聚合物膜催化接触器研究进展

doi:10.16085/j.issn.1000-6613.2015.02.003

摘要/Abstract

摘要： 对聚合物膜催化接触器的特点、所用催化膜材料及其制备方法进行归纳总结。与传统催化反应器相比,聚合物膜催化接触器具有结构紧凑,工艺及操作流程简单,催化活性、反应速率及转化率高等特点。所用聚合物膜材料分子主链和侧链具有丰富的功能基团,以便引入活性纳米粒子或基团,得到高活性的催化膜。聚合物催化膜制备方法主要有杂化法、浸渍法及化学接枝法。扩散过程为聚合物膜接触器催化反应过程的控制步骤,整个过程包括内扩散和外扩散两个步骤。文中最后提出聚合物膜催化接触器应用中存在的问题,即催化效率和使用寿命有待进一步提高;新型聚合物催化膜材料亟需开发,膜污染和催化膜失活问题亟待解决;膜催化反应动力学模型的建立和研究等关键性、基础性问题还需要更加深入地研究。

关键词: 膜, 反应动力学, 传质, 反应器

Abstract: In this paper, the characteristics of polymeric membrane catalytic contactor, catalytic membrane materials and preparation methods are summarized. Compared with the traditional catalytic reactor,polymeric membrane catalytic contactor has the advantages of compact structure,simple technology and operation process,high catalytic activity,high reaction rate and high conversion rate. Active nanoparticles or groups can be easily introduced onto molecular backbone and side chains which are bonded with lots of functional groups. The preparation methods of polymeric catalytic membrane mainly include hybrid method,dipping method and chemical grafting method. Diffusion process is the controlling step of catalytic reaction process of polymeric membrane catalytic contactor. The whole process includes internal diffusion and external diffusion. Some problems deserving further research and application prospects of polymeric membrane catalytic contactor are presented. Catalytic efficiency and service life need to be further improved;novel polymeric membrane materials need to be developed;membrane fouling and membrane catalytic deactivation problems need to be resolved;basic issues, such as establishing kinetic model of polymeric membrane catalytic reaction need to be further studied.

Key words: membranes, reaction kinetics, mass transfer, reactors

中图分类号:

TQ028.8

石文英, 李红宾, 周蓉. 聚合物膜催化接触器研究进展[J]. 化工进展, 2015, 34(02): 312-318.

SHI Wenying, LI Hongbin, ZHOU Rong. Research progress of polymeric membrane catalytic contactor[J]. Chemical Industry and Engineering Progree, 2015, 34(02): 312-318.

参考文献

[1] 曹阳,李遵龙. 膜技术在工业用水处理及废水处理的应用[J]. 化工进展,2013,32(s1):222-224.
[2] 高会元,李永丹,林跃生. 糠醛在Pd-Cu膜反应器中催化加氢合成糠醇[J]. 化工学报,2006,57(3):693-699.
[3] Harry P,Paul W R. Enzyme-coupled ultrafiltration membranes[J]. Biotechnology Bioengineering,1975,17:445-448.
[4] 陈龙祥,由涛,张庆文,等. 膜反应器研究及其应用[J]. 现代化工,2009,29(4):87-90.
[5] 王建宇,徐又一,朱宝库. 高分子催化膜及膜反应器研究进展[J]. 膜科学与技术,2007,27(6):82-88.
[6] 李治,钱孟平. 强酸型离子交换膜催化合成草酸二异戊酯[J]. 精细与专用化学品,2003,11(10):61-63.
[7] 周永华,叶红齐,陈春辉. 催化接触器O型膜反应器的研究进展[J]. 工业催化,2007,15(11):6-10.
[8] Casimiro M H,Silva A G,Alvarez R,et al. PVA supported catalytic membranes obtained by γ-irradiation for biodiesel production[J]. Radiation Physics and Chemistry,2014,94:171-175.
[9] Ma X H,Wen X,Gu S W,et al. Preparation and characterization of catalytic TiO₂-SPPESK-PES nanocomposite membranes and kinetics analysis in esterification[J]. Journal of Membrane Science,2013,430:62-69.
[10] Ma S N,Meng J Q,Li J H,et al. Synthesis of catalytic polypropylene membranes enabling visible-light-driven photocatalytic degradation of dyes in water[J]. Journal of Membrane Science,2014,453:221-229.
[11] Liguori F,Barbaro P,Giordano C,et al. Partial hydrogenation reactions over Pd-containing hybrid inorganic/polymeric catalytic membranes[J]. Applied Catalysis A:General,2013,459:81-88.
[12] Shi W Y,He B Q,Ding J C,et al. Preparation and characterization of the organic-inorganic hybrid membrane for biodiesel production[J]. Bioresource Technology,2010,101:1501-1505.
[13] Mac Leod T C O,Marques R S,Schiavon M,et al. An environmentally friendly triphasic catalytic system: Mn (salen) occluded in membranes based on PDMS/PVA[J]. Applied Catalysis B:Environmental,2010,100:55-61.
[14] Villalobos L F,Neelakanda P,Karunakaran M,et al. Peinemann. Poly-thiosemicarbazide/gold nanoparticles catalytic membrane:In-situ growth of well-dispersed,uniform and stable gold nanoparticles in a polymeric membrane[J]. Catalysis Today,2014,236:92-97.
[15] Emin C,Remigy J C,Lahitte J E. Influence of UV grafting conditions and gel formation on the loading and stabilization of palladium nanoparticles in photografted polyethersulfone membrane for catalytic reactions[J]. Journal of Membrane Science,2014,455:55-63.
[16] Keraani A,Rabiller-Baudry M,Fischmeister C,et al. Immobilisation of an ionically tagged Hoveyda catalyst on a supported ionic liquid membrane:An innovative approach for metathesis reactions in a catalytic membrane reactor[J]. Catalysis Today,2010,156:268-275.
[17] Domènecha B,Muñoza M,Muravieva D N,et al. Catalytic membranes with palladium nanoparticles:From tailored polymer to catalytic applications[J]. Catalysis Today,2012,193:158-164.
[18] Jia Z Q,Sun H J,Du Z X,et al. Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium nanoparticles[J]. Journal of Environmental Sciences,2014,26:478-482.
[19] Lu O Y,David M D,Seth R H,et al. Catalytic hollow fiber membranes prepared using layer-by-layer adsorption of polyelectrolytes and metal nanoparticles[J]. Catalysis Today,2010,156:100-106.
[20] Casimiro M H,Silva A G,Pinto J V,et al. Catalytic poly(vinyl alcohol) functionalized membranes obtained by gamma irradiation[J]. Radiation Physics and Chemistry,2012,81:1314-1318.
[21] Jia Z Q,Zhen T L,Zhang X Q. Application of phase-transfer catalytic membrane reactor in liquid-liquid nucleophilic substitution reaction:Effects of operating parameters[J]. Journal of Membrane Science,2014,454:316-321.
[22] Jia Z Q,Zhen Tianli,Zhang Xiaoqin,et al. Preparation of phase-transfer catalytic porous membrane by γ-ray irradiation grafting and its application in nucleophilic substitution reaction[J]. Journal of Membrane Science,2013,448:74-80.
[23] Shi W Y,Li J X,He B Q,et al. Biodiesel production from waste chicken fat with low free fatty acids by an integrated catalytic process of composite membrane and sodium methoxide[J]. Bioresource Technology,2013,139:316-322.
[24] Shi W Y,He B Q,Cao Y P,et al. Continuous esterification to produce biodiesel by SPES/PES/NWF composite catalytic membrane in flow-through membrane reactor:Experimental and kinetic studies[J]. Bioresource Technology,2013,129:100-107.
[25] Shi W Y,He B Q,Li J X. Esterification of acidified oil with methanol by SPES/PES catalytic membrane[J]. Bioresource Technology,2011,102:5389-5393.
[26] Zhu M L,He B Q,Shi W Y,et al. Preparation and characterization of PSSA/PVA catalytic membranefor biodiesel production[J]. Fuel,2010,89:2299-2304.
[27] 刘庆林,朱玉山,陈洪钫. 交联聚乙烯醇渗透蒸发膜用于酯化反应过程[J]. 高校化学工程学报,1997,11(2):172-176.
[28] Shi W Y,He B Q,Li J X,et al. Continuous esterification to produce biodiesel by SPES/PES/NWF composite catalytic membrane in flow-through membrane reactor:Experimental and kinetics studies[J]. Bioresource Technology,2013,129:100-107.
[29] 朱木兰,何本桥,石文英,等. 响应面法优化PSSA/PVA共混膜催化酯化制备生物柴油[J]. 膜科学与技术,2011,31(4):89-93.
[30] 刘庆林,肖剑,张志炳. PVA-Zr (Ⅳ) 膜催化乙酸和丁醇酯化反应的性能[J]. 化工学报,2003,54(1):64-67.
[31] Cheng Y,Feng Y,Ren Y,et al. Comprehensive kinetic studies of acidic oil continuous esterification by cation-exchange resin in fixed bed reactors[J]. Bioresource Technology,2012,113,65-72.
[32] Shah T N,Ritchie S M C. Esterification catalysis using functionalized membranes[J]. Applied Catalysis A,2005,296:12-20.
[33] Ilinich O M,Cuperus F B,Gemert R W,et al. Catalytic membrane in denitrification of water: A means to facilitate in traporous diffusion of reactants[J]. Separate Purification Technology,2000,21(1-2):55-60.
[34] Schmidt A,Schomäker R. Partial hydrogenation of sunflower oil in a membrane reactor[J]. Journal of Molecular Catalysis A:Chemical,2007,271:192-199.
[35] Lopes J P,Cardoso S S S,Rodrigues A E. Effectiveness factor for thin catalytic coatings:Improved analytical approximation using perturbation techniques[J]. Chemical Engineering Science,2012,71:46-55.
[36] Vospernik M,Pintar A,Bercic G,et al. Mass transfer studies in gas-liquid-solid membrane contactors[J]. Catalysis Today,2003,79:169-179.
[37] Schomarcker R,Schmidt A,Frank B,et al. Membranenals catalysatortraeger[J]. Chemie Ingenieur Technik,2005,77(5):1-9.
[38] Shah T N,Ritchie S M C. Esterification catalysis using functionalized membranes[J]. Applied Catalysis A:General,2005,296(1):12-20.