Influences of the [Co2+]/[Co3+] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air

›› 2009, Vol. 17 ›› Issue (4): 613-617.

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Influences of the [Co²⁺]/[Co³⁺] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air

TANG Shengwei, SHEN Wei, LIANG Bin

Multi-phases Transfer and Reaction Engineering Laboratory, College of Chemical Engineering, Sichuan University, Chengdu 610065, China

Received:2008-08-01 Revised:2009-06-15 Online:2010-12-30 Published:2009-08-28
Supported by:
Supported by the National Natural Science Foundation of China(20576081,20736009);the Ph.D. Programs Foundation of Ministry of Education of China(20070Å10128)

Influences of the [Co²⁺]/[Co³⁺] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air

唐盛伟, 沈伟, 梁斌

Multi-phases Transfer and Reaction Engineering Laboratory, College of Chemical Engineering, Sichuan University, Chengdu 610065, China

通讯作者: LIANG Bin, E-mail: liangbin@scu.edu.cn
作者简介:
基金资助:
Supported by the National Natural Science Foundation of China(20576081,20736009);the Ph.D. Programs Foundation of Ministry of Education of China(20070Å10128)

Abstract

Abstract: Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a ø48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH₃COO)₂.4H₂O as catalyst.The Co²⁺ concentration [Co²⁺] was determined by extraction spectrophotometry and hereby the Co³⁺ concentration [Co³⁺] was obtained by mass balance.The results showed that [Co³⁺] reached the maximum at about 25-30min.[Co³⁺] increased with increasing Co catalyst amount at total Co concentration<150 mg·L^-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co³⁺+/Co²⁺] max.A high [Co³⁺] and a high [Co³⁺]/[Co²⁺] ratio are beneficial to the reaction.

Key words: toluene, benzoic acid, liquid-phase oxidation, cobaltous acetate

摘要： Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a ø48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH₃COO)₂.4H₂O as catalyst.The Co²⁺ concentration [Co²⁺] was determined by extraction spectrophotometry and hereby the Co³⁺ concentration [Co³⁺] was obtained by mass balance.The results showed that [Co³⁺] reached the maximum at about 25-30min.[Co³⁺] increased with increasing Co catalyst amount at total Co concentration<150 mg·L^-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co³⁺+/Co²⁺] max.A high [Co³⁺] and a high [Co³⁺]/[Co²⁺] ratio are beneficial to the reaction.

关键词: toluene, benzoic acid, liquid-phase oxidation, cobaltous acetate

TANG Shengwei, SHEN Wei, LIANG Bin. Influences of the [Co²⁺]/[Co³⁺] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air[J]. , 2009, 17(4): 613-617.

唐盛伟, 沈伟, 梁斌. Influences of the [Co²⁺]/[Co³⁺] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air[J]. CIESC Journal, 2009, 17(4): 613-617.

References

1 Martin,A.,LÜcke,B.,“Ammoxidation and oxidation of substituted methyl aromatics on vanadium-containing catalysts”,Catal.Today, 57,61-70Å2000).
2 Messina,G.,“Upgrade toluene to benzoic acid”,Hydrocarbon Processing and Petroleum Refiner Petrochemical Developments,43(11), 191-192(1964).
3 Kaeding,W.W.,“How Dow makes phenol from toluene”,Hydrocarbon Processing and Petroleum Refiner Petrochemical Developments,43(11),173-176(1964).
4 Kamiya,Y.,Kashima,M.,“The autoxidation of aromatic hydrocarbons catalyzed with cobaltic acetate in acetic acid solution(I)The oxidation of toluene”,J.Catal.,25,326-333(1972).
5 Sakota,K.,Kamiya,Y.,Ohta,N.,“The autoxidation of toluene catalyzed with cobalt monobromide in acetic acid”,Bull.Chem.Soc. Japan,41,641-646(1968).
6 Scott,E.,Chester,W.,“Kinetics of the cobalt-catalyzed autoxidation of toluene in acetic acid—The role of cobalt”,J.Phys.Chem.,76 (11),1520-1524(1972).
7 Partenheimer,W.,“Characterization of the reaction of cobalt(Ⅱ) Acetate,dioxygen and acetic acid,and its significance in autoxidation reactions”,J.Mol.Catal.,67,35-46(1991).
8 Hendriks,C.F.,van Beek,H.C.A.,Heertjes,P.M.,“The oxidation of substituted toluenes by cobalt(III)Acetate in acetic acid solution”, Ind.Eng.Chem.Prod.Res.Dev.,17(3),256-260(1978).
9 Morimoto,T.,Ogata,Y.,“Kinetics of the autoxidation of toluene catalysed by cobaltic acetate”,J.Chem.Soc.B Phys.Org.,1,62-66 (1967).
10 Morimoto,T.,Ogata,Y.,“Kinetics of the autoxidation of toluene catalysed by cobaltic acetate(II)Effects of benzaldehyde,cobalt, and substituent”,J.Chem.Soc.B Phys.Org.,12,1353-1357(1967).
11 Bukharkina,T.V.,Digurov,N.G.,“Kinetics of aerobic liquid-phase oxidation of organic compounds”,Org.Process Res.Dev.,38(3), 320-329(2004).
12 Borgaonkar,H.V.,Raverkar,S.R.,Chandalla,S.B.,“Liquid phase oxidation of toluene to benzaldehyde by air”,Ind.Eng.Chem.Prod. Res.Dev.,23,455-458(1984).
13 Partenheimer,W.,“Methodology and scope of metal/bromide autoxidation of hydrocarbons”,Catal.Today,23,69-158(1995).
14 Tang,S.,Liang,B.,“Kinetics of the liquid-phase oxidation of toluene by air”,Ind.Eng.Chem.Res.,46(20),6442-6448(2007).
15 Cooper,T.A.,Clifford,A.A.,Mills,D.J.,Waters,W.A.,“Oxidation of organic compounds by cobaltic salts(VII)The Oxidation of toluene and its promotion by aliphatic acids”,J.Chem.Soc.B Phys.Org. Chem.,793-799(1966).
16 Hanotier,J.,Hanotier-Bridoux,M.,“Mechanism of the liquid phase homogeneous oxidation of alkylaromatic hydrocarbons by cobalt salts”,J.Mol.Catal.,12,133-147(1981).
17 Tanaka,K.,“Adipic acid in one step”,CHEMTECH,4,555-559 (1974).
18 Steinmetz,G.R.,Lafferty,N.L.,Sumner Jr.,C.E.,“The cobalt/zirconiumcatalyzed oxidation cyclohexane to adipic acid”,J.Mol.Catal.,49, L39-L42(1988).
19 Shen,W.,Tang,S.,Tan,P.,Liang,B.,“Photometric determination of Co(II)in organic matter”,Physical Testing and Chemical Analysis. Part B:Chemical Analysis,42(6),484-485(2006).(in Chinese)
20 Tang,S.,Liang,B.,“Scale formation and its mechanism in the liquid-phase oxidation of toluene by air”,Ind.Eng.Chem.Res.,46(24), 7826-7829(2007).
21 Tang,S.,Zhang,Q.,Liang,B.,“Analysis of the scale sample from toluene liquid-phase oxidation process”,Petrochem.Technol.,33(4), 372-376(2004).(in Chinese)
22 Tang,S.,Zhang,Q.,Liu,F.,Liang,B.,“Mechanism and influence factors of scaling phenomenon in liquid-phase oxidation of toluene by air”,J.Chem.Ind.Eng.(China),56(9),1685-1689(2005).(in Chinese)
23 Kamiya,Y.,Kashima,M.,“Autoxidation of aromatic hydrocarbons catalyzed with cobaltic acetate in acetic acid solution(II)Oxidation of ethylbenzene and cumene”,Bull.Chem.Soc.Japan,46,905-908 (1973).
24 Tang,S.,Liang,B.,Wu,P.,Zhang,Q.,Liu,C.,“Effects of operation parameters on the benzaldehyde formation in the liquid-phase oxidation of toluene”,Journal of Sichuan University(Engineering Science Edition),37(5),76-81(2005).(in Chinese)

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Influences of the [Co²⁺]/[Co³⁺] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air

Influences of the [Co²⁺]/[Co³⁺] Ratio on the Process of Liquid-phase Oxidation of Toluene by Air

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