Continuous flow oxidation of benzyl alcohol to benzaldehyde

doi:10.16085/j.issn.1000-6613.2020-0544

Abstract

Abstract:

Benzaldehyde was continuously synthesized using benzyl alcohol as raw material and 2,2,6,6-tetramethyl-piperidin-1-oxyl (TEMPO) over catalyst, by the oxidation of sodium hypochlorite solution in a continuous flow micro-channel reactor under the liquid-phase conditions. The effects of reactants molar ratio, amount of catalyst, reaction temperature, solvents and residence time on the yields of product were investigated and the process conditions were optimized. The results indicate that under the conditions of n(NaClO)∶n(benzyl alcohol)=1.25∶1, n(benzyl alcohol)∶n(TEMPO)=1∶0.01, V(benzyl alcohol)∶V(DMF)=1∶10, pH=8, reaction temperature at 0℃, and residence time at 10min, the yield of benzaldehyde reaches 95.1%.

Key words: benzyl alcohol, oxidation reaction, continuous flow technology, benzaldehyde, TEMPO catalyst

摘要：

在液相条件下以苯甲醇为原料，次氯酸钠溶液为氧化剂，2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）为氧化催化剂，在连续流微通道反应器中液相氧化合成苯甲醛。考察了苯甲醇与次氯酸钠溶液的物质的量配比、催化剂用量、反应温度、溶剂以及停留时间对苯甲醛合成的影响，并进行了工艺优化。结果表明：当次氯酸钠与苯甲醇的物质的量比为1.25∶1、苯甲醇与TEMPO的物质的量比为1∶0.01、苯甲醇与DMF的体积比为1∶10、 pH=8、反应温度为0℃、停留时间为10min时，苯甲醛的收率可达95.1%。

关键词: 苯甲醇, 氧化反应, 连续流工艺, 苯甲醛, TEMPO催化剂

CLC Number:

TQ244.3

Jianwu LIU, Shenghu YAN, Yue ZHANG, Jiefa SHEN. Continuous flow oxidation of benzyl alcohol to benzaldehyde[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 394-400.

刘建武, 严生虎, 张跃, 沈介发. 苯甲醇液相氧化合成苯甲醛的连续流工艺[J]. 化工进展, 2021, 40(1): 394-400.

Figures/Tables 13

References 25

1	张昕, 吴伟伟, 黄启权, 等. 苯甲醇液相氧化制苯甲醛催化剂的研究进展[J]. 石油化工, 2010, 39(2): 215-223.
	ZHANG Xin, WU Weiwei, HUANG Qiquan, et al. Research progress of catalysts for liquid phase oxidation of benzyl alcohol to benzaldehyde [J]. Petrochemical Technology, 2010, 39(2): 215-223.
2	GUMEL A M, ANNUAR M S M. Thermomyces lanuginosus lipase-catalyzed synthesis of natural flavor esters in a continuous flow microreactor [J]. Biotech, 2016, 6(1): 12-24.
3	SI Jingyan, LIU Ya, CHANG Shunzhou, et al. AgBr@TiO₂/GO ternary composites with enhanced photocatalytic activity for oxidation of benzyl alcohol to benzaldehyde [J]. Research on Chemical Intermediates, 2016, 43(4): 2067-2080.
4	ZHU Lin, XU Xiaohui, ZHENG Fuping. Synthesis of benzaldehyde by Swern oxidation of benzyl alcohol in a continuous flow microreactor system [J]. Turkish Journal of Chemistry, 2018, 42(1): 75-85.
5	李士玲, 梁斌, 唐盛伟. Co/Mn/Zr复合催化剂催化甲苯液相氧化[J]. 化学反应工程与工艺, 2012, 28(2): 143-148.
	LI Shiling, LIANG Bin, TANG Shengwei. Liquid phase oxidation of toluene catalyzed by CO/Mn/Zr composite catalyst[J]. Chemical Reaction Engineering and Technology, 2012, 28(2): 143-148.
6	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.
7	HE Ai, ZHANG Jie, ZHENG Wenjin, 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.
8	蔡妃妹. 锰氧化物催化氧化苯甲醇合成苯甲醛的研究[D]. 广州: 广东工业大学, 2012.
	CAI Feimei. Synthesis of benzaldehyde from benzyl alcohol catalyzed by manganese oxides[D]. Guangzhou: Guangdong University of Technology, 2012.
9	李达, 刘宏伟, 仵静, 等. 醇类选择性催化氧化的研究进展[J]. 工业催化, 2014, 22(11): 825-830.
	LI Da, LIU Hongwei, WU Jing, et al. Research progress of selective catalytic oxidation of alcohols[J]. Industrial Catalysis, 2014, 22(11): 825-830.
10	PARMEGGIANI C, CARDONA F. Transition metal based catalysts in the aerobic oxidation of alcohols[J]. Green Chemistry, 2012, 14(3): 547-564.
11	LEI Ming, HU Ruijun, WANG Yanguang. 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.
12	HUNSEN M. Pyridinium chlorochromate catalyzed oxidation of alcohols to aldehydes and ketones with periodic acid[J]. Tetrahedron Letters, 2005, 46(10): 1651-1653.
13	杨贯羽, 郭彦春, 武光辉, 等. 氮氧自由基TEMPO: 选择氧化醇的高效有机小分子催化剂[J]. 化学进展, 2007, 11(19): 1727-1734.
	YANG Guanyu, GUO Yanchun, WU Guanghui, et al. Nitroxide radical tempo: a highly efficient organic small molecule catalyst for selective oxidation of alcohols[J]. Progress in Chemistry, 2007, 11(19): 1727-1734.
14	王晨, 毛会玲, 薛云, 等. TEMPO功能化共轭微孔聚合物催化氧化醇性能[J]. 精细化工, 2019, 36(12): 25-30.
	WANG Chen, MAO Huiling, XUE Yun, et al. Catalytic performance of tempo functionalized conjugated microporous polymer for alcohol oxidation[J]. Fine Chemicals, 2019, 36(12): 25-30.
15	黄斌, 张宁, 洪三国, 等. 氮氧自由基催化有机物的分子氧氧化研究进展[J]. 分子催化, 2009, 23(4): 377-385.
	HUANG Bin, ZHANG Ning, HONG Sanguo, et al. Research progress of nitroxide radical catalyzed molecular oxygen oxidation of organic compounds[J]. Journal of Molecular Catalysis, 2009, 23(4): 377-385.
16	ANELLI P L, BIFFI C, MONTANARI F, et al. Fast and selective oxidation of primary alcohols to aldehydes or to carboxylic acids and of secondary alcohols to ketones mediated by oxoammonium salts under two-phase conditions[J]. Journal of Organic Chemistry, 1987, 52(12): 2559-2562.
17	余依玲, 高保娇, 李艳飞, 等. TEMPO/固载化席夫碱铜配合物共催化剂在分子氧氧化苯甲醇过程中的催化性能[J]. 分子催化, 2014, 6(3): 210-217.
	YU Yiling, GAO Baojiao, LI Yanfei, et al. Catalytic performance of TEMPO/supported Schiff base copper complex cocatalyst for the oxidation of benzyl alcohol by molecular oxygen[J]. Journal of Molecular Catalysis, 2014, 6(3): 210-217.
18	PANDARUS V, CIRIMINNA R, BELAND F, et al. Greening heterogeneous catalysis for fine chemicals[J]. Tetrahedron Letters, 2013, 54(9): 1129-1132.
19	SHELDON R A. Recent advances in green catalytic oxidations of alcohols in aqueous media[J]. Catalysis Today, 2015, 247(46): 4-13.
20	严生虎, 陈代祥, 沈卫, 等. 微通道反应器中苄亚甲基二氯水解制苯甲醛连续流工艺[J]. 化工进展, 2013, 32(2): 299-302.
	YAN Shenghu, CHEN Daixiang, SHEN Wei, et al. Continuous flow process of benzylidene dichloride hydrolysis to benzaldehyde in microchannel reactor[J]. Chemical Industry and Engineering Progress, 2013, 32(2): 299-302.
21	DE MICO A, MARGARITA R, PARLANTI L, et al. A versatile and highly selective hypervalent iodine ()/2,2,6,6-tetramethyl-1-piperidinyloxyl-mediated oxidation of alcohols to carbonyl compounds[J]. Journal of Organic Chemistry, 1997, 62(20): 6974-6977.
22	HUNTER D H, BARTON D H R, MOTHERWELL W J. Oxoammonium salts as oxidizing agents: 2,2,6,6-tetramethyl-1-oxopiperidinium chloride[J]. Tetrahedron Letters, 1984, 25(6): 603-606.
23	MILLER R A, HOERRNER R S. Iodine as a chemoseletive reoxidant of TEMPO: application to the oxidation of alcohols to aldehydes and ketones[J]. Organic Letters, 2003, 5(3): 285-287.
24	GANIEY I M, TIMERGHAZIN Q K, KHLIZOV A F, et al. Complex of chlorine dioxide with TEMPO and its conversion into oxoammonium salt[J]. Journal of Physical Organic Chemistry, 2001, 14(1): 38-42.
25	SHELDON R A, ARENDS I W C E. Organocatalytic oxidations mediated by nitroxyl radicals[J]. Advanced Synthesis & Catalysis, 2004, 346(9): 1051-1071.

参数	微通道反应器
参数	脉冲混合式	?0.8mm圆管	?2.0mm圆管
n(次氯酸钠)∶n(苯甲醇)	1.25∶1^①	1.30∶1^①	1.35∶1^①
n(TEMPO)∶n(苯甲醇)	0.01∶1^①	0.012∶1^①	0.015∶1^①
反应温度/℃	0^①	-5^①	8^①
停留时间/min	10^①	12^①	15^①
产品收率/%	95.1	93.6	92.5

参数	微通道反应器
参数	脉冲混合式	?0.8mm圆管	?2.0mm圆管
n(次氯酸钠)∶n(苯甲醇)	1.25∶1^①	1.30∶1^①	1.35∶1^①
n(TEMPO)∶n(苯甲醇)	0.01∶1^①	0.012∶1^①	0.015∶1^①
反应温度/℃	0^①	-5^①	8^①
停留时间/min	10^①	12^①	15^①
产品收率/%	95.1	93.6	92.5

传热和传质指标	微通道反应器	夹套式搅拌釜
单位体积换热面积/m²·m^-3	2500	2.5～10
总换热系数/kW·m^-3·K^-1	1700	1～10
安全性（反应持液量）/L	4	4000
物料配比（物质的量比）	1.25∶1	(1.30~1.36)∶1
催化剂用量（物质的量比）	0.01∶1	(0.05~0.08)∶1
溶剂用量（体积比）	1∶10	1∶(20~30)
反应温度/℃	0	0~20
停留时间/min	10	120~150
产品收率/%	95.1	91.8

传热和传质指标	微通道反应器	夹套式搅拌釜
单位体积换热面积/m²·m^-3	2500	2.5～10
总换热系数/kW·m^-3·K^-1	1700	1～10
安全性（反应持液量）/L	4	4000
物料配比（物质的量比）	1.25∶1	(1.30~1.36)∶1
催化剂用量（物质的量比）	0.01∶1	(0.05~0.08)∶1
溶剂用量（体积比）	1∶10	1∶(20~30)
反应温度/℃	0	0~20
停留时间/min	10	120~150
产品收率/%	95.1	91.8

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[12]	YU Wendi，HUA Min，PAN Xuhai，CHEN Faming，JIANG Juncheng. Application research on inherently safer design in nitric acid oxidation of alcohol [J]. Chemical Industry and Engineering Progree, 2014, 33(04): 1054-1059.
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