制备方法对含硅氧化铝载体性质的影响

doi:10.16085/j.issn.1000-6613.2017-0858

摘要/Abstract

摘要： 含硅氧化铝载体因其兼具SiO₂和Al₂O₃的共同优势，即具有较好的结构性能、力学性能和一定的表面酸性，在加氢催化剂领域得到广泛应用。本文详细介绍了含硅氧化铝催化剂载体的制备方法，包括溶胶-凝胶法、NaAlO₂-Al₂（SO₄）₃法、混合法、浸渍法及化学气相沉积法。对比了制备方法对载体物化性质的影响，其中采用溶胶-凝胶法制备的载体纯度高，物化性质较好。分析了不同制备方法导致含硅氧化铝载体物化性质存在差别的作用机制。在体相中引入硅有利于调变载体孔结构，反之硅暴露于亚表面或表面有利于调变载体酸性。并指出了当前研究中存在的问题及含硅氧化铝的发展方向。

关键词: 含硅氧化铝, 载体, 制备方法, 孔结构, 酸性

Abstract: The silicon-containing alumina support has been widely used in the field of hydrogenation catalysts because it possess the mutual advantage of SiO₂ and Al₂O₃.In other words,it exhibits better structural properties,mechanical properties and suitable surface acidity.In this paper,the preparation of silicon-containing γ-Al₂O₃ catalyst support were introduced in detail,including sol-gel method,NaAlO₂-Al₂(SO₄)₃ method,kneading method,impregnation and chemical vapor deposition.The effect of preparation method on the pore structure and acidity are discussed.γ-Al₂O₃ catalyst support synthesized by sol-gel method has high chemical purity and exhibits excellent physicochemical properties.The influence mechanism of physicochemical properties of silicon-containing alumina synthesized by different methods is analyzed.It is conducive to turn the pore structure by instructing silicon into alumina in bulk,whereas silicon exposure to the sub-surface or surface facilitates turning the acidity of support.The problems in the current research and the development trend of silicon-containing alumina are proposed.

Key words: silicon-containing γ-Al₂O₃, support, preparation, pore structure, acidity

中图分类号:

TQ133

王敏朵, 曾双亲, 贾燕子, 杨清河. 制备方法对含硅氧化铝载体性质的影响[J]. 化工进展, 2017, 36(S1): 235-240.

WANG Minduo, ZENG Shuangqin, JIA Yanzi, YANG Qinghe. Influence of preparation methods on the physical and chemical properties of silicon-containing γ-Al₂O₃ support[J]. Chemical Industry and Engineering Progress, 2017, 36(S1): 235-240.

参考文献

[1] HU F,WU X,WANG Y,et al.Ultrathin γ-Al₂O₃ nanofibers with large specific surface area and their enhanced thermal stability by Si-doping[J].Rsc Advances,2015,5(67):54053-54058.
[2] 赵振兴,夏春谷,薛群基,等.球形SiO₂-Al₂O₃的制备、结构和性能[J].物理化学学报,2007,23(4):549-553. ZHAO Z X,XIA C G,XUE Q J,et al.Preparation,structure and properties of spherical SiO₂-Al₂O₃ composites[J].Acta Physico-Chimica Sinica,2007,23(4):549-553.
[3] 吴雨航,凌凤香,赵国利,等.CoMo/Al₂O₃-SiO₂催化剂原位红外光谱研究[J].当代化工,2015(5):962-964. WU Y H,LING F X,ZHAO G L,et al.In-situ FT-IR study on the CoMo/Al₂O₃-SiO₂ catalyst[J].Contemporary Chemical Industry,2015(5):962-964.
[4] Zhu C X,Zhu S F.Preparation of Al₂O₃-SiO₂ Composite powder by sol-gel method[J].Advanced Materials Research,2014,1053:173-176.
[5] 杨南如,余桂郁.溶胶-凝胶法简介第一讲——溶胶-凝胶法的基本原理与过程[J].硅酸盐通报,1993(2):58-65. YANG N R,YU G Y A brief introduction to sol gel method-the basic principle and process of sol-gel method[J].Bulletin of the Chinese Ceramic Society,1993(2):58-65.
[6] POPA A F,ROSSIGNOL S,KAPPENSTEIN C.Influence of drying technique on silicon insertion into γ-alumina and consequences for the homogeneity and thermal stability of silica-alumina aquagels[J].Journal of Materials Chemistry,2002,12(10):2866-2868.
[7] ISLAM S,BIDIN N,RIAZ S,et al.Mesoporous nanocomposite coatings for photonic devices:sol-gel approach[J].Applied Physics A,2016,122(10):935.
[8] DANIELL W,SCHUBERT U,GLÖCKLER R,et al.Enhanced surface acidity in mixed alumina-silicas:a low-temperature FTIR study[J].Applied Catalysis A:General,2000,196(2):247-260.
[9] MARDKHE M K,KEYVANLOO K,BARTHOLOMEW C H,et al.Acid site properties of thermally stable,silica-doped alumina as a function of silica/alumina ratio and calcination temperature[J].Applied Catalysis A:General,2014,482(28):16-23.
[10] KHOSRAVI-MARDKHE M,WOODFIELD B F,BARTHOL-OMEWY C H,et al.Method of making highly porous,stable aluminum oxides doped with silicon:US9289750[P].2016-03-22.
[11] 姚楠,熊国兴,张玉红,等.溶胶凝胶法制备中孔分布集中的氧化物及混合氧化物催化材料[J].中国科学(化学),2001,31(4):355-363. YAO N,XIONG G X,ZHANG Y H,et al.Oxide and mixed oxide catalytic materials with concentrated hole distribution synthesized by sol -gel method[J].Science in China(Chemistry),2001,31(4):355-363.
[12] NAMPI P P,MOOTHETTY P,WUNDERLICH W,et al.High-surface-area alumina-silica nanocatalysts prepared by a hybrid sol-gel route using a boehmite precursor[J].Journal of the American Ceramic Society,2010,93(12):4047-4052.
[13] NAMPI P P,WARRIER K G K,PADMANABHAN M,et al.Structural aspects and porosity features of nano-size high surface area alumina-silica mixed oxide catalyst generated through hybrid sol-gel route[J].Materials Chemistry & Physics,2006,95(95):56-61.
[14] WUNDERLICH W,NAMPI P P,WARRIER K G K.TEM characterization of sol-gel-processed alumina-silica and alumina-titania nano-hybrid oxide catalysts[J].Journal of the European Ceramic Society,2004,24(2):313.
[15] 李大东.加氢处理工艺与工程[M].北京:中国石化出版社,2004. LI D D.Hydrotreating process and engineering[M].Beijing:China Petrochemical Press,2004.
[16] 刘文洁,隋宝宽,袁胜华,等.硫酸铝法制备拟薄水铝石过程研究[J].石油炼制与化工,2016,47(1):27-31. LIU W J,SUI B K,YUAN S H,et al.Study on the preparation of pseudo-boehmite by aluminum sulfate method[J].Petroleum Processing and Petrochemicals,2016,47(1):27-31.
[17] 李振华.重油加氢催化剂载体材料的研究[D].青岛:中国石油大学,2010. LI Z H.Study of catalytic materials for hydrotreating of heavy oil[D].Qingdao:China University of Petroleum,2010.
[18] XU B,YANG Y,XU Y,et al.Synthesis and characterization of mesoporous Si-modified alumina with high thermal stability[J].Microporous & Mesoporous Materials,2016,238:84-89.
[19] YANG Y,XU Y,HAN B,et al.Effects of synthetic conditions on the textural structure of pseudo-boehmite.[J].Journal of Colloid & Interface Science,2016,469(1):1-7.
[20] 李洪宝,曾双亲,夏国富,等.一种芳烃加氢饱和催化剂及其应用:102309963A[P].2012-01-11. LI H B,ZENG S Q,XIA G F,et al.An aromatic hydrogenation saturated catalyst and its application:102309963A[P].2012-01-11.
[21] 龙湘云,刘清河,张乐,等.一种拟薄水铝石与含硅化合物的组合物和由其制备的氧化硅-氧化铝:102160996A[P].2013-06-26. LONG X Y,LIU Q H,ZHANG L,et al.A composition of pseudo-boehmite and a silicon-containing compound and a silica-alumina prepared therefrom:102160996A[P].2013-06-26.
[22] 杨清河,曾双亲,任亮,等.含有水合氧化铝的成型物及其制备方法和氧化铝成型物和应用:103418357[P].2016-04-27. YANG Q H,ZENG S Q,REN L,et al.The preparation of hydrated alumina composite material and the application of alumina composite material:103418357[P].2016-04-27.
[23] 宋立民,李伟,张明慧,等.Ni₂P/SiO₂-Al₂O₃催化剂的制备、表征及其对4,6-二甲基二苯并噻吩加氢脱硫反应的催化性能[J].催化学报,2007,28(2):143-147. SONG L M,LI W,ZHANG M H,et al.Preparation and characterization of Ni₂P/SiO₂-Al₂O₃ and its catalytic performance for hydrodesulfurization of 4,6-dimethyldibenzothiophene[J].Chinese Journal of Catalysis,2007,28(2):143-147.
[24] 亢丽娜,郭江渊,张鸿喜,等.Ni/SiO₂-Al₂O₃催化剂在水相加氢体系中的活性及稳定性研究[J].分子催化,2014,28(2):119-125. KANG L N,GUO J Y,ZHANG H X,et al.Activity and stability of Ni/SiO₂-Al₂O₃ catalyst in the aqueous phase hydrogenation system[J].Journal of Molecular Catalysis,2014,28(2):119-125.
[25] SHUTILOV A A,ZENKOVETS G A,TSYBULYA S V,et al.Effect of silica on the stability of the nanostructure and texture of fine-particle alumina[J].Kinetics and Catalysis,2012,53(1):125-136.
[26] KATADA N,NIWA M.Silica monolayer solid-acid catalyst prepared by CVD[J].Chemical Vapor Deposition,1996,2(4):125-134.
[27] SATO S,TOITA M,SODESAWA T,et al.Catalytic and acidic properties of silica-alumina prepared by chemical vapour deposition[J].Applied Catalysis,1990,62(1):73-84.
[28] KOUADRI-MOSTEFA S,SERP P,HÉMATI M,et al.Silicon chemical vapor deposition (CVD)on microporous powders in a fluidized bed[J].Powder Technology,2001,120(1):82-87.
[29] BOATENG K,HILL J.Characterization of SiO₂ deposited by CVD on Mo_xO_y/Al₂O₃ using NMR and TOF-SIMS[J].Chemical Vapor Deposition,2008,14(1/2):25-32.