丙烷脱氢Cr系催化剂的研究进展

摘要/Abstract

摘要： 综述了Cr系催化剂在丙烷催化脱氢和氧化脱氢反应中的应用研究进展情况，介绍了在这两种脱氢反应中，Cr系催化剂的活性中心、脱氢反应机理以及催化性能影响因素，分析了催化剂的失活原因，探讨了催化剂再生的影响，并对Cr系催化剂的发展前景和方向进行了展望。开发新型低铬含量、高选择性和抗积炭的催化剂是Cr系催化剂当前的研究重点，提高丙烷氧化脱氢反应中丙烷的转化率和丙烯收率是今后的主要研究方向。

关键词: 丙烷脱氢, Cr系催化剂, 失活, 再生

Abstract: Progresses in propane catalytic dehydrogenation and propane oxidation dehydrogenation of Cr-based catalysts were reviewed. The active sites of catalyst，dehydrogenation mechanism and influence factors for the reaction in two processes were introduced. The reasons of catalyst deactivation were analyzed and the influence of regeneration on catalyst performance was discussed. The development of new type catalysts with lower Cr content, higher selectivity and better resistance to coke deposit is the current focus. While the Cr-based catalyst for propane oxidation dehydrogenation with improved propane conversion rate and higher propene yield is the main direction in future.

Key words: propane dehydrogenation, Cr-based catalyst, deactivation, regeneration

中图分类号:

卜婷婷李秋颖苟文甲马艳捷周金波董炳利. 丙烷脱氢Cr系催化剂的研究进展[J]. 石油炼制与化工, 2017, 48(11): 103-110.

参考文献

[1] 张凌峰,刘亚录,胡忠攀,等.丙烷脱氢制丙烯催化剂研究的进展[J].石油学报(石油加工),2015,31(2):400-417.
[2] 张艳惠,田爱珍,张忠东,等.丙烷脱氢制丙烯催化剂中国专利技术进展[J].应用化工,2014,43(6):1133-1135.
[3] Nawaz Z. Light alkane dehydrogenation to light olefin technologies: A comprehensive review[J].Rev Chem Eng, 2015, 31(5): 413-436.
[4] 谭晓林,马波,张喜文,等.Cr系丙烷脱氢催化剂研究进展[J].化工进展,2010, 29(1):51-57.
[5] 胡昌龙.丙烷脱氢制丙烯含铬催化剂制备与催化性能的研究[D].上海:上海师范大学,2014.
[6] Pisduangdaw S, Panpranot J, Methastidsook, et al. Characteristics and catalytic properties of Pt-Sn/Al2O3 nanoparticles synthesized by one-step flame spray pyrolysis in the dehydrogenation of propane[J]. Appl Catal A:Gen, 2009, 370(1/2):1-6.
[7] Richardson PC, Rossington DR. The activity of transition metal oxides for cyclohexane dehydrogenation[J]. J Catal, 1969, 14(2): 175-181.
[8] Grunert W, Saffert W, Feldhaus R, et al. Reduction and aromatization activity of chromia-alumina catalysts:Reduction and break-in behavior of a potassium- promoted chromia-alumina catalyst[J]. J Catal, 1986, 99(1):149-158.
[9] Shee D, Abdelhamid, Sayari. Light alkane dehydrogenation over mesoporous Cr2O3/Al2O3 catalysts[J]. Appl Catal A:Gen, 2010, 389:155-164.
[10] 上海师范大学.一种薄片状氧化铬/氧化铝催化剂及其制备方法和应用:中国, 201310234194.7[P].2013-06-13.
[11] Takehira K, Ohishi Y, Shishido T, et al. Behavior of active sites on Cr-MCM-41 catalysts during the dehydrogenation of propane with CO2[J]. J Catal, 2004, 224(2):404-416.
[12] Cutrufello M G, De Rossi S, Ferino I, et al. Preparation, characterization and activity of chromia-zirconia catalysts for propane dehydrogenation[J]. Thermochimica Acta, 2005, 434(l/2):62-68.
[14] Yue Hongyong, Zheng Bo, Yue Yinghong, et al. Characterization and dehydrogenation activity of SBA-15 and HMS supported chromia catalysts[J]. Chin J Chem, 2002, 20(11): 1192-1198.
[15] Hardcastlefd，Wachsie. Raman spectroscopy of chromium oxide supported on A12O3,TiO2 and SiO2:A comparative study[J].J Mol Catal, 1988, 46(1):173-186.
[16] Gorriz O F, Cadu L E. Supported chromium oxide catalysts using metal carboxylate complexes: dehydrogenation of propane]J]. App1 Cata1 A: General, 1999, 180: 247-260．
[17] Cimino A, Cordishi D, Derossi S, et a1. Studies on chromia zirconia catalysts III. Propene hydrogenation[J]. Catal, 1991, 127: 777-787.
[18] Cavani F, Koutyrev M, Trifirò F, et a1. Chemical and physical characterization of alumina-supported chromia-based catalysts and their activity in dehydrogenation of isobutane[J]. Cata1, 1996, 158: 236-250.
[19] 吴同旭, 杨玉旺, 蔡奇, 等. CrOx/Al2O3丙烷脱氢催化剂性能研究[J]. 天然气化工?C1化学与化工, 2016, 41(3): 16-20.
[20] Kumar MS, Hammer N, R?ning M, et al. The nature of active chromium species in Cr-catalysts for dehydrogenation of propane: New insights by a comprehensive spectroscopic study[J]. J Catal, 2009, 261:116-128.
[21] Weckhuysen BM, Schoonheydt RA. Alkane dehydrogenation over supported chromium oxide catalysts[J]. Catal Today, 1999, 51:223-232.
[22] Cabrera F, Ardissone D, Gorriz OF. Dehydrogenation of propane on chromia/alumina catalysts promoted by tin[J].Catal Today, 2008, 133-135:800-804.
[23] Li Peipei, Lang Wanzhong, Xia Ke, et al. The promotion effects of Ni on the properties of Cr/Al catalysts for propane dehydrogenation reaction[J]. Appl Catal A:Gen, 2016, 522:172-179.
[24] 王振宇, 郑步梅, 张淑梅. CuO、Ga2O3改性Cr2O3/γ-Al2O3催化剂丙烷脱氢反应性能研究[J]. 2016, 41(5): 15-19.
[25] Liu Daolan, Bai Peng, Wu Pingping, et al. Surface chemistry and catalytic performance of chromia/alumina catalysts derived from different potassium impregnation sequences[J]. Appl Surf Sci, 2015, 351:250-259.
[26] Martyanov I, Sayari A. Sol-gel assisted preparation of chromia-silica catalysts for non-oxidative dehydrogenation of propane[J]. Catal Lett, 2008, 126:164-172.
[27] Didenko LP, Kolesnikova AM, Voronetskii MS, et al. Chromia-alumina catalysts for the dehydrogenation of propane prepared by a modified method of codeposition[J]. Catal Ind, 2011, 3(2):128-135.
[28] Gadzhizade SM, Dzhamalova SA, Aliev NA, et al. A study of the reaction of propane dehydrogenation on a Cr,Co,Ni,Bi,K/γ-Al2O3 catalyst in the presence of atmospheric oxygen[J]. Russ J Appl Chem, 2009, 8(5): 880-883.
[29] De León MA, De Los Santos C, Latrónica L, et al. High catalytic activity at low temperature in oxidative dehydrogenation of propane with Cr-Al pillared clay[J]. Chem Eng J, 2014, 241:336-343.
[30] Xu Bingjun, Zheng Bo, Hua Weiming, et al. Support effect in dehydrogenation of propane in the presence of CO2 over supported gallium oxide catalysts [J].J Catal, 2006, 239:470-477.
[31] Ogonowski J, Skrzyńska E. Activity of vanadium magnesium oxide supported catalysts in the dehydrogenation of isobutane[J].Catal Lett, 2006, 111(1):79-85.
[32] Botavina MA, Evangelisti C, Agafonov YA, et al. CrOx/SiO2 catalysts prepared by metal vapour synthesis: Physical-chemical characterization and functional testing in oxidative dehydrogenation of propane[J]. Chem Eng J, 2011, 166: 1132-1138.
[33] Ma Fei, Chen Shu, Wang Yang, et al. Characterization of redox and acid properties of mesoporous Cr-TiO2 and its efficient performance for oxidative dehydrogenation of propane[J].Appl Catal A:Gen, 2012, 427-428:145-154.
[34] 张帆，聂颖颖，缪长喜，等. Cr/NaZSM-5催化剂上CO2氧化丙烷脱氢反应[J]. 高等学校化学学报，2012，33（1）：1-6.
[35] Li Lina, Zhu Wenliang, Shi Lei, et al. The effect of ethanol on the performance of CrOx/SiO2 catalysts during propane dehydrogenation[J].Chin J Catal, 2016, 37(3):359-366.
[36] Janas J, Gurgul J, Socha RP, et al. Influence of the content and environment of chromium in CrSiBEA zeolites on the oxidative dehydrogenation of propane[J]. J Phys Chem C, 2009, 113:13273-13281.
[37] Zou Hu, Han Yuwang, Ji Weijie, et al. ESR study on the nature of active site of silica-supported chromia in propane dehydrogenation reaction[J]. Chem Lett, 1999, 28(8):761-762.
[38] 柳海涛, 李会泉, 杨玮娇, 等.Cr/MSU-1催化剂中Cr含量对CO2氧化丙烷脱氢反应催化性能的影响[J]. 化学学报, 2009, 15: 1749-1753.
[39] Shishido T, Shimamura K, Teramura K, et al. Role of CO2 in dehydrogenation of propane over Cr-based catalysts[J]. Catal Today, 2012, 185:151-156.
[40] Michorczyk P, Pietrzyk P, Ogonowski J. Preparation and characterization of SBA-1-supported chromium oxide catalysts for CO2 assisted dehydrogenation of propane[J]. Microporous and Mesoporous Mater, 2012, 161:56-66.
[41] 缪建文,周静,宋国华,等.CrOx/SBA-15介孔催化剂上丙烷在二氧化碳气氛中脱氢反应的研究[J].无机化学学报, 2005, 21(10): 1541-1545.
[42] W?grzyniaka A, Jarczewski S, Wach A, et al. Catalytic behaviour of chromium oxide supported on CMK-3 carbonreplica in the dehydrogenation propane to propene[J]. Appl Catal A:Gen, 2015, 508:1-9.
[43] 布仁特古斯. 丙烷氧化脱氢反应的热力学及反应机理[J]. 内蒙古电大学刊, 2003, 54(2): 43-44.
[44] Kaidong Chen, Enrique Iglesia, Alexis T Bell. Kinetic isotopic effects in oxidative dehydrogenation of propane on vanadium oxide catalyst[J]. J Catal, 2000, 192: 197-203.
[45] Kaidong Chen, Andrei Khodakov, Jun Yang, et al. Isotopic tracer and kinetic studies of oxidative dehydrogenation pathways on vanadium oxide catalyst[J]. J Catal, 1999,186: 325-333.
[46] J Gascón, C Téllez, J Herguido, et al. Propane dehydrogenation over a Cr2O3/Al2O3 catalyst: transient kinetic modeling of propene and coke formation[J]. Appl Catal A: Gen, 2003, 248: 105-116.
[47] Olsbye U, Virnovskaia A, Prytz ?, et al. Mechanistic Insight in the Ethane Dehydrogenation Reaction over Cr/Al2O3 Catalysts[J]. Catal Lett, 2005,103(1-2): 143-148.
[48] Weckhuysen BM, Bensalem A, Schoonheydt RA. In situ UV-VIS diffuse reflectance spectroscopy-on-line activity measurements Significance of Crn+ species (n=2,3,6) in n-butane dehydrogenation catalyzed by supported chromium oxide catalysts[J].J Chem Soc, Faraday Trans, 1998, 94(14):2011-2014.
[49] Derossi S, Ferraris G, Fremiotti S, et al. Propane Dehydrogenation on Chromia/Silica and Chromia/Alumina Catalysts[J]. J Catal, 1994, 148(1):36-46.
[50] Delley MF, Silaghi MC, Nun?ez-Zarur F, et al. X-H bond activation on Cr(III)，O sites (X=R,H): key steps in dehydrogenation and hydrogenation processes[J]. organomet Chem, 2017, 36:234-244.
[51] Zou Hu, Ge Xin, Li Mingshi, et al. Dehydrogenation of propane over CrOx/SiO2 catalysts under CO2 atmosphere[J]. Chin Inorg Chem, 2000, 16(5):775-782.
[52] Takahara I, Chang WC, Mimura N, et al. Promoting effects of CO2 on dehydrogenation of propane over a SiO2-supported Cr2O3 catalyst[J]. Catal Today, 1998, 45(1-4):55-59.
[53] Kocoń M, Michorczyk P, Ogonowski J. Effect of supports on catalytic activity of chromium oxide-based catalysts in the dehydrogenation of propane with CO2[J]. Catal Lett, 2005, 101(1-2):53-57.
[54] Wu Runxia, Xie Pengfei, Cheng Yanhu, et al. Hydrothermally prepared Cr2O3-ZrO2 as a novel efficient catalyst for dehydrogenation of propane with CO2[J]. Catal Commun, 2013, 39:20-23.
[55] Cutrufello MG, Rossi SD, Ferino I, et al. Preparation, characterisation and activity of chromia-zirconia catalysts for propane dehydrogenation[J]. Thermochim Acta, 2005, 434:62-68.
[56] 蔡奇,杨玉旺,吴同旭,等.Mg对Cr2O3/Al2O3催化剂及其丙烷脱氢性能的影响[J].石油炼制与化工,2016,47(3):72-76.
[57] Ki Hyukkang, Tae Hyeopkim, Won Choonchoi, et al. Dehydrogenation of propane to propylene over CrOy-CeO2-K2O/γ-Al2O3 catalysts: Effect of cerium content[J]. Catal Commun, 2015, 72:68-72.
[58] 武润霞.水热法制备的及稀土氧化物修饰的催化剂上丙烷二氧化碳脱氢制丙烯研究[D].上海:复旦大学,2013.
[59] Puurunen RL, Weckhuysen BM. Spectroscopic study on the irreversible deactivation of chromia/alumina dehydrogenation catalysts[J]. J Catal, 2002, 210(2):418-430.
[60] Hakuli A, Kyt?kivi A, Krause AOI, et al. Initial activity of reduced chromia/alumina catalyst in n-butane dehydrogenation monitored by on-line FT-IR gas analysis[J]. J Catal, 1996, 161:393-400.
[61] De Rossi S, Casaletto MP, Ferraris G, et al. Chromia/zirconia catalysts with Cr content exceeding the monolayer. A comparison with chromia/alumina and chromia/silica for isobutane dehydrogenation[J]. Appl Catal A:Gen, 1998, 167(2):257-270.
[62] Nijhuis TA, Tinnemans SJ, Visser T, et al. Towards real-time spectroscopic process control for the dehydrogenation of propane over supported chromium oxide catalysts[J]. Chem Eng Sci, 2004, 59:5487-5492.
[63] Gascón J, Téllez C, Herguido J, et al. Propane dehydrogenation over a Cr2O3/Al2O3 catalyst: transient kinetic modeling of propene and coke formation[J]. Appl Catal A:Gen, 2003, 248:105-116.
[64] Sattler JJ, González-Jiménez ID, Mens AM, et al. Operando UV-Vis spectroscopy of a catalytic solid in a pilot-scale reactor: deactivation of a CrOx/Al2O3 propane dehydrogenation catalyst[J].Chem Commun, 2013, 49:1518-1520.
[65] Zhang Xinping, Sui Zhijun, Zhou Xinggui, et al. Modeling and simulation of coke combustion regeneration for coked Cr2O3/Al2O3 propane dehydrogenation catalyst[J]. Chin J Chem Eng, 2010, 18(4):618-625.
[66] 刘尚,赵金波,房德仁,等.再生过程对Cr2O3/Al2O3催化剂性能的影响[J]. 石油化工, 2016, 4(1):36-41.

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