Catalysis and Simulation of SBA-15 Zeolite Supported p-Toluenesulfonic Acid for the Synthesis of Dicumyl Peroxide

doi:10.7503/cjcu20240067

Abstract

Abstract:

SBA-15 zeolite suppored p-toluenesulfonic acid（TsOH/SBA-15） was prepared using the impregnation method. The catalytic activity of TsOH/SBA-15 in synthesis of dicumyl peroxide（DCP） from α-methylstyrene（α-MS） reacted with isopropylbenzene hydroperoxide（CHP） was evaluated. Under the conditions of m（TsOH/SBA-15）/ m（CHP）=0.15%， n（α-MS）/n（CHP）=2.0， 44 ℃ and 2.5 h， the yield of DCP was 62.1%. Simulation analysis suggested that the reaction process follows two mechanisms of asynchronous synergistic reaction and step-by-step reaction. α-MS， CHP， and TsOH undergo a single transition state in the asynchronous synergistic reaction process， while there are two transition states and one intermediate in the step-by-step reaction， both requiring H⁺ proton transformation. The reaction energy barrier in the asynchronous synergistic reaction was calculated to be 121.8 kJ/mol at 44 ℃， while the reaction energy barriers were 74.1 and 78.3 kJ/mol in the two transition states in the step-by-step reaction， respectively.

Key words: p-Toluenesulfonic acid, SBA-15 zeolite, Dicumyl peroxide, Isopropylbenzene hydroperoxide, Reaction energy barrier

CLC Number:

O643.36

TrendMD:

ZHANG Xiaolong, ZHANG Yicheng, LI Qingchao, ZHA Fei, CHANG Yue, TANG Xiaohua. Catalysis and Simulation of SBA-15 Zeolite Supported p-Toluenesulfonic Acid for the Synthesis of Dicumyl Peroxide[J]. Chem. J. Chinese Universities, 2024, 45(6): 20240067.

Figures/Tables 7

References 22

1	Wu S. H.， Shyu M. L.， Yet⁃Pole I.， Chi J. H.， Shu C. M.， J. Loss Prevent Proc.， 2009， 22（6）， 721—727
2	Somma I. D.， Marotta R.， Andreozzi R.， Caprio V.， J. Hazard. Mater.， 2011， 187（1—3）， 157—163
3	Zhang Y. C.， Zha F.， Tang X. H.， Chang Y.， Tian H. F.， Guo X. J.， Chin. J. Appl. Chem.， 2023， 40（6）， 769—788
	张毅城，查飞，唐小华，常玥，田海锋，郭效军. 应用化学， 2023， 40（6）， 769—788
4	Philippe M.， Serge H.， Use of a Sulfonic Acid and Mineral Acid as a Catalyst in the Preparation of Organic di⁃Tertiary Peroxides from Tertiary Alcohols and Tertiary Hydroperoxides， WO 2015018996A1， 2015⁃02⁃12
5	Gillner D.， Zawadiak J.， Mazurkiewicz R.， Kurczewska J.， Schroeder G.， Orlinska B.， Monatsh. Chem.， 2010， 141， 143—147
6	Konopińska A.， Orlińska B.， Gillner D.， Modern. Chem.， 2017， 5（2）， 29—34
7	Ren D. Z.， Yu F.， Chang S. Y.， Yang D. X.， Ma L. J.， Zhao Y. K.， Precious Metals， 2022， 43（3）， 75—81， 88
	任德志，于飞，常仕英，杨冬霞，马丽江，赵云昆. 贵金属， 2022， 43（3）， 75—81， 88
8	Feng Y. C.， Yu Q. J.， Yi H. H.， Tang X. L.， Huang Y. H.， Zhang Y. Y.， Zhuang R. J.， Materials Reports， 2020， 34（17）， 17089—17098
	冯勇超，于庆君，易红宏，唐晓龙，黄永海，张媛媛，庄瑞杰. 材料导报， 2020， 34（17）， 17089—17098
9	Hui F.， Catalytic Synthesis of Methyl Ethyl Ketone Peroxide by Zirconium（titanium）⁃modified HZSM⁃5 Molecular Sieves and UiO⁃66， Northwest Normal University， Lanzhou， 2020
	惠菲. 锆（钛）改性HZSM-5分子筛和UiO⁃66催化合成过氧化甲乙酮，兰州：西北师范大学， 2020
10	Liu P. L.， Liu H. J.， Fu Y. F.， Luo H. A.， Yang H.， Wang C.， a Preparation Method of Cyclohexanone Peroxide， CN 107266344B， 2021⁃09⁃14
	刘平乐，刘华杰，符雅芬，罗和安，阳海，王聪. 一种过氧化环己酮的制备方法， CN 107266344B， 2021⁃09⁃14
11	Huang Y. M.， Chen T. J.， Zhai Z. Q.， Xue Y. Y.， Wang G. Q.， Kong X. L.， Synthesis of Alkyl Peroxycarboxylates Using Titanium⁃silicon Molecular Sieve Composite Catalysts， CN 112624948A， 2021⁃04⁃09
	黄燕民，陈唐建，翟志强，薛育宴，王跟泉，孔祥伦. 利用钛硅分子筛复合催化剂合成过氧化羧酸烷基酯的方法， CN 112624948A， 2021⁃04⁃09
12	Lin M.， Liu Y. D.， Zhu B.， Zheng J. Y.， Ru Y. C.， Jiao Y. D.， a Preparation Method of Tert⁃butyl Hydroperoxide， CN 1699339， 2006⁃11⁃29
	林民，刘郁东，朱斌，郑金玉，汝迎春，焦永东. 一种叔丁基过氧化氢的制备方法， CN 1699339， 2006⁃11⁃29
13	Subbaramaiah V.， Srivastava V.， Mall I.， Ind. Eng. Chem. Res.， 2013， 52（26）， 9021—9029
14	Zhai Q. Z.， Cai J. Y.， Yu H.， Qin L.， J. Chin. Ceramic Soc.， 2006， 34（3）， 385—388
	翟庆洲，蔡建岩，于辉，秦亮. 硅酸盐学报， 2006， 34（3）， 385—388
15	Tian Z. M.， Deng Q. G.， Sun H.， Zhao D. F.， Appl. Chem. Ind.， 2007， 36（8）， 785—788
	田志茗，邓启刚，孙慧，赵德丰. 应用化工， 2007， 36（8）， 785—788
16	Rao P.， Wolfson A.， Kababya S.， Vega S.， Landau M.， J. Catal.， 2005， 232（1）， 210—225
17	Ji G. J.， Zhang Y. B.， Fu N. N.， Tang L.， Liu P.， Shen J.， J. Fuel Chem. Technol.， 2015， 43（4）， 449—455
	纪桂杰，张耀兵，付宁宁，唐磊，刘鹏，沈健. 燃料化学学报， 2015， 43（4）， 449—455
18	Cao Y.， Wang J.， Kang M.， Zhu Y.， J. Mol. Catal. A： Chem.， 2014， 381， 46—53
19	Dong B.， Zhang B.， Wu H.， Li S.， Zhang K.， Zhang. X.， Micropor. Mesopor. Mater.， 2013， 176， 186—193
20	Li B.， Xu Z.， Jing F.， Luo S.， Chu W.， Appl. Catal. A： Gen.， 2017， 533， 17—27
21	Kholdeeva O.， Maksimchuk N.， Catalysts， 2021， 11（2）， 283
22	Conley M. L.， Mohammed F. S.， Winslow C.， Eldridge H.， Cogen J.， Chaudhary B.， Pollet P.， Liotta C.， Ind. Eng. Chem. Res.， 2016， 55（20）， 5865—5873

Catalyst	Conversion（%）	Yield（%）	Catalyst	Conversion（%）	Yield（%）
TsOH	82.1	48.3	TsOH/MCM⁃41	98.3	51.5
SBA⁃15	6.8	6.5	TsOH/SBA⁃15	98.7	47.4
MCM⁃41	6.5	8.9

Catalyst	Conversion（%）	Yield（%）	Catalyst	Conversion（%）	Yield（%）
TsOH	82.1	48.3	TsOH/MCM⁃41	98.3	51.5
SBA⁃15	6.8	6.5	TsOH/SBA⁃15	98.7	47.4
MCM⁃41	6.5	8.9

[1]	GAO Yongping, LIU Bai, KANG Jianing, LYU Jieqiong, YU Zeguang, ZHANG Zhihui, GAO Wenxiu. Nitrogen-doped Carbon Material MG-T Heterogeneous Catalyzed Hydrogenation of Nitrobenzene to Aniline [J]. Chem. J. Chinese Universities, 2024, 45(5): 20240040.
[2]	ZHAO Yutong, WANG Shikai, ZHAO Fuping, CHEN Zhihe, ZHAO Lijie, ZHANG Dafeng, GE Bo, PU Xipeng. Construction and Visible Photocatalytic Hydrogen Performance of Hydrangea-like ZnIn₂S₄/CoWO₄ S-scheme Heterojunction [J]. Chem. J. Chinese Universities, 2024, 45(5): 20240055.
[3]	CHEN Hao, CHEN Gui, SONG Dandan, ZENG Yanhong, LIU Wenhu, ZHANG Ming. High-performance Cu-ZnO@SiO₂ Nano-catalyst for CO₂ Hydrogenation to Methanol [J]. Chem. J. Chinese Universities, 2023, 44(11): 20230268.
[4]	WANG Yazhi, JIA Xianzhi, ZHANG Honggang, LIU Lu, ZHAO Binran. 5Ni-5La/SiO₂ Catalysts Prepared by Dielectric Barrier Discharge Plasma Applying in the Dry Reforming of Methane [J]. Chem. J. Chinese Universities, 2023, 44(2): 20220503.
[5]	KUANG Huayi, CHEN Chen. Synthesis Methods and Electrocatalytic Performance of Noble-metal Nanoframes Catalysts [J]. Chem. J. Chinese Universities, 2023, 44(1): 20220586.
[6]	WANG Zumin, MENG Cheng, YU Ranbo. Doping Regulation in Transition Metal Phosphides for Hydrogen Evolution Catalysts [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220544.
[7]	ZHAO Wanjun, LI Xiao, Dang Hui, WANG Yongzhao, ZHAO Yongxiang. Preparation of Supported Pd-Cu Catalyst and Its Preferential Oxidation of CO Under Hydrogen-rich Atmosphere [J]. Chem. J. Chinese Universities, 2022, 43(3): 20210754.
[8]	ZHANG Xiang, XIE Xulan, XIONG Likun, PENG Yang. Urchin-like Gold Nanoneedle for Efficient Electrocatalytic CO₂ Reduction [J]. Chem. J. Chinese Universities, 2021, 42(9): 2824.
[9]	JI Xiaohao, WANG Zumin, CHEN Xiaoyu, YU Ranbo. Overview of Transition Metal Phosphide Catalysts and Hydrogen Production by Electrolyzed Water [J]. Chem. J. Chinese Universities, 2021, 42(5): 1377.
[10]	SU Gaoming, SHEN Ruichen, TAN Jie, YUAN Quan. Progress on the Application of Long Persistent Phosphors in Photocatalytic System [J]. Chem. J. Chinese Universities, 2020, 41(11): 2404.
[11]	WU Hao, WANG Changzhen, QIU Yuan, TIAN Yani, ZHAO Yongxiang. Effect of Steric Confinement Dimension on Metal Site Anti-carbon Deposition Ability of Ni-SiO₂ Catalysts in CH₄-CO₂ Reforming [J]. Chem. J. Chinese Universities, 2020, 41(11): 2488.
[12]	LI Xiao,XING Lisha,ZHAO Wanjun,WANG Yongzhao,ZHAO Yongxiang. Preparation and Characterization of Pd-Cu/hydroxyapatite Catalyst and Its Catalytic Performance for Room-temperature CO Oxidation in Humid Circumstances^† [J]. Chem. J. Chinese Universities, 2020, 41(7): 1600.
[13]	HAO Yan, YANG Hua, WANG Xiang, LI Qingyang, ZHAO Pan, TANG Qinghu, SONG Shili, XI Guoxi. Palladium-based Nanocatalysts Supported on Polybenzoxazine for Aromatic Alcohol Oxidation ^† [J]. Chem. J. Chinese Universities, 2020, 41(4): 757.
[14]	MENG Qingnan, WANG Kai, TANG Yufei, ZHAO Kang, XIANG Siyuan, ZHANG Kai, ZHAO Lang. Preparation of Gold Nanoparticles Loaded Hollow Silica Spheres and Their Catalytic Performance^† [J]. Chem. J. Chinese Universities, 2017, 38(3): 503.
[15]	WANG Huichun, WANG Fachun, LI Baolin. Preparation of Cyclodextrin-based Mesoporous Carbon and Its Catalytic Performance^† [J]. Chem. J. Chinese Universities, 2016, 37(11): 2076.