化工学报 ›› 2016, Vol. 67 ›› Issue (8): 3170-3178.doi: 10.11949/j.issn.0438-1157.20160427

• 综述与专论 • 上一篇    下一篇

零长柱技术用于分子筛晶内扩散的研究进展

陈振涛, 武云, 徐春明   

  1. 中国石油大学化学工程学院, 重质油国家重点实验室, 北京 102249
  • 收稿日期:2016-04-05 修回日期:2016-07-04 出版日期:2016-08-05 发布日期:2016-07-07
  • 通讯作者: 徐春明 E-mail:xcm@cup.edu.cn
  • 基金资助:

    国家重点基础研究发展计划项目(2012CB215001);国家自然科学基金青年基金项目(21106183)。

Progress on diffusion studies in zeolites using ZLC techniques

CHEN Zhentao, WU Yun, XU Chunming   

  1. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum, Beijing 102249, China
  • Received:2016-04-05 Revised:2016-07-04 Online:2016-08-05 Published:2016-07-07
  • Supported by:

    supported by the National Basic Research Program of China (2012CB215001) and the National Natural Science Foundation of China (21106183).

摘要:

分子筛晶内扩散系数对吸附分离和择形催化具有重要的指导作用。概述了重量法、核磁共振法和分子模拟等分子筛晶内扩散研究方法,并对零长柱技术用于分子筛晶内扩散的原理和应用等方面研究进行了详细阐述,包括两种进样方式(气相进样和液相进样)的单组分气相扩散、二元体系气相扩散和互扩散、液相扩散以及吸附扩散数学模型修正和拓展,还探讨了当前存在的一些问题,最后对零长柱法用于烃类分子在多孔材料中的扩散研究进行了展望。

关键词: 零长柱, 扩散, 分子筛

Abstract:

The intrapartical diffusivity plays an important role in guiding the process of shape-selective catalysis and adsorptive separation. The methods of study on intracrystalline diffusion in zeolites, such as gravimetric method, NMR technique and molecular simulation, were summarized firstly. Furthermore, recent progress in development and application of Zero Length Column (ZLC) method to the measurement of intracrystalline diffusion in zeolites was reviewed, including single component in gas-phased diffusion with two sampling patterns (gas phase and liquid phase sampling),gas-phased diffusion of binary system and counter diffusion, liquid-phased diffusion, and development of the mathematical models. Some existing problems were also discussed. Finally, application of ZLC method for diffusion of hydrocarbon molecules in the porous materials in the future was prospected.

Key words: zero length column, diffusion, zeolite

中图分类号: 

  • TQ021.4

[1] DURAND E,CLEMANCEY M,QUOINEAUD A A,et al.H1 diffusion-ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR) as a powerful tool for the analysis of hydrocarbon mixtures and asphaltenes[J].Energy&Fuels,2008,22(4):2604-2610.
[2] JOBIC H,KÄRGER J,KRAUSE C,et al.Diffusivities of n-alkanes in 5A zeolite measured by neutron spin echo,pulsed-field gradient NMR,and zero length column techniques[J].Adsorption,2005,11(1):403-407.
[3] RUTHVEN D M.Diffusion in zeolites-a continuing saga[J].Adsorption,2010,16(6):511-514.
[4] SONG L,SUN Z L,REES L V.Experimental and molecular simulation studies of adsorption and diffusion of cyclic hydrocarbons in silicalite-1[J].Microporous and Mesoporous Materials,2002,55(1):31-49.
[5] 张国.有机分子在分子筛中的吸附和扩散过程的计算机模拟[D].长春:吉林大学,2008.ZHANG G.Computer simulation of the adsorption and diffusion of organic molecules in zeolite[D].Changchun:Jilin University,2008.
[6] 朱萌萌,郑兰歌,秦玉才,等.芳烃在FCC催化剂上的吸附扩散行为[J].辽宁石油化工大学学报,2015,28(3):7-11.ZHU M M,ZHENG L G,QIN Y C,et al.Adsorption and diffusion of aromatic hydrocarbons on FCC catalysts[J].Journal of Liaoning Shihua University,2015,28(3):7-11.
[7] 蒋施,段林海,张晓彤,等.环戊烷在silicalite-1分子筛上吸附的动力学研究[J].石油化工高等学校学报,2003,16(4):8-11.JIANG S,DUAN L H,ZHANG X T,et al.Kinetics of adsorption for cyclopentane in silicalite-1[J].Journal of Petrochemical Universities,2003,16(4):8-11.
[8] BELMABKHOUT Y,FRERE M,DE WEIRELD G.High-pressure adsorption measurements.A comparative study of the volumetric and gravimetric methods[J].Measurement Science and Technology,2004,15(5):848-858.
[9] EI? M,RUTHVEN D M.A new experimental technique for measurement of intracrystalline diffusivity[J].Zeolites,1988,8(1):40-45.
[10] EI? M,RUTHVEN D M.Intracrystalline diffusion of linear paraffins and benzene in silicalite studied by the ZLC method[J].Studies in Surface Science and Catalysis,1989,49:897-905.
[11] RUTHVEN D,BRANDANI S.Measurement of diffusion in porous solids by ZLC methods[M]//Recent Advances in Gas Separation by Microporous Ceramic Membranes.Amsterdam:Elsevier,2000:187-212.
[12] HUFTON J R,RUTHVEN D M.Diffusion of light alkanes in silicalite studied by the zero length column method[J].Industrial&Engineering Chemistry Research,1993,32(10):2379-2386.
[13] CHERNTONGCHAI P,BRANDANI S.Liquid phase counter-diffusion measurements of aromatics in silicalite using the ZLC method[J].Adsorption,2003,9(3):197-204.
[14] EI? M,RUTHVEN D M.Diffusion of linear paraffins and cyclohexane in NaX and 5A zeolite crystals[J].Zeolites,1988,8(6):472-479.
[15] BRANDANI S,RUTHVEN D M.Analysis of ZLC desorption curves for gaseous systems[J].Adsorption,1996,2(2):133-143.
[16] RUTHVEN D M,EI? M,RICHARD E.Diffusion of C8 aromatic hydrocarbons in silicalite[J].Zeolites,1991,11(7):647-653.
[17] BRANDANI S.Effects of nonlinear equilibrium on zero length column experiments[J].Chemical Engineering Science,1998,53(15):2791-2798.
[18] BRANDANI S,JAMA M A,RUTHVEN D M.ZLC measurements under non-linear conditions[J].Chemical Engineering Science,2000,55(7):1205-1212.
[19] ZIKÁNOVÁ A,BÜLOW M,SCHLODDER H.Intracrystalline diffusion of benzene in ZSM-5 and silicalite[J].Zeolites,1987,7(2):115-118.
[20] LOUGHLIN K F.Effect of nonlinear equilibrium on zero length column experiments in mesoporous or macroporous sorbents:limiting analytical asymptotic forms[C]//The Annual Meeting.Dhahran,Saudi Arabia,2005.
[21] PETKOVSKA M.Nonlinear FR-ZLC method for investigation of adsorption equilibrium and kinetics[J].Adsorption,2008,14(2/3):223-239.
[22] PALMAS S,POLCARO A M,CARTA R,et al.Sorption and diffusion of light hydrocarbons on NaY zeolites[J].Journal of Chemical and Engineering Data,1991,36(1):1-4.
[23] BRANDANI S,HUFTON J,RUTHVEN D M.Self-diffusion of propane and propylene in 5A and 13X zeolite crystals studied by the tracer ZLC method[J].Zeolites,1995,15(7):624-631.
[24] BRANDANI S,RUTHVEN D M,KÄRGER J.Diffusion in a unidimensional zeolite pore system:propane in AlPO4-5[J].Microporous Materials,1997,8(3):193-200.
[25] LIAO B,EI? M,RUTHVEN D M,et al.Diffusion of C10-C24 n-paraffins and perfluorotributylamine in clay catalysts[J].Studies in Surface Science and Catalysis,1995,97:251-258.
[26] DENAYER J F M,BARON G V.Adsorption of normal and branched paraffins in faujasite zeolites NaY,HY,Pt/NaY and USY[J].Adsorption,1997,3(4):251-265.
[27] BOULICAUT L,BRANDANI S,RUTHVEN D M.Liquid phase sorption and diffusion of branched and cyclic hydrocarbons in silicalite[J].Microporous and Mesoporous Materials,1998,25(1/2/3):81-93.
[28] RUTHVEN D M,EI? M,XU Z.Diffusion of hydrocarbons in A and X zeolites and silicalite[J].Catalysis and Adsorption by Zeolites,1991,65:233-246.
[29] MICKE A,BÜLOW M,KO?I?IK M.Zero length column chromatography to characterise microporous sorbents by means of kinetic data[J].Berichte der Bunsengesellschaft für Physikalische Chemie,1994,98(2):242-248.
[30] BÜLOW M,MICKE A.Determination of transport coefficients in microporous solids[J].Adsorption,1995,1(1):29-48.
[31] ÁVILA A M,BIDABEHERE C M,SEDRAN U.Diffusion and adsorption selectivities of hydrocarbons over FCC catalysts[J].Chemical Engineering Journal,2007,132(1):67-75.
[32] ZAMAN S F,LOUGHLIN K F,AL-KHATTAF S A.Kinetics of desorption of 1,3-diisopropylbenzene and 1,3,5-triisopropylbenzene (2):Diffusion in FCC catalyst particles by zero length column method[J].Industrial&Engineering Chemistry Research,2015,54(16):4572-4580.
[33] VIDONI A,RUTHVEN D M.Diffusion of methane in DD3R zeolite[J].Microporous and Mesoporous Materials,2012,159:57-65.
[34] VIDONI A,RUTHVEN D M.Diffusion of C2H6 and C2H4 in DDR zeolite[J].Industrial&Engineering Chemistry Research,2012,51(3):1383-1390.
[35] RUTHVEN D M,STAPLETON P.Measurement of liquid phase counter-diffusion in zeolite crystals by the ZLC method[J].Chemical Engineering Science,1993,48(1):89-98.
[36] GUNADI A,BRANDANI S.Diffusities of n-alkanes in silicalite using the ZLC method[C]//The AIChE 2005 Annual Meeting.Cincinnati,USA,2005.
[37] FAKHRUZ ZAMAN S.Diffusion and adsorption of aromatics in zeolites by zero length column technique[D].King Fahd University of Petroleum and Minerals,2004.
[38] JIANG M,EI? M.Transport properties of ethane,butanes and their binary mixtures in MFI-type zeolite and zeolite-membrane samples[J].Adsorption,2003,9(3):225-234.
[39] HUANG Q,QAMAR R A,EI? M.Single component and binary diffusion of n-heptane and toluene in SBA-15 materials[J].Adsorption,2011,17(1):27-38.
[40] BRANDANI S,JAMA M,RUTHVEN D M.Diffusion,self-diffusion and counter-diffusion of benzene and p-xylene in silicalite[J].Microporous and Mesoporous Materials,2000,35:283-300.
[41] BRANDANI S,JAMA M,RUTHVEN D M.Counterdiffusion of p-xylene/benzene and p-xylene/o-xylene in silicalite studied by the zero-length column technique[J].Industrial&Engineering Chemistry Research,2000,39(3):821-828.
[42] HUFTON J R,DANNER R P.Chromatographic study of alkanes in silicalite:transport properties[J].AIChE Journal,1993,39(6):962-974.
[43] PARAVAR A,HAYHURST D T.Direct measurement of diffusivity for butane across a single large silicalite crystal[C]//Proc.6th Int.Zeolite Conf.Reno,USA,1983.
[44] DA SILVA F A,RODRIGUES A E.Adsorption equilibria and kinetics for propylene and propane over 13X and 4A zeolite pellets[J].Industrial&Engineering Chemistry Research,1999,38(5):2051-2057.
[45] IUCOLANO F,APREA P,CAPUTO D,et al.Adsorption and diffusion of propane and propylene in Ag+-impregnated MCM-41[J].Adsorption,2008,14(2/3):241-246.
[46] LIU Z,FAN W,XUE Z,et al.Diffusion of n-alkanes in mesoporous 5A zeolites by ZLC method[J].Adsorption,2013,19(1):201-208.
[47] CAVALCANTE JR C L,SILVA N M,SOUZA-AGUIAR E F,et al.Diffusion of paraffins in dealuminated Y mesoporous molecular sieve[J].Adsorption,2003,9(3):205-212.
[48] BOURDIN V,BRANDANI S,GUNADI A,et al.Diffusion of n-alkanes in MFI-type zeolites:a comparative study with different measuring techniques[M]//Diffusion Fundamentals.Leipzig:Leipziger Universitätsverlag,2005:430-431.
[49] GUNADI A,BRANDANI S.Diffusion of linear paraffins in NaCaA studied by the ZLC method[J].Microporous and Mesoporous Materials,2006,90(1):278-283.
[50] GUIMARÃES A P,MÜLLER A,STAUDT R,et al.Diffusion of linear paraffins in silicalite studied by the ZLC method in the presence of CO2[J].Adsorption,2010,16(1/2):29-36.
[51] VOOGD P,BEKKUM H,SHAVIT D.Effect of zeolite structure and morphology on intracrystalline n-hexane diffusion in pentasil zeolites studied by the zero-length column method[J].J.Chem.Soc.Faraday Trans.,1991,87(21):3575-3580.
[52] LIU Z,FAN W,MA J,et al.Adsorption,diffusion and catalysis of mesostructured zeolite HZSM-5[J].Adsorption,2012,18(5/6):493-501.
[53] ZHAO H,MA J,ZHANG Q,et al.Adsorption and diffusion of n-heptane and toluene over mesoporous ZSM-5 zeolites[J].Industrial&Engineering Chemistry Research,2014,53(35):13810-13819.
[54] CAVALCANTE C L,EI? M,RUTHVEN D M,et al.Diffusion of n-paraffins in offretite-erionite type zeolites[J].Zeolites,1995,15(4):293-307.
[55] GORRING R L.Diffusion of normal paraffins in zeolite T:occurrence of window effect[J].Journal of Catalysis,1973,31(1):13-26.
[56] CAVALCANTE JR C L,AZEVÊDO D C S,SOUZA I G,et al.Sorption and diffusion of p-xylene and o-xylene in aluminophosphate molecular sieve AlPO4-11[J].Adsorption,2000,6(1):53-59.
[57] RUTHVEN D M.Diffusion of aromatic hydrocarbons in silicalite/HZSM-5[J].Adsorption,2007,13(3/4):225-230.
[58] CAVALCANTE C L,BRANDANI S,RUTHVEN D M.Evaluation of the main diffusion path in zeolites from ZLC desorption curves[J].Zeolites,1997,18(4):282-285.
[59] HOANG V T,HUANG Q,EI? M,et al.Structure and diffusion characterization of SBA-15 materials[J].Langmuir,2005,21(5):2051-2057.
[60] HUANG Q,EI? M,XIAO H,et al.Characterization of the diffusion path in micro-and meso-porous materials from ZLC analysis[J].Adsorption,2010,16(6):531-539.
[61] LOUGHLIN K F,AL-KHATTAF S S,ZAMAN S F.Kinetics of sorption of 1,3-di-isopropyl benzene and 1,3,5-tri-isopropyl benzene in NaY crystals,alumina matrix and FCC catalyst particles by zero length column method[C]//Proceedings of the 2005 Annual Meeting.USA,2005.
[62] RUTHVEN D M,VIDONI A.ZLC diffusion measurements:combined effect of surface resistance and internal diffusion[J].Chemical Engineering Science,2012,71:1-4.
[63] 陈云超.多孔材料的吸附和扩散性能:案例研究[D].金华:浙江师范大学,2013.CHEN Y C.Adsorption and diffusion properties of porous materials:case studies[D].Jinhua:Zhejiang Normal University,2013.
[64] KRISHNA R.Multicomponent surface diffusion of adsorbed species:a description based on the generalized Maxwell-Stefan equations[J].Chemical Engineering Science,1990,45(7):1779-1791.
[65] 王维德.Maxwell-Stefan方程及其在多元相间传质中的应用[J].化学工程,2002,30(4):8-12.WANG W D.Maxwell-Stefan equation and its application in multicomponent mass transfer[J].Chemical Engineering,2002,30(4):8-12.
[66] KRISHNA R,WESSELINGH J A.The Maxwell-Stefan approach to mass transfer[J].Chemical Engineering Science,1997,52(6):861-911.
[67] 曾勇平.传质教学过程中Fick关系的Maxwell-Stefan方程解释[J].科教文汇,2009,31:203-204.ZENG Y P.Explanation of the relationship between Fick equation and Maxwell-Stefan equation in the process of mass transfer teaching[J].The Science Education Article Collects,2009,31:203-204.
[68] ILIYAS A,EI? M,ZAHEDI-NIAKI M H,et al.Toward observation of single-file diffusion using the tracer zero-length column method[J].The Journal of Physical Chemistry B,2008,112(12):3821-3825.
[69] AWUM F,NARAYAN S,RUTHVEN D M.Measurement of intracrystalline diffusivities in NaX zeolite by liquid chromatography[J].Industrial&Engineering Chemistry Research,1988,27(8):1510-1515.
[70] BANAS K,BRANDANI F,RUTHVEN D M,et al.Combining macroscopic and microscopic diffusion studies in zeolites using NMR techniques[J].Magnetic Resonance Imaging,2005,23(2):227-232.
[71] KÄRGER J,RUTHVEN D M,THEODOROU D N.Diffusion in Nanoporous Materials[M].John Wiley&Sons,2012.
[72] DUNCAN W,MÖLLER K.The effect of a crystal size distribution on ZLC experiments[J].Chemical Engineering Science,2002,57(14):2641-2652.
[73] SILVA J A C,RODRIGUES A E.Analysis of ZLC technique for diffusivity measurements in bidisperse porous adsorbent pellets[J].Gas Separation&Purification,1996,10(4):207-224.
[74] BRANDANI S,RUTHVEN D M.Analysis of ZLC desorption curves for liquid systems[J].Chemical Engineering Science,1995,50(13):2055-2059.
[75] BRANDANI S,CAVALCANTE C,GUIMARÃES A,et al.Heat effects in ZLC experiments[J].Adsorption,1998,4(3):275-285.
[76] SILVA J A C,MATA V G,DIAS M M,et al.Effect of coke in the equilibrium and kinetics of sorption on 5A molecular sieve zeolites[J].Industrial&Engineering Chemistry Research,2000,39(4):1030-1034.

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