Catalytic performance of Co(acac)2 catalyst for liquid-phase oxidation of toluene by air

doi:10.3969/j.issn.0438-1157.2013.04.019

Abstract

Abstract: Liquid-phase oxidation of toluene by air was carried out by using Co(acac)₂ as catalyst in a 1 L stirred tank reactor.The product distributions of toluene oxidation and the effect of Co concentrations on the oxidation reaction of toluene were investigated.The life of Co(acac)₂ catalyst was studied under different reaction temperatures and Co concentrations.The results showed that toluene oxidation was multiple reactions in parallel and series steps.A phenomenon of "catalyst- inhibitor" transition was found for Co(acac)₂ catalyst like other Co salt catalyst.The appropriate Co(acac)₂ dosage was 0.0044%(mass).Co(acac)₂ catalyst life changed with reaction temperature and had the longest value at 165℃.Co(acac)₂ catalyst might lose its activity easily at a lower reaction temperature (<165℃).The conversion of toluene and yield of benzoic acid could reach 19% and 80% respectively at reaction time 4 hours,reaction temperature 165℃ and Co concentration 0.0044%.Co(acac)₂ catalyst has less catalyst dosage and longer lifetime than other Co salt catalysts like cobalt acetate,cobalt naphthenate,etc.,which could slow down the scaling of cobalt oxalate during reaction.Therefore Co(acac)₂ catalyst has a good application prospect as catalyst in liquid-phase oxidation of toluene.

Key words: toluene, liquid-phase oxidation, Co(acac)₂, benzoic acid

摘要： 以乙酰丙酮钴(Co(acac)₂)为催化剂,在1 L高压搅拌反应釜中研究了其对甲苯液相空气氧化反应的催化性能和反应产物分布,考察了催化剂用量对甲苯转化率和苯甲酸收率的影响,并考察了不同温度下不同催化剂用量时的催化剂寿命。结果表明,Co(acac)₂催化甲苯液相氧化是平行连串的复杂反应,Co(acac)₂的催化活性存在"催化-抑制转换"现象,适宜的催化剂用量为0.0044%(质量分数);催化剂的寿命随反应温度变化存在一个最大值,165℃时催化剂寿命最长,反应温度较低(<165℃)时催化剂更容易失活;在165℃、Co(acac)₂用量为0.0044%时,反应4 h,甲苯转化率为19%,苯甲酸收率为80%;与醋酸钴、环烷酸钴等钴盐催化剂相比,Co(acac)₂催化剂具有用量少、催化活性时间长的优点,可有效地减缓钴盐结垢现象,Co(acac)₂催化剂对甲苯液相空气氧化反应具有良好的催化性能。

关键词: 甲苯, 液相氧化, 乙酰丙酮钴, 苯甲酸

CLC Number:

O643.32

JIN Shaojin, CHEN Jizhong. Catalytic performance of Co(acac)₂ catalyst for liquid-phase oxidation of toluene by air[J]. CIESC Journal, 2013, 64(4): 1256-1262.

金少瑾, 陈纪忠. 乙酰丙酮钴(Ⅱ)对甲苯液相空气氧化反应的催化性能[J]. 化工学报, 2013, 64(4): 1256-1262.

References 22

[1]	Wu Xingan(吴鑫干),Chen Shufa(陈舒伐).Synthesis and refining of benzoic acid[J].Modern Chemical Industry(现代化工),2000,20(8): 10-14
[2]	Messina G.Upgrade toluene to benzoic acid[J].Petrochem.Dev.,1964,43: 191-192
[3]	Tang S W,Liang B.Scale formation and its mechanism in the liquid-phase oxidation of toluene by air[J].Ind.Eng.Chem.Res.,2007,46: 7826-7829
[4]	Saffer A,Roberts B.Preparation of aromatic polycarboxylic acid[P]:US,2833816.1958-05-06
[5]	Partenheimer W.Methodology and scope of metal/bromide autoxidation of hydrocarbons[J].Catal.Today,1995,23: 69-158
[6]	Ishii Y.A novel catalysis of N-hydroxyphthalimide(NHPI) combined with Co(acac)em>n(n=2 or 3) in the oxidation of organic substrates with molecular oxygen[J].J.Mol.Catal.A: Chem.,1997,117: 123-137
[7]	Ishii Y,Sakaguchi S.A new strategy for alkane oxidation with O2 using N-hydroxyphthalimide(NHPI) as a radical catalyst[J].Catal.Surv.Jpn.,1999,3: 27-35
[8]	Ishii Y,Iwahama T,Sakaguchi S,Nakayama K,Nishiyama Y.Alkane oxidation with molecular oxygen using a new efficient catalytic system:N-hydroxyphthalimide(NHPI) combined with Co(acac)em>n (n=2 or 3)[J].J.Org.Chem.,1996,61: 4520-4526
[9]	Ishii Y,Kato S,Iwahama T,Sakaguchi S.Hydroxylation of polycyclic alkanes with molecular oxygen catalyzed by N-hydroxyphthalimide(NHPI) combined with transition metal salts[J].Tetrahedron.Lett.,1996,37: 4993-4996
[10]	Fang Yahui(方亚辉),Hu Anjun(户安军),Li Bindong(李斌栋),Lü Chunxu(吕春绪).Oxidation of toluene catalyzed by NHPI/transition metals [J].Chemical Industry and Engineering Progress (化工进展),2006,25(11): 1358-1361
[11]	Zhuo Guanglan(卓广澜),Zhao Weijuan(赵卫娟),Jiang Xuanzhen(姜玄珍).A novel catalyst system for the oxidation of toluene to benzoic acid [J].Chinese Journal of Organic Chemistry (有机化学),2004,24(8): 962-965
[12]	Hu Anjun(户安军),Lü Chunxu(吕春绪),Li Bindong(李斌栋),Huo Ting(霍婷).Study on a novel catalysis system for the selective oxidation of p-chlorotoluene[J].Chinese Journal of Organic Chemistry (有机化学),2006,26(8): 1083-1086
[13]	Li Zhigang(李志刚),Chen Li(陈丽),Deng Lisheng(邓立生),Li Xianjun(李贤均).Study on the catalyze oxidation of p-nitrotoluene in liquid-phase[J].Chemical Research and Applications (化学研究与应用),2001,13(6): 661-664
[14]	Fan Qian(范谦),Li Yaozhong(黎耀忠),Cheng Puming(程溥明),Hu Jiayuan(胡家元),Li Xianjun(李贤均).Study on allylic oxidation in cyclohexene[J].Chemical Research and Applications(化学研究与应用),2001,13(5): 557-559
[15]	Liu Jiansong(刘建松).Kinetic of liquid-phase oxidation of toluene[D].Hangzhou: Zhejiang University,2006
[16]	Zou Yinwen(邹隐文),Gu Xiongyi(顾雄毅),Cheng Zongze(程宗泽),Yu Guangxin(于广欣),Wang Zhikan(王志侃).Kinetics of liquid-phase oxidation of toluene[J].Chemical Engineering (China)(化学工程),2007,35(9): 33-36
[17]	Hoorn J A A,Soolingen J V,Versteeg G F.Modelling toluene oxidaton incorporation of mass transfer phenomena[J].Chem.Eng.Res.Des.,2005,83: 187-195
[18]	Hoorn J A A,Alsters P L,Versteeg G F.A kinetic model for toluene oxidation comprising benzylperoxy benzoate ester as reactive intermediate in the formation of benzaldehyde[J].Int.J.Chem.Reac.Eng.,2005,3: 1
[19]	Kamiya Y,Ingold K U.The metal-catalyzed autoxidation of tetralin(Ⅳ): The effect of solvent and temperature[J].Can.J.Chem.,1964,42: 2424-2433
[20]	Black J F.Metal-catalyzed autoxidation the unrecognized consequences of metal-hydroperoxide complex formation[J].J.Am.Chem.Soc.,1978,100: 527-535
[21]	Guo C C,Liu Q,Wang X T,Hu H Y.Selective liquid phase oxidation of toluene with air[J].Appl.Catal.A,2005,282: 55-59
[22]	Tang Shengwei(唐盛伟),Liang Bin(梁斌),Wu Pan(吴潘),Zhang Quanzhong(张全忠),Liu Changjun(刘长军).Kinetics of liquid-phase oxidation of toluene to benzoic acid by air[J].Chemical Reaction Engineering and Technology(化学反应工程与工艺),2005,21(4): 333-339

Catalytic performance of Co(acac)₂ catalyst for liquid-phase oxidation of toluene by air

乙酰丙酮钴(Ⅱ)对甲苯液相空气氧化反应的催化性能

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