans.,79, 1099 (1983).

    Google Scholar 

  21. Bülow, M., W. Mietk, and M. Nywlt, inProc. 9th Internat. Zeolite Conf. (Eds.: R. von Ballmoos, J.B. Higgins and M.M.J. Treacy), Butterworth-Heinemann, Boston, Vol. 2, p. 113, 1993.

    Google Scholar 

  22. Bülow, M., P. Struve, G. Finger, C. Redszus, K. Ehrhardt, W. Schirmer, and J. Kärger,J. Chem. Soc. Faraday Trans. I,76, 597 (1980).

    Google Scholar 

  23. Bülow, M., P. Struve, C. Redszus, and W. Schirmer, inProc. 5th Inernat. Zeolite Conf. (Ed.: L.V.C. Rees), Heyden, London, p. 580, 1980.

    Google Scholar 

  24. Bülow, M.,Stud. Surf. Sci. Catal.,60, 199 (1991).

    Google Scholar 

  25. Bülow, M.,Z. Chem., Leipzig,25, 81 (1985).

    Google Scholar 

  26. Bülow, M. and A. Micke,ZEUS-ZEolite Uptake Simulator-Software, VCH Verlagsgesellschaft, DECHEMA-Monografien Bd.118, p. 349, 1990.

  27. Bülow, M., W. Mietk, P. Struve, and P. Lorenz,J. Chem. Soc. Faraday I,79, 2457 (1983).

    Google Scholar 

  28. Carlson, N.W. and J.S. Dranoff, inFundamentals of Adsorption (Ed.: A.I. Liapis), Engineering Foundation, New York, p. 129, 1987.

    Google Scholar 

  29. Caro, J., M. Bülow, H. Jobic, J. Kärger, and B. Zibrowius,Adv. Catalysis,39, 351 (1993).

    Google Scholar 

  30. Caro J., Habilitationsschrift, Academy of Sciences of the G.D.R., Berlin, 1989.

  31. Carslaw, H.S. and J.C. Jaeger,Conduction of Heat in Solids, Clarendon Press, Oxford, 1959.

    Google Scholar 

  32. Catlow, C.R.A., C.M. Freemann, B. Vessal, S.M. Tomlinson, and M. Leslie,J. Chem. Soc. Faraday Trans.,87, 1947 (1991).

    Google Scholar 

  33. Cheetham, A.K. and M.L. Bull,Catal. Letters,13, 267 (1992).

    Google Scholar 

  34. Chen, Y.D., R.T. Yang, and P. Uawithya,AIChE J.,40, 577 (1994).

    Google Scholar 

  35. Chiang, A.S., A.G. Dixon, and Y.H. Ma,Chem. Eng. Sci.,39, 1461 (1984).

    Google Scholar 

  36. Crank, J.,Mathematics of Diffusion, Oxford University Press, 1956.

  37. Cussler, E.L.,Multicomponent Diffusion, Elsevier, Amsterdam, 1976.

    Google Scholar 

  38. Dahlke, K., G. Emig, and E. Aust, inFundamentals of Adsorption (Ed.: M. Suzuki), Kodansha, Tokyo, p. 129, 1993.

    Google Scholar 

  39. Demontis, P., E.S. Fois, G.B. Suffriti, and S. Quartieri,J. Phys. Chem.,94, 4329 (1990).

    Google Scholar 

  40. Chiang, A. S., A.G. Dixon, and Y.H. Ma,Chem. Eng. Sci.,39, 1451 and 1461 (1984).

    Google Scholar 

  41. Do, D.D.,Chem. Eng. Sci.,45, 1373 (1990).

    Google Scholar 

  42. Do, D.D., R.G. Jordi, and D.M. Ruthven,J. Chem. Soc. Faraday Trans.,88, 121 (1992).

    Google Scholar 

  43. Dubinin, M.M. and L.V. Radushkevich, (Eds.),Kinetics and Dynamics of Physical Adsorption, Nauka, Moscow, 1973.

    Google Scholar 

  44. Dubinin, M.M. and V.V. Serpinsky, (Eds.),Adsorption in Micropores, Naukal, Moscow, p. 114; 119; 124; 129, 1983.

    Google Scholar 

  45. Dubinin, M.M.,ACS Symp. Ser.,40, 1 (1977).

    Google Scholar 

  46. Eic, M., M. Goddard, and D.M. Ruthven,Zeolites,8, 259 (1988).

    Google Scholar 

  47. Eic, M. and D.M. Rutin,Zeolites,8, 40 (1988).

    Google Scholar 

  48. Fick, A.,Ann. Phys.,170, 59 (1855).

    Google Scholar 

  49. Fourier, J.B.,Théorie analytique de la chaleur, Paris, 1822.

  50. Fu, C.-C., M.S.P. Ramesh, and H.W. Haynes Jr.,AIChE J.,32, 1848 (1986).

    Google Scholar 

  51. Glückauf, E.,Trans. Faraday Soc.,51, 1540 (1955).

    Google Scholar 

  52. Goddard, M. and D.M. Ruthven,Zeolites,6, 283 (1986).

    Google Scholar 

  53. Grenier, Ph., F. Meunier, P.G. Gray, J. Kärger, Z. Xu, and D.M. Ruthven,Zeolites,14, 242 (1994).

    Google Scholar 

  54. Haq, N. and D.M. Ruthven,J. Coll. Interf. Sci.,112, 164 (1986).

    Google Scholar 

  55. Hashimoto, K., T. Masuda, and N. Murakami,Stud. Surf. Sci. Catal.,69, 477 (1991).

    Google Scholar 

  56. Haynes, H.W. Jr.,Chem. Eng. Sci.,30, 995 (1975).

    Google Scholar 

  57. Heink, W., J. Kärger, H. Pfeifer, K.P. Datema, and A.K. Nowak,J. Chem. Soc. Faraday Trans.,88, 3305 (1992).

    Google Scholar 

  58. Henson, N.J., A. K. Cheetham, B.K. Peterson, S.D. Pickett, and J.M. Thomas,J. Computer-Aided Mat. Design,1, 41 (1993).

    Google Scholar 

  59. Hsu, L.K.P. and H.W. Haynes Jr.,AIChE J.,27, 81 (1981).

    Google Scholar 

  60. Hu, X. and D.D. Do,Chem. Eng. Sci.,48, 1317 (1993).

    Google Scholar 

  61. Hu, X., G.N. Rao, and D.D. Do,Gas. Sep. Purif.,7, 197 (1993).

    Google Scholar 

  62. Hufton, J.R. and D.M. Ruthven,Ind. Eng. Chem. Res.,32, 2379 (1993).

    Google Scholar 

  63. Hufton, J.R., S. Brandani, and D.M. Ruthven,Stud. Surf. Sci. Catal.,84B, 1323 (1994).

    Google Scholar 

  64. Jobic, H., M. Bée, and A. Renouprez,Surf. Sci.,140, 307 (1984).

    Google Scholar 

  65. Jobic, H., A. Renouprez, M. Bée, and C. Poinsignon,J. Phys. Chem.,90, 1059 (1986).

    Google Scholar 

  66. Jordi, R.G. and D.D. Do,Chem. Eng. Sci.,48, 1103 (1993).

    Google Scholar 

  67. Jordi, R.G. and D.D. Do,J. Chem. Soc. Faraday Trans.,88, 2411 (1992).

    Google Scholar 

  68. Jost, W.,Diffusion in Solids, Liquids and Gases, Academic Press, New York, 1960.

    Google Scholar 

  69. June, R.L., A.T. Bell, and D.N. Theodorou,J. Phys. Chem.,96, 1051 (1992).

    Google Scholar 

  70. Karge, H.G. and W. Nießen,Catal. Today,8, 451 (1991).

    Google Scholar 

  71. Kärger, J., H. Pfeifer, and W. Heink,Adv. Magn. Res.,12, 1 (1988).

    Google Scholar 

  72. Kärger, J. and M. Bülow,Chem. Eng. Sci.,30, 893 (1975).

    Google Scholar 

  73. Kärger, J. and D.M. Ruthven,Diffusion in Zeolites and Other Microporous Solids, Wiley, New York, 1992.

    Google Scholar 

  74. Kärger, J., M. Bülow, V.I. Ulin, A.M. Voloshchuk, P.P. Zolotarev, M. Kocirik, and A. Zikanova,J. Chem. Tech. Biotechnol.,32, 376 (1982).

    Google Scholar 

  75. Kärger, J., H. Pfeifer, and R. Haberlandt,J. Chem. Soc. Faraday Trans. I,76, 1569 (1980).

    Google Scholar 

  76. Kärger, J., H. Pfeifer, M. Rauscher, and A. Walter,J. Chem. Soc. Faraday Trans. I,76, 717 (1980).

    Google Scholar 

  77. Kawano, M., B. Vessal, and C.R.A. Catlow,J. Chem. Soc. Chem. Commun.,12, 879 (1992).

    Google Scholar 

  78. Kocirik, M. and A. Zikanova,Ind. Eng. Chem. Fundam.,13, 347 (1974).

    Google Scholar 

  79. Kocirik, M. and A. Micke,Transport of Labelled and Unlabelled Molecules in ZSM5 Zeolites.—A Model with Immobilisation of Sorbing Species, Langmuir, in press.

  80. Kocirik, M., P. Struve, and M. Bülow,J. Chem. Soc. Faraday Trans. I,80, 2167 (1984).

    Google Scholar 

  81. Krishna, R.,Gas Sep. Purif.,2, 91 (1993).

    Google Scholar 

  82. Lee, L.-K. and D.M. Ruthven,Canad. J. Chem. Eng.,57, 65 (1979).

    Google Scholar 

  83. Lee, L.K. and D.M. Ruthven,J. Chem. Soc. Faraday Trans. I,75, 2406 (1979).

    Google Scholar 

  84. Ma, Y.H. and C. Mancel,AIChE J.,18, 1148 (1972).

    Google Scholar 

  85. March, H. and W. Weaver,Phys. Rev.,31, 1081 (1928).

    Google Scholar 

  86. Marutovsky, R.M. and M. Bülow,Chem. Eng. Sci.,42, 2745 (1987).

    Google Scholar 

  87. Marutovsky, R.M. and M. Bülow,Gas. Sep. Purif.,1, 66 (1987).

    Google Scholar 

  88. Marutovsky, R.M. and M. Bülow,Z. Phys. Chem. Leipzig,262, 849 (1982).

    Google Scholar 

  89. Marutovsky, R.M. and M. Bülow,Zeolites,7, 111 (1987).

    Google Scholar 

  90. McKay, A.T.,Proc. Phys. Soc. London,42, 547 (1930).

    Google Scholar 

  91. Micke, A. and M. Bülow,Chem. Eng. Sci.,48, 2777 (1993).

    Google Scholar 

  92. Micke, A. and M. Bülow,Gas Sep. Purif.,4, (1990), part I, p. 158, part II p. 165.

    Google Scholar 

  93. Bülow, M. and A. Micke,J. Chem. Soc. Faraday Trans.,90, 2585 (1994).

    Google Scholar 

  94. Micke, A., M. Bülow, and M. Kocirik,Ber. Bunsenges. Phys. Chem.,98, 27 (1994).

    Google Scholar 

  95. Micke, A., M. Bülow, and M. Kocirik,J. Phys. Chem.,98, 924 (1994).

    Google Scholar 

  96. Micke, A., M. Bülow, M. Kocirik, and P. Struve,J. Phys. Chem.,98, 12337 (1994).

    Google Scholar 

  97. Micke, A., M. Kocirik, and M. Bülow,Microporous Materials,1, 363 (1993).

    Google Scholar 

  98. Micke, A., M. Kocirik, and J. Caro,J. Chem. Soc. Faraday Trans.,86, 3087 (1990).

    Google Scholar 

  99. Naphtali, L.M. and L.M. Polinski,J. Phys. Chem.,67, 369 (1963).

    Google Scholar 

  100. Nießen, W. and H.G. Karge,Microporous Mat.,1, 1 (1993).

    Google Scholar 

  101. Nießen, W. and H.G. Karge,Stud. Surf. Sci. Catal.,60, 213 (1991).

    Google Scholar 

  102. Nießen, W. and H.G. Karge,Stud. Surf. Sci. Catal.,84B, 1191 (1994).

    Google Scholar 

  103. Oprescu, D., L.V.C. Rees, and D. Shen,J. Chem. Soc. Faraday Trans.,88, 2955 (1992).

    Google Scholar 

  104. Paravar, A. and D.T. Hayhurst, inProc. 6thInternat. Zeolite Conf. (Eds.: D. Olson and A. Bisio), Butterworths, Guilford, p. 217, 1984.

    Google Scholar 

  105. Pfeifer, H.,NMR Basic Principles and Progress,7, 53 (1972).

    Google Scholar 

  106. Pickett, S.D., A.K. Nowak, J.M. Thomas, B.K. Peterson, J.F.P. Swift, A.K. Cheetham, C.J.J. den Ouden, B. Smit, and M.F.M. Post,J. Phys. Chem.,94, 1233 (1990).

    Google Scholar 

  107. Prinz, D. and L. Riekert,Ber. Bunsenges, Phys. Chem.,90, 413 (1986).

    Google Scholar 

  108. Qureshi, W.R. and J. Wei,J. Catal.,126, 126 (1990).

    Google Scholar 

  109. Rees, L.V.C. and D. Shen,Gas Sep. Purif.,2, 7 (1993).

    Google Scholar 

  110. Rees, L.V.C.,Stud. Surf. Sci. Catal.,84B, 1133 (1994).

    Google Scholar 

  111. Richter, W., A. Roethe, K.P. Roethe, and D. Gelbin,Chem. Techn.,29, 276 (1977).

    Google Scholar 

  112. Riekert, L.,AIChE J.,17, 446 (1971).

    Google Scholar 

  113. Roethe, A., K.P. Roethe, K. Fiedler, and D. Gelbin,Ber. Bunsenges. Phys. Chem.,83, 47 (1979).

    Google Scholar 

  114. Ruckenstein, E., A.S. Vaidyanathan, and G.R. Youngquist,Chem. Eng. Sci.,26, 1305 (1971).

    Google Scholar 

  115. Ruthven, D.M. and M. Eic,ACS Symp. Ser.,368, 362 (1988).

    Google Scholar 

  116. Ruthven, D.M. and R. Kumar,Canad. J. Chem. Eng.,57, 342 (1979).

    Google Scholar 

  117. Ruthven, D.M., M. Eic, and Z. Xu,Stud. Surf. Sci. Catal.,65, 233 (1991).

    Google Scholar 

  118. Ruthven, D.M.,Principles of Adsorption and Adsorption Processes, Wiley, New York, 1984.

    Google Scholar 

  119. Shah, D.B. and H.Y. Liou,Stud. Surf. Sci. Catal.,84B, 1347 (1994).

    Google Scholar 

  120. Shah, D.B., C.J. Guo, and D.T. Hayhurst,Fundamentals of Adsorption (Ed.: M. Suzuki), Kodansha, Tokyo, p. 575, 1993.

    Google Scholar 

  121. Shavit, D., P. Voogd, and H.W. Kouwenhoven,Collect. Czech. Chem. Commun.,57, 698 (1992).

    Google Scholar 

  122. Shen, D. and L.V.C. Rees, inProc. 9thInternat. Zeolite Conf. (Eds.: R. von Ballmoos, Higgins J.B. and M.M.J. Treacy), Butterworth-Heinemann, Boston, vol. 2, p. 45, 1993.

    Google Scholar 

  123. Struve, P., M. Kocirik, M. Bülow, A. Zikanova, and A.G. Bezus,Z. Phys. Chem. Leipzig,264, 49 (1983).

    Google Scholar 

  124. Sun, L.M. and V. Bourdin,Chem. Eng. Sci.,48, 3783 (1993).

    Google Scholar 

  125. Sun, L.M. and F. Meunier,Chem. Eng. Sci.,42, 1585 (1987).

    Google Scholar 

  126. Suzuki, M. and J.M. Smith,Adv. Chrom.,13, 213 (1975).

    Google Scholar 

  127. Syrkin, J.K. and A.J. Kondrashev,Kolloid-Z.,56, 295 (1931).

    Google Scholar 

  128. Timofejev, D.P.,Adsorptionskinetik, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1967.

    Google Scholar 

  129. Tsykalo, A.L., G.D. Kuzenko, and I.I. Novikov,Dokl. Akad. Nauk SSSR,301, 1438 (1988).

    Google Scholar 

  130. Tunickij, N.N., V.A. Kaminskij, and S.F. Timashev,Methods of Physicochemical Kinetics, Chimija, Moscow, 1972.

    Google Scholar 

  131. Van-Den-Begin, N., L.V.C. Rees, J. Caro, and M. Bülow,Zeolites,9, 287 (1989).

    Google Scholar 

  132. Voogd, P. and H. van Bekkum,Stud. Surf. Sci. Catal.,46, 519 (1989).

    Google Scholar 

  133. Wernick, D.L. and E.J. Osterhuber, inProc. 6thInternat. Zeolite Conf. (Eds.: D. Olson and A. Bisio), Butterworths, Guildford, p. 122, 1984.

    Google Scholar 

  134. Yang, R.T., Y.T. Chen, and Y.T. Yeh,Chem. Eng. Sci.,46, 3089 (1991).

    Google Scholar 

  135. Yang, R.T.,Gas Separation by Adsorption Processes, Butterworths, Boston, 1987.

    Google Scholar 

  136. Yashonath, S. and P. Santikary,J. Phys. Chem.,97, 13778 (1993).

    Google Scholar 

  137. Yasuda, Y.,Heterogeneous Chem. Rev.,1, 000 (1994).

    Google Scholar 

  138. Yasuda, Y.,J. Phys. Chem.,80, 1867 (1976).

    Google Scholar 

  139. Yasuda, Y.,Stud. Surf. Sci. Catal.,84B, 1331 (1994).

    Google Scholar 

  140. Yasuda, Y., Y. Suzuki, and F. Hirofumi,J. Phys. Chem.,95, 2486 (1991).

    Google Scholar 

  141. Zikanova, A., M. Bülow, and H. Schlodder,Zeolites,7, 115 (1987).

    Google Scholar 

  142. Zikanova, A., M. Kocirik, and O. Kadlec, inKinetics and Dynamics of Physical Adsorption (Eds.: M.M. Dubnin and L.V. Radushkevich), Nauka, Moscow, p. 103, 1973.

    Google Scholar 

  143. Zolotarev, P.P. and M.M. Dubinin,Dokl. Akad. Nauk SSSR,210, 136 (1973).

    Google Scholar 

  144. Zolotarev, P.P. and V.V. Ugrozov, inAdsorption and Adsorbents (Eds.: M.M. Dubinin, V.V. Serpinsky, and K.O. Murdmaa) Nauka, Moscow, p. 127, 1987.

    Google Scholar 

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Bülow, M., Micke, A. Determination of transport coefficients in microporous solids. Adsorption 1, 29–48 (1995). https://doi.org/10.1007/BF00704144

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