Alkylation Desulfurization of FCC Gasoline over Brönsted-Lewis Organic-inorganic Heteropoly Acid Catalyst†

doi:10.7503/cjcu20160533

Abstract

Abstract:

A series of Brönsted-Lewis organic-inorganic heteropoly acids was synthesized and used for catalyzing alkylation desulfurization of model fluid catalytic cracking(FCC) gasoline. Among these prepared Brönsted-Lewis organic-inorganic heteropoly acids, Sm_0.33[MIM-PS]HPW₁₂O₄₀ has the highest acid strength and exhibits the best catalytic activity for the alkylation of three thiophenic sulfides including thiophene(T), 2-methyl thiophene(2-MT) and 3-methyl thiophene(3-MT) in model FCC gasolines. The effects of the dosage of the catalyst, reaction temperature and reaction time on the conversions of three thiophenic sulfides catalyzed by Sm_0.33[MIM-PS]HPW₁₂O₄₀ were investigated. The selected optimal conditions as follows: the mass ratio of the catalyst to model FCC gasoline 1:50, reaction temperature 125 ℃ and reaction time 1 h. Under the optimal conditions, T, 2-MT and 3-MT all can be nearly completely transformed. The recyclability of the catalyst Sm_0.33[ MIM-PS]HPW₁₂O₄₀ was investigated. The results show the catalyst exhibits very excellent recyclability. Under the above selected reaction conditions, the catalytic activity of Sm_0.33[MIM-PS]HPW₁₂O₄₀ for the alkylation of three thiophenic sulfides nearly remains unchanged during 12 recycles.

Key words: Alkylation desulfurization, FCC gasoline, Thiophenic sulfide, Brönsted-Lewis heteropoly acid

CLC Number:

O643
O621

TrendMD:

YU Fengli, WANG Qingyu, LI Guixiao, YUAN Bing, XIE Congxia, YU Shitao. Alkylation Desulfurization of FCC Gasoline over Brönsted-Lewis Organic-inorganic Heteropoly Acid Catalyst^†[J]. Chem. J. Chinese Universities, 2017, 38(1): 72.

Figures/Tables 6

References 34

[1]	Maedeh E., Hossein F., J. Fuel Chem. Technol., 2015, 43(2), 195—201
[2]	Zhu W. S., Li H. M., Jiang X., Yan Y. S., Lu J. D., Xia J. X., Energy Fuels,2007, 21(5), 2514—2516
[3]	Obame H., Toussaint G., Laurenti D., Tayakout M., Geantet C., Top Catal., 2013, 56(18), 1731—1739
[4]	Stanislaus A., Marafi A., Rana R. S., Catal. Today,2010, 153(1), 1—68
[5]	Shi R. H., Li Y. H., Wang R., Guo B. S., Catal. Lett., 2010, 139(3), 114—122
[6]	Jiang W., Zhu W. S., Li H. P., Wang X., Yin S., Chang Y. H., Li H. M., Fuel,2015, 140, 590—596
[7]	Jiang B., Yang H. W., Zhang L. H., Zhang R. Y., Sun Y. L., Huang Y., Chem. Eng. J., 2016, 283, 89—96
[8]	Song H., Yu Q., Xu X. W., Song H. L., Jiang N., Li F., Chen Y. G., Chem. J. Chinese Universities,2016, 37(8), 1528—1534
	(宋华, 于祺, 徐晓伟, 宋华林, 姜楠, 李锋, 陈彦广. 高等学校化学学报, 2016, 37(8), 1528—1534)
[9]	Zhao T. Q., Li W. J., Wang H. Y., Meng F. Y., Chem. Res. Chinese Universities,2014, 30(2), 200—204
[10]	Cecilia D. W. M., Zulhaziman M. S. M., Ibrahim B. M. M., Separation Science and Technology,2015, 50(2), 159—163
[11]	Zhang Z. K., Jiang H., Liu S. L., Wang Q. X., Xun L. Y., Chin. J. Catal., 2006, 27(4), 309—313
	(张泽凯, 蒋晖, 刘盛林, 王清遐, 徐龙伢. 催化学报, 2006, 27(4), 309—313)
[12]	Zhao Y. Z., Li Y. H., Li L. F., Zhang L. P., Chin. J. Mol. Catal., 2008, 22(1), 17—21
	(赵玉芝, 李永红, 李兰芳, 张丽萍. 分子催化, 2008, 22(1), 17—21)
[13]	Li C. P., Li D., Zou S. S., Li Z., Yin J. G., Wang A. L., Cui Y. N., Yao Z. L., Zhao Q., Green Chem., 2013, 15, 2793—2799
[14]	Sébastien B., Bruce P., Patrick D., Jérôme M., Emmanuel M., Tetrahedron Letters,2015, 56(13), 1682—1686
[15]	Sentorun S. C., Saha S. K., Ma X. L., Song C. S., Appl. Catal., B,2011, 101(4), 718—726
[16]	Song H., Wan X., Dai M., Zhang J. J., Li F., Song H. L., Fuel Process Technology,2013, 116, 52—62
[17]	Silva T. P., Paixao S. M., Teixeira A. V., Roseiro J. C., Alves L., J. Chem. Technol. Biotechnol., 2013, 88(5), 919—923
[18]	Babich I. V., Moulijn J. A., Fuel,2003, 82(6), 607—631
[19]	Dupuy B., Laforge S., Bachmann C., Magnoux P., Richard F., J. Mol. Catal. A: Chem., 2012, 363, 273—282
[20]	Bellière V., Geantet C., Vrinat M., Taârit Y. B., Yoshimura Y., Energy Fuels,2004, 18, 1806—1813
[21]	Zhang Z., Liu D., Zhu X., Yu H., Liu S., Xu L., J. Nat. Gas Chem., 2008, 17(1), 45—50
[22]	Wang R., Wan J. B., Li Y. H., Sun H. W., Fuel,2015, 143, 504—511
[23]	Zeng D. L., Zhang Q., Chen S. Y., Liu S. L., Chen Y., Wang G. H., Materials Research Bulletin,2015, 72, 276—279
[24]	Richard F., Celerier S., Vilette M., Comparot J. D., Montouillout V., Applied Catalysis B,2014, 152, 241—249
[25]	Wei X. L., Lu X. H., Ma X. T., Peng C., Jiang H. Z., Zhou D., Xia Q. H., Green Chem., 2011, 13, 2619—2637
[26]	Sharma R. K., Pandey A., Gulati S., Polyhedron,2012, 45(1), 86—93
[27]	Rafiee E., Eavani S., J. Mol. Catal. A: Chem., 2013, 380, 18—27
[28]	Zhang C., Cai J. R., Duan Y. Q., Xu L., Fang G. Z., Wang S., Chem. Res. Chinese Universities,2014, 30(3), 374—378
[29]	Yu F. L., Tang H. B., Liu C. Y., Xie C. X., Yu S. T., Acta Chim. Sinica,2014, 72(11), 1152—1156
	(于凤丽, 唐会宝, 柳春玉, 解从霞, 于世涛. 化学学报, 2014, 72(11), 1152—1156)
[30]	Yu F. L., Wang Y. Y., Liu C. Y., Xie C. X., Yu S. T., Chem. Eng. J., 2014, 255, 372—376
[31]	Yu F. L., Liu C. Y., Xie P. H., Yuan B., Xie C. X., Yu S. T., RSC Advances,2015, 5, 85540—85546
[32]	Zhang X., Mao D., Leng Y., Zhou Y., Wang J., Catal. Lett., 2013, 143, 193—199
[33]	Yuan B., Xie C. X., Yu F. L., Yang X. Y., Yu S. T., Zhang J. L., Chen X. B., Springer Plus,2016, 5, 460—464
[34]	Vazquez P., Pizzio L., Caceres C., Blanco M., Thomas H., Alesso E., Finkielsztein L., Lantano B., Moltrasio G., Aguirre J., J. Mol. Catal. A: Chem., 2000, 161(2), 223—232

Catalyst	Acid strength/ mV	Conversion(%)
Catalyst	Acid strength/ mV	T	2-MT	3-MT
[MIM-PS]H₂PW₁₂O₄₀	715	100	100	100
Al_0.33[MIM-PS]HPW₁₂O₄₀	584	93.4	97.6	95.1
Fe_0.33[MIM-PS]HPW₁₂O₄₀	551	87.8	95.8	93.3
Zn_0.5[MIM-PS]HPW₁₂O₄₀	522	89.8	95.6	92.4
Sm_0.33[MIM-PS]HPW₁₂O₄₀	605	99.7	99.9	99.7
Sm_0.66[MIM-PS]PW₁₂O₄₀	452	48.5	51.8	48.4
Cu_0.5[MIM-PS]HPW₁₂O₄₀	504	86.3	92.6	90.8
Cr_0.33[MIM-PS]HPW₁₂O₄₀	510	81.4	88.2	85.5
Zr_0.5[MIM-PS]HPW₁₂O₄₀	514	93.6	96.4	94.2

Catalyst	Acid strength/ mV	Conversion(%)
Catalyst	Acid strength/ mV	T	2-MT	3-MT
[MIM-PS]H₂PW₁₂O₄₀	715	100	100	100
Al_0.33[MIM-PS]HPW₁₂O₄₀	584	93.4	97.6	95.1
Fe_0.33[MIM-PS]HPW₁₂O₄₀	551	87.8	95.8	93.3
Zn_0.5[MIM-PS]HPW₁₂O₄₀	522	89.8	95.6	92.4
Sm_0.33[MIM-PS]HPW₁₂O₄₀	605	99.7	99.9	99.7
Sm_0.66[MIM-PS]PW₁₂O₄₀	452	48.5	51.8	48.4
Cu_0.5[MIM-PS]HPW₁₂O₄₀	504	86.3	92.6	90.8
Cr_0.33[MIM-PS]HPW₁₂O₄₀	510	81.4	88.2	85.5
Zr_0.5[MIM-PS]HPW₁₂O₄₀	514	93.6	96.4	94.2