Regeneration of zeolite catalyst for dimethyl ether carbonylation

doi:10.11949/j.issn.0438-1157.20170489

Abstract

Abstract:

The H-MOR zeolite catalysts were prepared by hydrothermal synthesis.An inactivated catalyst which was used in dimthyl ether carbonylaiton was regenerated.The effects of gas,coke-burning temperature,O₂ volume fraction and heating rate on the coke-burning process were investigated.The results of TPO and XRD analysis showed that there was different property coke on the inactivated catalyst.In the optimum conditions for the coke-burning of the inactivated catalyst,temperature 550℃,heating rate of 2℃·min^-1 and O₂ volume fraction of 3%,the catalyst activity was almost completely restored.The fresh and regenerated catalysts were characterized by means of NH₃-TPD and N₂ adsorption-desorption.The results showed that the coke was removed cleanly and channels were protected in the optimum condition.

Key words: zeolite, catalyst, dimethyl ether, carbonylation, deactivation, regeneration

摘要：

以水热合成的H-MOR分子筛催化剂，通过对二甲醚羰基化反应失活后催化剂进行再生，考察了不同再生气体、再生温度、O₂体积分数、烧炭升温速率等条件，烧炭后催化剂上二甲醚羰基化活性性能。TPO表征结果表明：反应后H-MOR分子筛上有两种不同性质的积炭。积炭催化剂在3%（体积） O₂/N₂气氛中，从室温以2℃·min^-1升温至320℃恒温一段时间，然后以相同速率升温至550℃进行烧炭，再生催化剂活性几乎完全恢复。NH₃-TPD和BET表征结果表明，再生催化剂活性得以恢复是因为优化了烧炭方案，分子筛表面积炭能够被烧除干净同时分子筛孔道不被破坏。

关键词: 分子筛, 催化剂, 二甲醚, 羰基化, 失活, 再生

CLC Number:

O643.3

LIU Yahua, LI Yang, WANG Ke, YE Qiuyun, LIU Peng. Regeneration of zeolite catalyst for dimethyl ether carbonylation[J]. CIESC Journal, 2017, 68(10): 3816-3822.

刘亚华, 李扬, 王科, 叶秋云, 刘芃. 二甲醚羰基化催化剂的烧炭再生[J]. 化工学报, 2017, 68(10): 3816-3822.

References 30

[1]	SUBRANMANI V, GANGWA S K. A review of recent literature to search for an efficient catalytic process for the conversion of syngas to ethanol[J]. Journal of the International Phonetic Association, 2008, 22(2):117-136.
[2]	黄守莹, 王悦, 吕静, 等. 合成气经二甲醚/乙酸甲酯制无水乙醇的研究进展[J]. 化工学报, 2016, 67(1):240-247. HUANG S Y, WANG Y, LÜ J, et al. Advances in direct synthesis of ethanol from syngas via dimethyl ether/methyl acetate[J]. CIESC Journal, 2016, 67(1):240-247.
[3]	JOHNSTON V J, CHEN L Y, KIMMICH B F. Direct and selective production of ethanol from acetic acid utilizing a platinum catalyst:US7863489[P]. 2013-08-01.
[4]	LI X G, SAN X G, ZHANG Y, et al. Direct synthesis of ethanol from dimethyl ether and syngas over combined h-mordenite and Cu/ZnO catalysts[J]. ChemSusChem, 2010, 3(10):1192-1199.
[5]	SONG A, FENG X J, XIE H, et al. Comparative analysis on two technologies of ethanol production from syngas[J]. Chinese Journal of Bioprocess Engineering, 2012, 10(5):72-78.
[6]	SAN X, ZHANG Y, SHEN W, et al. New synthesis method of ethanol from dimethyl ether with a synergic effect between the zeolite catalyst and metallic catalyst[J]. Energy & Fuels, 2009, 23(5):2843-2844.
[7]	PATRICIA C, ADITYA B, SUNLEY G J, et al. Selective carbonylation of dimethyl ether to methyl acetate catalyzed by acidic zeolites[J]. Angewandte Chemie, 2006, 45(10):1617-1620.
[8]	RASMUSSEN D B, CHRISTENSEN J M, STUDT F, et al. Reaction mechanism of dimethyl ether carbonylation to methyl acetate over mordenite-a combined DFT/experimental study[J]. Catalysis Science & Technology, 2017, 7(5):1141-1152.
[9]	WANG M, HUANG S, JING L, et al. Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether[J]. Chinese Journal of Catalysis, 2016, 37(9):1530-1537.
[10]	REULE A, SAWADA J, SEMAGINA N. Effect of selective 4-membered ring dealumination on mordenite-catalyzed dimethyl ether carbonylation[J]. Journal of Catalysis, 2017, 349:98-109.
[11]	ZHOU H, ZHU W, SHI L, et al. In situ DRIFT study of dimethyl ether carbonylation to methyl acetate on h-mordenite[J]. Journal of Molecular Catalysis A Chemical, 2016, 417:1-9.
[12]	CHIACA A, DIAZ U, FORNES, et al. Changing the hydroisomerization to hydrocracking ratio of long chain alkaned by varying the level of delamination in zeolitic(ITQ-6) materials[J]. Catalysis Today, 2009, 147(3/4):179-185.
[13]	·HE H, HUANG X, DITZEL E, et al. Coking on micrometer-and nanometer-size mordenite during dimethyl ether carbonyaltion to methyl acetate[J]. Chinese Journal Catalysis, 2013, 34(8):1496-1503.
[14]	倪友明, 朱文良, 刘红超, 等. 一种生产乙酸甲酯的方法:103896766[P]. 2014-07-02. NI Y M, ZHU W L, LIU H C, et al. A method for producing methyl acetate:103896766[P]. 2014-07-02.
[15]	LIU J, XUE H, HUANG X, et al. Stability enhancement of h-mordenite in dimethyl ether carbonylation to methyl acetate by pre-adsorption of pyridine[J]. Chinese Journal of Catalysis, 2010, 31(7):729-738.
[16]	VOLKOA G, PLYASOVA L M, SHKURATOVA L.Solid superacids for halide-free carbonylation of dimethyl ether to methyl acetate[J]. Studies in Surface Science and Catalysis, 2004, 147(4):403-408.
[17]	XUE H, HUANG X, DITZEL E, et al. Dimethyl ether carbonylation to methyl acetate over nanosized mordenites[J]. Industrial & Engineering Chemistry Research, 2013, 52(33):11510-11515.
[18]	刘欣萍, 洪爱珠, 颜桂炀, 等. 失活V-P/HZSM-5分子筛的再生及催化性能研究[J]. 福建师大学报(自然科学版), 2010, 26(1):69-72. LIU X P, HONG A Z, YAN G S, et al. Study on refreshing V-P/HZSM-5 zeolite catalyst and its catalystic activity[J]. Journal of Fujian Normal University, 2010, 26(1):69-72.
[19]	王晓婷. N2O一步氧化苯制苯酚Fe-ZSM-5分子筛催化剂失活与再生研究[D]. 北京:北京化工大学, 2008. WANG X T. Coke on Fe-ZSM-5 catalyst for one-step oxidation of benzene with N2O to phenol and its regeneration[D]. Beijing:Beijing University of Chemical Technology, 2008.
[20]	刘亚华. 丝光沸石分子筛制备及二甲醚羰基化反应性能研究[D]. 天津:天津大学, 2015. LIU Y H. Investigation of dimethyl ether carbonylation over synthesized h-mordenite zeolite[D]. Tianjin:Tianjin University, 2015.
[21]	杜明仙, 程昌瑞, 李源, 等. HDN催化剂氧化烧炭条件的考察[J]. 燃料化学学报, 1997, 25(6):528-532. DU M X, CHEN C R, LI Y, et al. Effects of oxidative carbon burnoff conditions on HDN catalyst[J]. Journal of Fuel Chemistry and Technology, 1997, 25(6):528-53
[22]	李经球, 杜鸿章, 孙承林, 等. 长链烷烃脱氢催化剂的烧炭研究[J]. 工业催化, 2005, 12(1):320-324. LI J Q, DU H Z, SUN C L, et al. Study on carbonation of long-chain alkane dehydrogenation catalyst[J]. Industrial Catalysis, 2005, 12(1):320-324.
[23]	张晓静, 刘雁, 陈永生. 负载型ZSM-5分子筛催化剂再生方法研究[J]. 工业催化, 2008, 16(6):23-26. ZHANG X J, LIU Y, CHEN Y S. Study on regeration of supported ZSM-5 zeolite catalysts[J]. Industrial Catalysis, 2008, 16(6):23-26.
[24]	米冠杰, 李建伟, 陈标华, 等. Fe-ZSM-5分子筛催化剂的再生烧炭[J]. 石油学报, 2010, 26(6):946-950. MI G J, LI J W, CHEN B H, et al. Coke burning during regeneration of Fe-ZSM-5 zeolite catalyst[J]. Acta Petrolei Sinica, 2010, 26(6):946-950.
[25]	金永明, 钟思青, 王菊, 等. 低碳烃芳构化催化剂烧炭再生动力学[J]. 化学反应工程与工艺, 2015, 31(2):177-182. JIN Y M, ZHONG S Q, WANG J, et al. Kinetics of coke combustion regeneration of light hydrocarbon aromatization catalyst[J]. Chemical Reaction Engineering and Technology, 2015, 31(2):177-182.
[26]	LIU Y H, ZHAO N, XIAN H, et al. Facilely synthesized h-mordenite nanosheet assembly for carbonylation of dimethyl ether[J]. ACS Applied Materials & Interfaces, 2015, 7(16):8398-8405.
[27]	LIU J L, XUE H F, HUANG X M, et al. Stability enhancement of h-mordenite in dimethyl ether carbonylation to methyl acetate by pre-adsorption of pyridine[J]. Chinese Journal of Catalysis, 2010, 31(7):729-738.
[28]	PINARD L, HAMIEH S, CANAFF C, et al. Growth mechanism of coke on HBEA zeolite during ethanol transformation[J]. Journal of Catalysis, 2013, 299(2):284-297.
[29]	BUSCA G. The surface acidity of solid oxides and its characterization by IR spectroscopic methods. An attempt at systematization[J]. Physical Chemistry Chemical Physics, 1999, 1(5):723-736.
[30]	POUR A, NAKAEI, HOUSAINDOKHT M R. Fischer-Tropsch synthesis on iron catalyst promoted with H-ZSM-5 zeolite:regeneration studies of catalyst[J]. Journal of Natural Gas Science Engineering, 2013, 14(9):49-54.