选择性催化加氢合成氯代苯胺最新进展

doi:10.16085/j.issn.1000-6613.2018-0200

摘要/Abstract

摘要： 如何抑制脱氯氢解副反应是实现高效绿色合成氯代芳胺的核心问题。依据氯代硝基苯催化加氢合成氯代苯胺反应的抑制脱氯方法，选择性加氢催化剂设计思路可分为调变催化剂金属组分与载体的相互作用，制备双/多金属催化剂、非晶态合金催化剂、聚合物稳定的贵金属催化剂和杂原子修饰的贵金属催化剂等。本文分别综述了近年来各类抑制脱氯方法的研究进展及抑制脱氯机理，并进一步分析比较了不同反应介质对催化反应性能的影响。现有研究表明，杂原子修饰的贵金属催化剂表现出更好的催化性能，无溶剂条件下合成氯代苯胺彰显了绿色友好化工理念。两者有望成为今后的研究热点。

关键词: 催化, 选择性, 加氢, 催化剂载体, 无溶剂

Abstract: The core issue of efficient and green synthesis of chlorinated aromatic amines is to prevent the side reaction of dichlorination. The paper gives the recent progress of catalytic hydrogenation of chloronitrobenzene to chloroaniline. From the perspective of inhibiting dechlorination, the design strategies of selective hydrogenation catalysts can be divided into five types:modulating the interaction of metal components and supports, constructing double/multi metal catalyst, preparing amorphous alloy catalysts, employing polymer-stabilized noble metal catalysts and the heteroatoms modified noble metal catalysts. Research progress of all kinds of the methods and the mechanism of inhibiting dechlorination are introduced. The advantages and disadvantages of different reaction media are also discussed. It can be concluded that the heteroatoms modified noble metal catalyst exhibits superior catalytic performance, while the solvent-free method reflects the green concept of chemical industry. These two research directions will become the hot topics in the future.

Key words: catalysis, selectivity, hydrogenation, catalyst support, solvent-free

中图分类号:

O643.38

齐亚妮, 冯振龙, 季豪克, 王昊, 朱倩文, 张雪洁, 周烨彬, 卢春山, 李小年. 选择性催化加氢合成氯代苯胺最新进展[J]. 化工进展, 2018, 37(12): 4669-4678.

QI Yani, FENG Zhenlong, JI Haoke, WANG Hao, ZHU Qianwen, ZHANG Xuejie, ZHOU Yebin, LU Chunshan, LI Xiaonian. Latest progress on synthesis of chloroaniline by selective catalytic hydrogenation[J]. Chemical Industry and Engineering Progress, 2018, 37(12): 4669-4678.

参考文献

[1] CÁRDENAS-LIZANA F, HAO Y F, CRESPO-QUESADA M, et al. Selective gas phase hydrogenation of p-chloronitrobenzene over Pd[J]. ACS Catalysis, 2013, 3:1386-1396.
[2] MA L, WANG J G, ZHANG H B, et al.High halogenated nitrobenzene hydrogenation selectivity over nano Ir particles[J]. Chinese Journal of Chemical Engineering, 2018, 25(3):306-312.
[3] LI H, XU C F, MU X-L, et al.Acetylene-mediated synthesis of supported Pt nanocatalyst for selective hydrogenation of halonitrobenzene[J]. ChemNanoMat, 2018, 4(5):518-523.
[4] DONGIL A B, PASTOR-PEREZ L, FIERRO J L G, et al.Synthesis of palladium nanoparticles on carbon nanotubes and graphene for the chemoselective hydrogenation of para-chloronitrobenzene[J]. Catalysis Communications, 2016, 75:55-59.
[5] DONGIL A B, PASTOR-PEREZ L, FIERRO J L G, et al.Synthesis of palladium nanoparticles over graphite oxide and carbon nanotubes by reduction in ethylene glycol and their catalytic performance on the chemoselective hydrogenation of para-chloronitrobenzene[J]. Applied Catalysis A:General, 2016, 513:89-97.
[6] WANG Y, RONG Z M, WANG Y, et al.Ruthenium nanoparticles loaded on multiwalled carbon nanotubes for liquid-phase hydrogenation of fine chemicals:an exploration of confinement effect[J]. Journal of Catalysis, 2015, 329:95-106.
[7] OUBENALI M, VANUCCI G, MACHADO B, et al.Hydrogenation of p-chloronitrobenzene over nanostructured-carbon-supported ruthenium catalysts[J]. ChemSusChem, 2011, 4(7):950-956.
[8] BESWICK O, LAMEY D, MURISET F, et al.Ni-based structured catalyst for selective 3-phase hydrogenation of nitroaromatics[J]. Catalysis Today, 2016, 273:244-251.
[9] LI X, ZHAO S, ZHANG W, et al.Ru nanoparticles supported on nitrogen-doped porous carbon derived from ZIF-8 as an efficient catalyst for the selective hydrogenation of p-chloronitrobenzene and p-bromonitrobenzene[J]. Dalton Trans, 2016, 45(39):15595-15602.
[10] WANG X, LI Y W.Chemoselective hydrogenation of functionalized nitroarenes using MOF-derived Co-based catalysts[J]. Journal of Molecular Catalysis A:Chemical, 2016, 420:56-65.
[11] XIE Y L, XIAO N, YU C, et al. Magnetically recyclable Pt/C(Ni) nanocatalysts with improved selectivity for hydrogenation of o-chloronitrobenzene[J]. Catalysis Communications, 2012, 28:69-72.
[12] XU X S, LI X Q, GU H Z, et al. A highly active and chemoselective assembled Pt/C(Fe) catalyst for hydrogenation of o-chloronitrobenzene[J]. Applied Catalysis A:General, 2012, 429/430:17-23.
[13] TSU Y T, CHEN Y W.Hydrogenation of p-chloronitrobenzene on Au nano-clusters:effect of support[J]. Journal of Nanoscience and Nanotechnology, 2018, 18(1):301-308.
[14] ZHANG Q F, MA L, LU C S, et al.Solvent-free selective hydrogenation of o-chloronitrobenzene over large palladium particles on oxygen-poor activated carbon[J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(2):629-638.
[15] EVAGELISTI C, ARONICA L A, BOTAVINA M, et al. Chemoselective hydrogenation of halonitroaromatics over γ-Fe₂O₃-supported platinum nanoparticles:the role of the support on their catalytic activity and selectivity[J]. Journal of Molecular Catalysis A:Chemical, 2013, 366:288-293.
[16] LIU H Q, LIANG M H, XIAO C, et al.An excellent Pd-based nanocomposite catalyst for the selective hydrogenation of para-chloronitrobenzene[J]. Jourmal of Molecular Catalysis A:Chemical, 2009, 308:79-86.
[17] 宋华, 汪淑影, 李锋, 等.微乳液法制备Pt/Al₂O₃催化剂及其催化氯代硝基苯选择加氢活性[J]. 化工进展, 2011, 30(3):771-776. SONG H, WANG S Y, LI F, et al.Preparation of Pt/Al₂O₃ catalyst by microemulsion and its activity in selective hydrogenation of chloronitrobenzene[J]. Chemical Industry and Engineering Progress, 2011, 30(3):771-776.
[18] LI F, CAO B, MA R, et al.Preparation of Pt/Al₂O₃ catalyst in CTAB microemulsion and kinetics of m-chloronitrobenzene hydrogenation[J]. Russian Journal of Physical Chemistry A, 2016, 90(2):276-281.
[19] LI Y Z, YU J Y, LI W, et al.The promotional effect of surface defects on the catalytic performance of supported nickel-based catalysts[J]. Physical Chemistry Chemical Physics, 2016, 18(9):6548-6558.
[20] PIETROWSKI M, WOJCIECHOWSKA M.The origin of increased chemoselectivity of platinum supported on magnesium fluoride in the hydrogenation of chloronitrobenzene[J]. Catalysis Today, 2011, 169(1):217-222.
[21] PIETROWSKI M, ZIELINSKI M, WOJCIECHOWSKA M. Nanocolloidal Ru/MgF₂ catalyst for hydrogenation of chloronitrobenzene and toluene[J]. Polish Journal of Chemical Technology, 2014, 16(2):63-68.
[22] HAN X X, ZHOU R X, LAI G H, et al.Influence of rare earth (Ce, Sm, Nd, La, and Pr) on the hydrogenation properties of chloronitrobenzene over Pt/ZrO₂ catalyst[J]. Catalysis Letters, 2003, 89(3/4):255-259
[23] XIE Y L, XIAO N, LING Z, et al.Flower-like Co-Ni/C bimetallic catalysts for the selective hydrogenation of o-chloronitrobenzene[J]. Chinese Journal of Catalysis, 2012, 33(11/12):1883-1888.
[24] MAHATA N, SOARES O S G P, RODRIGUEZ-RAMOS I, et al. Promotional effect of Cu on the structure and chloronitrobenzene hydrogenation performance of carbon nanotube and activated carbon supported Pt catalysts[J].Applied Catalysis A:General, 2013, 464/465:28-34.
[25] MISTRI R, LLORCA J, RAY B C, et al.Pd_0.01Ru_0.01Ce_0.98O_2-δ:a highly active and selective catalyst for the liquid phase hydrogenation of p-chloronitrobenzene under ambient conditions[J]. Journal of Molecular Catalysis A:Chemical, 2013, 376:111-119.
[26] LIU M H, BAI Q, XIAO H L, et al.Selective hydrogenation of o-chloronitrobenzene over tin dioxide supported platinum-ruthenium bimetallic nanocatalysts without solvent[J]. Chemical Engineering Journal, 2013, 232:89-95.
[27] LIHAMA S, FURUKAWA S, KOMATSU T. Efficient catalytic system for chemoselective hydrogenation of halonitrobenzene to haloaniline using PtZn intermetallic compound[J]. ACS Catalysis, 2016, 6(2):742-746.
[28] WU M, XU Y, JU J X, et al.Preparation of Pd-B/palygorskite amorphous catalyst for the selective hydrogenation of o-chloronitrobenzene to o-chloroaniline[J]. Micro & Nano Letters, 2016, 11(6):315-318.
[29] LI F, MA R, CAO B, et al.Effect of Co-B supporting methods on the hydrogenation of m-chloronitrobenzene over Co-B/CNTs amorphous alloy catalysts[J].Applied Catalysis A, 2016, 14:248-252.
[30] LI F, CAO B, MA R, et al.Preparation of Pt-B/Al₂O₃ amorphous alloy catalysts via microemulsion methods and application into hydrogenation of m-chloronitrobenzene[J]. The Canadian Journal of Chemical Engineering, 2016, 94(1):89-93.
[31] LIU H, DENG J, LI W.Synthesis of nickel nanoparticles supported on boehmite for selective hydrogenation of p-nitrophenol and p-chloronitrobenzene[J]. Catalysis Letters, 2010, 137(3/4):261-266.
[32] CHEN Y W, LEE D S.Hydrogenation of p-chloronitrobenzene on nanosized modified NiMoB catalysts[J]. Catalysis Surveys from Asia, 2012, 16(4):198-209.
[33] ZHAO B, CHEN Y W.The effect of poly-N-vinylpyrrolidone modification on NiCoB catalysts for hydrogenation of p-chloronitrobenzene[J]. Materials Chemistry and Physics, 2011, 125(3):763-768.
[34] LIU M H, ZHANG J, LIU J Q, et al.Synthesis of PVP-stabilized Pt/Ru colloidal nanoparticles by ethanol reduction and their catalytic properties for selective hydrogenation of ortho-chloronitrobenzene[J]. Journal of Catalysis, 2011, 278(1):1-7.
[35] LI F, CAO B, MA R, et al.Polyvinylpyrrolidone-stabilized Pt colloidal catalysts in chloronitrobenzene hydrogenation and modification with rare earth ions[J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 116(2):479-489.
[36] LI F, MA R, SONG H L, et al.Selective hydrogenation of m-chloronitrobenzene to m-chloroaniline over polyvinyl-pyrrolidone-stabilized Pt and Pt/Sn catalysts[J].Russian Journal of Physical Chemistry A, 2015, 89(5):766-770.
[37] DANI A, CROCELLA V, MADDALENA L, et al.Spectroscopic study on the surface properties and catalytic performances of palladium nanoparticles in poly(ionic liquid)s[J].The Journal of Physical Chemistry C, 2016, 120(3):1683-1692.
[38] LU C S, WANG M J, FENG Z L, et al.A phosphorus-carbon framework over activated carbon supported palladium nanoparticles for the chemoselective hydrogenation of para-chloronitrobenzene[J]. Catalysis Science & Technology, 2017, 7(7):1581-1589.
[39] SHI W, ZHANG B S, LIN Y M, et al.Enhanced chemoselective hydrogenation through tuning the interaction between pt nanoparticles and carbon supports:insights from identical location transmission electron microscopy and X-ray photoelectron spectroscopy[J].ACS Catalysis, 2016, 6(11):7844-7854.
[40] ZHANG Q F, SU C, CEN J, et al.The modification of diphenyl sulfide to Pd/C catalyst and its application in selective hydrogenation of p-chloronitrobenzene[J].Chinese Journal of Chemical Engineering, 2014, 22(10):1111-1116.
[41] WEI Q, SHI Y S, SUN K Q, et al. Pd-on-Si catalysts prepared via galvanic displacement for the selective hydrogenation of para-chloronitrobenzene[J].Chemical Communications, 2016, 52(14):3026-3029.
[42] HU Z, TAN S Q, MI R L, et al.Solvent-controlled reactivity of Au/CeO₂ towards hydrogenation of p-chloronitrobenzene[J]. Catalysis Letters, 2018, 148(5):1490-1498.
[43] 卢春山.氯代苯胺合成中金属催化剂性能与溶剂效应研究[D].杭州:浙江工业大学, 2011. LU C S.Solvent effects and the catalytic performance of metallic catalysis in the highly selective hydrogenation of chloronitrobenzenes to chloroanilines[D]. Hangzhou:Zhejiang University of Technology, 2011.
[44] NING J B, XU J, LIU J, et al.A remarkable promoting effect of water addition on selective hydrogenation of p-chloronitrobenzene in ethanol[J]. Catalysis Communications, 2007, 8(11):1763-1766.
[45] XIAO C, WANG H, MU X, et al.Ionic-liquid-like copolymer stabilized nanocatalysts in ionic liquids Ⅰ. Platinum catalyzed selective hydrogenation of o-chloronitrobenzene[J]. Journal of Catalysis, 2007, 250(1):25-32.
[46] XI C Y, CHENG H Y, HAO J M, et al.Hydrogenation of o-chloronitrobenzene to o-chloroaniline over Pd/C in supercritical carbon dioxide[J]. Journal of Molecular Catalysis A:Chemical, 2008, 282(1/2):80-84.
[47] ICHIKAWA S, TADA M, IWASAWA Y, et al.The role of carbon dioxide in chemoselective hydrogenation of halonitroaromatics over supported noble metal catalysts in supercritical carbon dioxide[J]. Chem Commun (Camb), 2005(7):924-926.
[48] WANG X D, PERRET N, KEANE M A.The role of hydrogen partial pressure in the gas phase hydrogenation of p-chloronitrobenzene over alumina supported Au and Pd:a consideration of reaction thermodynamics and kinetics[J].Chemical Engineering Journal, 2012, 210:103-113.
[49] PERRET N, CARDENAS-LIZANA F, LAMEY D, et al.Effect of crystallographic phase (beta vs. gamma) and surface area on gas phase nitroarene hydrogenation over Mo₂N and Au/Mo₂N[J].Topics in Catalysis, 2012, 55(14/15):955-968.
[50] YU W, LIN H W, TAN C S, et al.Direct synthesis of Pd incorporated in mesoporous silica for solvent-free selective hydrogenation of chloronitrobenzenes[J]. Chemical Engineering Journal, 2017, 325:124-133.
[51] 李小年, 卢春山, 吕井辉, 等.一种无溶剂条件下高选择性液相加氢合成卤代芳胺的方法:CN201010153731.1[P]. 2010-08-25. LI X N, LU C S, LÜ J H, et al. A highly selective hydrogenation of halogenated aromatic amines under solvent-free conditions in liquid phase:CN201010153731.1[P]. 2010-08-25.
[52] LIAN C, LIU H Q, XIAO C, et al. Solvent-free selective hydrogenation of chloronitrobenzene to chloroaniline over a robust Pt/Fe₃O₄ catalyst[J]. Chemical Communications, 2012, 48(25):3124-3126.
[53] WANG Y A, YANG Y X, LI Y W, et al.A green synthesis route of ortho-chloroaniline:solvent-free selective hydrogenation of ortho-chloronitrobenzene over Pt-Ru/Fe₃O₄/C catalyst[J].Catalysis Communications, 2012, 19:110-114.
[54] LIU M H, BAI Q, XIAO H L, et al.Selective hydrogenation of o-chloronitrobenzene over tin dioxide supported platinum-ruthenium bimetallic nanocatalysts without solvent[J].Chemical Engineering Journal, 2013, 232:89-95.
[55] YU W, LIN H W, TAN C S.Direct synthesis of Pd incorporated in mesoporous silica for solvent-free selective hydrogenation of chloronitrobenzenes[J]. Chemical Engineering Journal, 2017, 325:124-133.