镍基芳烃加氢催化剂硫中毒的失活动力学

doi:10.3969/j.issn.0438-1157.2012.10.018

化工学报 ›› 2012, Vol. 63 ›› Issue (10): 3131-3137.DOI: 10.3969/j.issn.0438-1157.2012.10.018

• 催化、动力学与反应器 • 上一篇下一篇

镍基芳烃加氢催化剂硫中毒的失活动力学

郑进保¹, 赵愉生², 伊晓东¹, 李清彪¹, 陈秉辉¹, 方维平¹

1. 厦门大学化学化工学院, 福建厦门 361005;
2. 中国石油天然气股份有限公司石油化工研究院, 北京 100195

收稿日期:2012-02-27 修回日期:2012-07-04 出版日期:2012-10-05 发布日期:2012-10-05
通讯作者: 方维平
作者简介:方维平,郑进保(1982- ),男,博士,工程师。
基金资助:
国家重点基础研究发展计划项目(2010CB226903);国家自然科学基金项目(21073147,20973140)。

Deactivation kinetics of sulfur poisoning of nickel catalyst during ethylbenzene hydrogenation

ZHENG Jinbao¹, ZHAO Yusheng², YI Xiaodong¹, LI Qingbiao¹, CHEN Binghui¹, FANG Weiping¹

1. School of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China;
2. Research Institute of Petroleum and Petrochemicals, CNPC, Beijing 100195, China

Received:2012-02-27 Revised:2012-07-04 Online:2012-10-05 Published:2012-10-05
Supported by:
supported by the National Basic Research Program of China(2010CB226903)and the National Natural Science Foundation of China(21073147,20973140).

摘要/Abstract

摘要： 将某一时刻催化剂表面上活性中心数目与初始时刻活性中心数目之比定义为催化剂表观活性因子,并认为此活性因子包含在主催化反应速率系数的指前因子中。考虑活性中心在催化剂表面分布的不均匀性,在现有级数型失活动力学模型基础上,经推导得到表观活性因子的具体表达式及其极限式,该式在一般情况下为不可分。最后,结合之前报道的具有较高普适性的反应转化率方程式,得到催化反应转化率与运转时间的关系方程,并以Ni-B/SiO₂催化剂在噻吩存在下芳烃加氢反应为例加以验证。结果表明,所提出的失活动力学表达式可以较好地描述镍基催化剂硫中毒的行为,方程参量具有物理意义,方程可以较精确地拟合实验数据。

关键词: 中毒, 失活, 反应动力学, 芳烃加氢, 燃料油

Abstract: Based on the current power-kinetic model for catalyst deactivation,the apparent activity factor usually in a non-separable form was derived by taking the non-uniform distribution of catalyst active sites into account.Combined with the relatively comprehensive conversion relationship reported previously,a model correlating conversion with reaction time was proposed.Its validity was verified by fitting experimental data from ethylbenzene hydrogenation with Ni-B/SiO₂ catalyst in the presence of thiophene.The results showed that the model with predictive capability could describe the nickel catalyst deactivation behavior,and the model parameters were endowed with physical meaning.

Key words: poisoning, deactivation, reaction kinetics, aromatics hydrogenation, fuel oil

中图分类号:

TQ426
O643.3

郑进保, 赵愉生, 伊晓东, 李清彪, 陈秉辉, 方维平. 镍基芳烃加氢催化剂硫中毒的失活动力学[J]. 化工学报, 2012, 63(10): 3131-3137.

ZHENG Jinbao, ZHAO Yusheng, YI Xiaodong, LI Qingbiao, CHEN Binghui, FANG Weiping. Deactivation kinetics of sulfur poisoning of nickel catalyst during ethylbenzene hydrogenation[J]. CIESC Journal, 2012, 63(10): 3131-3137.

参考文献 26

[1]	Pawelec B,Castano P,Arandes J M,Bilbao J,Thomas S,Pena M A,Fierro J L.Factors influencing the thioresistance of nickel catalysts in aromatics hydrogenation[J].Appl.Catal.A:Gen.,2007,317:20-33
[2]	Stanislaus A,Cooper B H.Aromatic hydrogenation catalysis:a review[J].Catal.Rev.Sci.Eng.,1994,36:75-123
[3]	Song C S.An overview of new approaches to deep desulfurization for ultra-clean gasoline,diesel fuel and jet fuel[J].Catal.Today,2003,86(1/2/3/4):211-263
[4]	Liu Dapeng(刘大鹏),Li Yongdan(李永丹).Recent advances in sulfur resistant aromatic hydrogenation catalysts[J].Prog.Chem.(化学进展),2004,16(6):891-899
[5]	Cooper B H,Donnis B B L.Aromatic saturation of distillates:an overview[J].Appl.Catal.A:Gen.,1996,137:203-223
[6]	Porto L M,Butt J B.Deactivation kinetic parameters of nickel sulfur poisoning during benzene hydrogenation[J].Ind.Eng.Chem.Res.,2002,41:5420-5426
[7]	Seoane X L,Arcoya A,Gonzalez J A,Travieso N.Hydrogenation of ethylbenzene over a nickel/mordenite catalyst:catalytic decay by thiophene poisoning[J].Ind.Eng.Chem.Res.,1989,28:260-264
[8]	Aguinaga A,Montes M,de la Cal J C,Asua J M.Kinetics of the poisoning by thiophene of supported nickel catalysts[J].Ind.Eng.Chem.Res.,1992,31:155-163
[9]	Zrncevic S,Gomzi Z,Kotur E.Thiophene poisoning of Ni-SiO2-A12O3 in benzene hydrogenation:deactivation kinetics[J].Ind.Eng.Chem.Res.,1990,29:774-777
[10]	Bartholomew C H.Catalyst deactivation[J].Chem.Eng.,1984,91(23):96-122
[11]	Butt J B,Wachter C K,Billimoria R M.On the separability of catalytic deactivation kinetics[J].Chem.Eng.Sci.,1978,33(10):1321-1329
[12]	Tan Yanan(谭亚南),Li Feng(李枫),Jia Lishan(贾立山),Yi Xiaodong(伊晓东),Wang Yuemin(王跃敏),Fang Weiping(方维平),Wan Huilin(万惠霖).Reactor model with cross-flow for aromatics catalytic hydrogenation[J].Journal of Chemical Industry and Engineering(China)(化工学报),2008,59(12):3061-3066
[13]	Liu Zhaotie(刘昭铁),Zhou Jinglai(周敬来),Zhang Bijiang(张碧江).Study on deactivation model and mechanism of catalysts[J].J.Petro.Uni.Sino.(石油化工高等学校学报),1994,7(3):24-30
[14]	Liu Ying(刘颖),Han Chongren(韩崇仁),Fang Weiping(方维平),Wan Huilin(万惠霖).Study on reaction kinetics of coke deposition and deactivation of catalysts[J].Chin.J.Catal.(催化学报),2004,25(2):107-109
[15]	Liu Dazhuang(刘大壮),Zhang Li(张丽),Guo Xinwen(郭新闻),Wang Xiangsheng(王祥生).Experiment design of GPLE deactivation kinetics model[J].J.Zhengzhou Uni.Technol.(郑州工业大学学报),1999,20(1):4-6
[16]	Tian Liang(田亮),Jiang Da(蒋达),Qian Feng(钱锋).Simulation and optimization of acetylene converter with decreasing catalyst activity[J].CIESC Journal(化工学报),2012,63(1):185-192
[17]	Zhang Guotai(张国泰),Zhi Yuzhen(支玉珍).Catalyst deactivation and its reaction kinetic[J].Chem.React.Eng.Tech.(化学反应工程与工艺),1985(4):97-106
[18]	Castano P,van Herk D,Kreutzer M T,Moulijn J A,Makkee M.Kinetic and deactivation modelling of biphenyl liquid-phase hydrogenation over bimetallic Pt-Pd catalyst[J].Appl.Catal.B:Environ.,2009,88:213-223
[19]	Erena J,Sierra I,Aguayo A T,Ateka A,Olazar M,Bilbao J.Kinetic modelling of dimethyl ether synthesis from(H2 + CO2)by considering catalyst deactivation[J].Chem.Eng.J.,2011,174:660-667
[20]	Weng Yanbo(翁延博),Jiang Lijing(蒋立敬),Geng Xinguo(耿新国).Study on kinetics model for residue hydrotreating catalyst life[J].Petro.Refin.Eng.(炼油技术与工程),2012,40(3):42-44
[21]	Weng Yanbo(翁延博),Jiang Lijing(蒋立敬),Geng Xinguo(耿新国).Kinetics and deactivation model of residue hydrotreating reaction[J].Acta Petrolei Sinica:Petro.Process.Sec.(石油学报:石油加工),2010(S1):37-40
[22]	Zhang Lichang(张立昌),Xu Xiankun(许先焜),Weng Huixin(翁惠新).Hydrodemetallization kinetic model for Maoming's residue hydrodesulfurization treatment unit[J].J.Chem.Eng.Chin.Uni.,(高校化学工程学报),2006,20(2):227-232
[23]	Levenspiel O.Chemical Reaction Engineering[M].New York:Wiley,1972:538
[24]	Weng H S,Eigenberger G,Butt J B.Catalyst poisoning and fixed bed reactor dynamic[J].Chem.Eng.Sci.,1975, 30:1341-1351
[25]	Zheng J B,Xia Z Q,Li J J,Lai W K,Yi X D,Chen B H,Fang W P,Wan H L.Promoting effect of boron with high loading on Ni-based catalyst for hydrogenation of thiophene-containing ethylbenzene[J].Catal.Commun.,2012,21:18-21
[26]	Li Qiaoling(李巧灵),Zhang Yuanhua(张元华),Chen Shiping(陈世萍),Fang Weiping(方维平),Yang Yiquan(杨意泉).Development of a novel conversion equation as a function of catalytic reaction conditions in tubular reactors[J].Chin.J.Catal.(催化学报),2011,32(3):446-450

镍基芳烃加氢催化剂硫中毒的失活动力学

Deactivation kinetics of sulfur poisoning of nickel catalyst during ethylbenzene hydrogenation

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