甲苯液相氧化合成苯甲醛的研究

摘要以甲苯为底物，醋酸为溶剂，乙酸钴为催化剂，溴化钠为助催化剂，在双氧水液相氧化催化作用下生成苯甲醛。实验考察了催化剂种类、助催化剂、双氧水浓度、氧化剂用量、催化剂用量、反应时间和温度对氧化反应的影响。结果表明：n（甲苯）∶n（过氧化氢）=1∶3，n（乙酸钴）∶n（甲苯）=1∶50，n（溴化钠）∶n（甲苯）=1∶30，w（过氧化氢）为25%，θ=105℃，t=20 min时，甲苯转化率达49.2%，苯甲醛选择性达70.4%。与传统间歇工艺相比，甲苯液相氧化法通过Co²⁺与过氧乙酸协同催化效应，扩大工艺条件选择区间，实现对氧化反应过程的有效控制。

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	刘建武
	严生虎
	张跃

关键词：甲苯乙酸钴液相氧化苯甲醛

Abstract： Benzaldehyde was synthesized by liquid phase oxidation of hydrogen peroxide in a solution consisting of acetic acid, with toluene as substrate, cobalt acetate and sodium bromide as the catalyst and co-catalyst respectively. The effects of the kinds of catalysts, co-catalysts, the concentration of hydrogen peroxide, oxidant, catalyst, reaction time and temperature on oxidation were investigated. The results showed that under the conditions of n (toluene):n (hydrogen peroxide)=1:3, n(cobalt acetate):n (toluene)=1:50, n (sodium bromide):n (toluene)=1:30, the concentration of hydrogen peroxide of 25%, at temperature 105℃, time for 20 min, the conversion of toluene reached 49.2%, and the selectivity of benzaldehyde reached 70.4%. Compared with the traditional batch reaction process, the liquid-phase oxidation of toluene was carried out by concerted catalytic effect of Co²⁺ and peracetic acid, which can expand the selection range of process conditions and realize effective control on the oxidation reaction process.

Keywords： toluene； cobalt acetate； liquid phase oxidation； benzaldehyde

Received 2020-05-01;

Fund:江苏省产学研前瞻性联合研究项目（BY2014037-19）。

Corresponding Authors: 刘建武,E-mail liujianwu@cczu.edu.cn。 Email: liujianwu@cczu.edu.cn

About author: 刘建武(1973-),男,博士,高级工程师,硕士生导师,主要从事化学工程及工艺优化方面研究。

引用本文:

刘建武, 严生虎, 张跃.甲苯液相氧化合成苯甲醛的研究[J]. 化学工业与工程, 2020,37(6): 48-53,71

Liu Jianwu, Yan Shenghu, Zhang Yue.Synthesis of Benzaldehyde by Liquid Phase Oxidation of Toluene[J]. Chemcial Industry and Engineering, 2020,37(6): 48-53,71

[1] Kantam M L, Sreekanth P, Rao K, et al. An improved process for selective liquid-phase air oxidation of toluene[J]. Catalysis Letters, 2002, 81(3):223-232
[2] Xu W, Su W. Improved sommelet reaction catalysed by lanthanum triflate[J]. Journal of Chemical Research, 2014, 38(12):710-714
[3] 张跃, 张勇超, 严生虎, 等. 微通道反应器中甲苯连续液相氧化工艺研究[J]. 现代化工, 2018, 38(5):85-89 Zhang Yue, Zhang Yongchao, Yan Shenghu, et al. Study on continuous liquid phase oxidation of toluene in microchannel reactor[J]. Modern Chemical Industry, 2018, 38(5):85-89(in Chinese)
[4] Adam W, Hajra S, Herderich M, et al. A highly chemoselective oxidation of alcohols to carbonyl products with iodosobenzene diacetate mediated by chromium(Ⅲ)(salen) complexes:Synthetic and mechanistic aspects[J]. Organic Letters, 2000, 2(18):2773-2776
[5] He A, Zhang J, Zheng W, et al. Rapid oxidation of alcohols to aldehydes and ketones with chromium trioxide catalyzed by kieselguhr under solvent-free conditions[J]. Research on Chemical Intermediates, 2013, 39(3):1015-1020
[6] 江勤. 苯甲醇氧化脱氢制苯甲醛绿色催化工艺研究[D]. 杭州:浙江大学, 2018 Jiang Qin. Study on green catalytic process for oxidative dehydrogenation of benzyl alcohol to benzaldehyde[D]. Hangzhou:Zhejiang University, 2018(in Chinese)
[7] Lei M, Hu R, Wang Y. Mild and selective oxidation of alcohols to aldehydes and ketones using NaIO₄/TEMPO/NaBr system under acidic conditions[J]. Tetrahedron, 2006, 62(38):8928-8932
[8] Mo H. Pyridinium chlorochromate catalyzed oxidation of alcohols to aldehydes and ketones with periodic acid[J]. Tetrahedron Letters, 2005, 46(10):1651-1653
[9] 曹怀宝.以Saccharin/TEMPO高效催化氧化醇制备醛酮的研究[J].化学研究与应用,2019,31(9):1702-1706 Cao Huaibao. Study on preparation of aldehydes and ketones by high efficient catalytic oxidation of alcohols with saccharin/tempo[J]. Chemical Research and Application, 2019, 31(9):1702-1706(in Chinese)
[10] Parmeggiani C, Cardona F. Transition metal based catalysts in the aerobic oxidation of alcohols[J]. Green Chem, 2012, 14:547-564
[11] Bulushev D A, Kiwi-Minsker L, Zaikovskii V I, et al. Formation of active sites for selective toluene oxidation during catalyst synthesis via solid-state reaction of V₂O₅ with TiO₂[J]. Journal of Catalysis, 2000, 193(1):145-153
[12] Hao G, Guang W, Quan Y. Gas phase partial oxidation of toluene over modified V₂O₅/TiO₂ catalysts in a microreactor[J]. Chem Eng J, 2007, 127:39-46
[13] Bulushev D A, Rainone F, Kiwi-Minsker L. Partial oxidation of toluene to benzaldehyde and benzoic acid over model vanadia/titania catalysts:Role of vanadia species[J]. Catalysis Today, 2004, 96(4):195-203
[14] Bottino A, Capannelli G, Comite A, et al. Vapour phase oxidation of toluene in V/Al₂O₃-TiO₂ catalytic reactors[J]. Catalysis Today, 2005, 99(1/2):171-177
[15] Lu B, Cai N, Sun J, et al. Solvent-Free oxidation of toluene in an ionic liquid with H₂O₂ as oxidant[J]. Chemical Engineering Journal, 2013, 225:266-270
[16] Williams R M, Medlin J W. Benzyl alcohol oxidation on Pd(111):Aromatic binding effects on alcohol reactivity[J]. Langmuir, 2014, 30(16):4642-4653
[17] Sebbar N, Bozzelli J W, Bockhorn H. Thermochemistry and reaction paths in the oxidation reaction of benzoyl radical:C₆H₅C·(O)[J]. Journal of Physical Chemistry A, 2011, 115(42):11897-11914
[18] Wang H, Lu Y, Han Y, et al. Enhanced catalytic toluene oxidation by interaction between copper oxide and manganese oxide in Cu-O-Mn/γ-Al₂O₃ catalysts[J]. Applied Surface Science, 2017, 420:260-266
[19] Jiang C, Wang H, Lin S, et al. Low-Temperature photothermal catalytic oxidation of toluene on a core/shell SiO₂@Pt@ZrO₂ nanostructure[J]. Industrial & Engineering Chemistry Research, 2019, 58(36):256-262
[20] Yogish K, Sastri N V S. A kinetic study of liquid-phase catalytic oxidation of styrene to benzaldehyde with Wilkinson complex[J]. Industrial & Engineering Chemistry Research, 1988, 27(6):909-915