环已酮合成邻苯基苯酚的研究
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摘要
邻苯基苯酚是一种应用广泛的精细化工产品,可用于制备杀菌防腐剂、表面活性剂、染料中间体、塑料热稳定剂和阻燃剂等。以环己酮为原料先经缩合脱水得环己酮二聚体(Dimer),Dimer再脱氢生产邻苯基苯酚的工艺过程是一条过程简单、经济合理的路线,国外已经实现工业化,但我国还没有大型工业化装置。本文研究了以环己酮为原料生产OPP的工艺,重点研究了Dimer脱氢催化剂的制备方法和添加金属钾盐对其性能的影响。
首先,本文系统地研究了以硫酸、氧化铝等多种酸性催化剂催化环己酮缩合脱水反应。实验结果表明:以Al_2O_3作为缩合反应的催化剂不但具有较高的活性和选择性而且具有催化剂易分离,产品精制过程简单的优点。环己酮的转化率可达74%,二聚体的选择性为87%。
以γ-Al_2O_3为载体,氯铂酸为前驱体,通过等体积浸渍法制备Pt/γ-Al_2O_3脱氢催化剂,并添加钾盐助剂进行改性。重点研究了载体γ-Al_2O_3的性能,载铂量、助剂种类与添加量和催化剂制备条件等因素对催化剂催化性能的影响。研究结果表明:载体γ-Al_2O_3的杂质含量对催化剂的性能具有较大的影响,其SiO_2的含量应低于0.3%,Fe_2O_3的含量应低于0.1%,以360℃为焙烧温度,载铂量以0.5%(载体质量为基准)为宜。在催化剂上K含量相同的情况下以K_2SO_4为助剂的催化剂OPP收率最高,可达93%。采用XRD、NH_3-TPD和CO_2-TPD程序升温脱附法对催化剂表面性质进行研究表明,以K_2SO_4作助剂的催化剂的对产物OPP高选择性和稳定性主要与其较低的表面酸量有关。在T=355℃,LHSV=0.2 h~(-1),H_2=40ml/min条件下反应达最佳效果,且在此条件下连续运转240h,Dimer的转化率和OPP收率未发生显著的变化,OPP的平均收率可达92%,催化剂稳定性良好。
O-phenylphenol(OPP)is a fine chemical product which is widely used for the preparation of bactericides,preservatives,surfactants, intermediates of dyes,plastic stabilizers and fire retardants.Using cyclohexanone as a starting material,OPP can be prepared by a tow-stage process comprising the condensation of cyclohexanone to its dime and subsequent dehydrogenation of Dimer to OPP.This process is simple, economic and has been industrialized abroad.However,in China such unit has not been available in big and industrial scale.In this thesis the preparation of the OPP from cyclohexanone via the two-stage process was investigated.The study is focused on the preparation method of the dehydrogenation catalyst and the influence of alkali-metal salts on the catalytic performance.
Firstly,condensation of cyclohexanone using acidic catalysts such as sulfuric acid and alumina was systematically studied.The result showed that Al_2O_3 owned a high activity and selectivity when it was adopted as the condensation catalyst,the conversion of cyclohexanoe was up to 74%, and the selectivity of Dimer reached 87%.Using Al_2O_3 as a catalyst has the advantages that separation of the catalyst from the liquid product and is easy,subsequent purification of the product is simplified.
The Pt/γ-Al_2O_3 dehydrogenation catalyst was prepared by equal-volume impregnation usingγ-Al_2O_3 as the support,chloroplatinic acid as a precursor and K-salts as promoters to improve the catalyst performance.Factors that influence the performance of the dehydrogenation catalyst were investigated including the properties of the support,the amount of platinum supported,the type and amount of the promoters and preparation conditions.The results showed that the impurities in Al_2O_3 support had a significant influence on the catalyst performance.The content of SiO_2 should be lower that 0.3%and Fe_2O_3 should be lower than 0.1%.at 360℃to calcine the catalyst,With the amount of supported Pt of 0.5%(based the quality of the cartier),and K_2SO_4 as a promoter,the catalyst showed highly activity,selectivity and stability.The yield of OPP amounted 93%.Characterization using XRD, NH_3-TPD and CO_2-TPD revealed that the high OPP yield and stability of the catalyst with K_2SO_4 as a promoter is mainly due to the lower amount of the acidic sites on its surfaces.Optimization of the reaction conditions indicated that at T= 355℃,LHSV=0.2 h~(-1),H_2=40ml/min,the catalyst showed its best performance.In the duration of 240h stability test,the average yield of OPP amounted 92%and no significant decrease in the activity was observed,indicating that the catalyst had a good stability.
首先,本文系统地研究了以硫酸、氧化铝等多种酸性催化剂催化环己酮缩合脱水反应。实验结果表明:以Al_2O_3作为缩合反应的催化剂不但具有较高的活性和选择性而且具有催化剂易分离,产品精制过程简单的优点。环己酮的转化率可达74%,二聚体的选择性为87%。
以γ-Al_2O_3为载体,氯铂酸为前驱体,通过等体积浸渍法制备Pt/γ-Al_2O_3脱氢催化剂,并添加钾盐助剂进行改性。重点研究了载体γ-Al_2O_3的性能,载铂量、助剂种类与添加量和催化剂制备条件等因素对催化剂催化性能的影响。研究结果表明:载体γ-Al_2O_3的杂质含量对催化剂的性能具有较大的影响,其SiO_2的含量应低于0.3%,Fe_2O_3的含量应低于0.1%,以360℃为焙烧温度,载铂量以0.5%(载体质量为基准)为宜。在催化剂上K含量相同的情况下以K_2SO_4为助剂的催化剂OPP收率最高,可达93%。采用XRD、NH_3-TPD和CO_2-TPD程序升温脱附法对催化剂表面性质进行研究表明,以K_2SO_4作助剂的催化剂的对产物OPP高选择性和稳定性主要与其较低的表面酸量有关。在T=355℃,LHSV=0.2 h~(-1),H_2=40ml/min条件下反应达最佳效果,且在此条件下连续运转240h,Dimer的转化率和OPP收率未发生显著的变化,OPP的平均收率可达92%,催化剂稳定性良好。
O-phenylphenol(OPP)is a fine chemical product which is widely used for the preparation of bactericides,preservatives,surfactants, intermediates of dyes,plastic stabilizers and fire retardants.Using cyclohexanone as a starting material,OPP can be prepared by a tow-stage process comprising the condensation of cyclohexanone to its dime and subsequent dehydrogenation of Dimer to OPP.This process is simple, economic and has been industrialized abroad.However,in China such unit has not been available in big and industrial scale.In this thesis the preparation of the OPP from cyclohexanone via the two-stage process was investigated.The study is focused on the preparation method of the dehydrogenation catalyst and the influence of alkali-metal salts on the catalytic performance.
Firstly,condensation of cyclohexanone using acidic catalysts such as sulfuric acid and alumina was systematically studied.The result showed that Al_2O_3 owned a high activity and selectivity when it was adopted as the condensation catalyst,the conversion of cyclohexanoe was up to 74%, and the selectivity of Dimer reached 87%.Using Al_2O_3 as a catalyst has the advantages that separation of the catalyst from the liquid product and is easy,subsequent purification of the product is simplified.
The Pt/γ-Al_2O_3 dehydrogenation catalyst was prepared by equal-volume impregnation usingγ-Al_2O_3 as the support,chloroplatinic acid as a precursor and K-salts as promoters to improve the catalyst performance.Factors that influence the performance of the dehydrogenation catalyst were investigated including the properties of the support,the amount of platinum supported,the type and amount of the promoters and preparation conditions.The results showed that the impurities in Al_2O_3 support had a significant influence on the catalyst performance.The content of SiO_2 should be lower that 0.3%and Fe_2O_3 should be lower than 0.1%.at 360℃to calcine the catalyst,With the amount of supported Pt of 0.5%(based the quality of the cartier),and K_2SO_4 as a promoter,the catalyst showed highly activity,selectivity and stability.The yield of OPP amounted 93%.Characterization using XRD, NH_3-TPD and CO_2-TPD revealed that the high OPP yield and stability of the catalyst with K_2SO_4 as a promoter is mainly due to the lower amount of the acidic sites on its surfaces.Optimization of the reaction conditions indicated that at T= 355℃,LHSV=0.2 h~(-1),H_2=40ml/min,the catalyst showed its best performance.In the duration of 240h stability test,the average yield of OPP amounted 92%and no significant decrease in the activity was observed,indicating that the catalyst had a good stability.
引文
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[2]http://www.chemyq.com/xz/xzl/5006nkgjb.htm
[3]王大全.精细化工辞典[M].化学工业出版社,1998.
[4]Gartner,Charles D.Suspension formulations of ortho-phenylphenol[P].US:5629350,1997:5-13.
[5]佳文.邻苯基苯酚生产应用与技术进展.精细化工原料及中间体[J].2005,(9):38-41
[6]顾小焱.一种新型的阻燃剂中间体DOPO及其应用[J].化学试剂.2007,29(4):254-255
[7]龙夏株.邻苯基苯酚合成工艺研究[D1.淅江大学.2007,5
[8]石磊.邻苯基苯酚的生产与应用[J].化工中间体.2003,(16):12-14
[9]李玉华.邻苯基苯酚[J].精细与专用化学品.2002,(16):8-9.
[10]钱松.邻苯基苯酚消费市场[J].精细化工原料及中间体.2004(2):35
[11]http://www.ydjjxx.gov.cn/more1.asp?id=6868
[12]岳丽丽.邻苯基苯酚的化学合成[D].四川大学硕士论文.2003
[13]卫延安.合成邻苯基苯酚的催化剂的制备及性能研究[D].南京理工大学.2004
[14]Lee,GS,Garces,et al.Method to prepare ortho substituted phenol[P].US:5583268,1996-12-10
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[17]李瑞硕,王心葵.环己酮双聚合成环己烯环己酮新型催化剂的研究[J].石油化工.1995
[18]Elliott C S.Production of O-phenylphenol from Cyclohexanone[P].US:3980716,1976～09～14
[19]蔡春,吕春绪.邻苯基苯酚的合成[J].南京理下大学学报,2001,2(4):436-439
[20]Naresh F.Shah.Cross-dimerization of a-methylstyrene with isomylene and aldol condensation of cyclohexanone using a cation-exchange resin and acid-treated clay catalysts [J].Reactive Polymers.1994,22:19-34.
[21]邢其毅.基础有机化学(2版)[M].北京:高等教育出版社,1983,480-482
[22]Takahahashi T,Hara Kimihiko,Osugi J.The Self-condensation of Cyclohexanone and Methyl Cyclohexanones under very High Pressure[J].Rev Phys.Chem Japan,1974,44(2):93-7
[23]蔡春,吕春绪.用环己酮合成邻苯基苯酚的方法[J]:CN1371897A[P].2002～10～02
[24]Imafuku K,Oda J,Kenshi I.Dehydrogenation of 2-(1-cyclohexenyl)cyclohexanone with Palladium Catalyst.Bull Chem Sco Japan,1974,47(5):1201-1202
[28]Klein F,Joseph M,Stijfs A,M.Petrus:US 4052458[P].1975
[29]King I R,Warrington,Hildon A.M.Process for the Production of O-Phenylphenol.US:4002693,1977
[30]杨飘萍.环己酮合成邻苯基苯酚的研究[D].长春:吉林大学,2005
[31]陈红艳,尹笃林,胡伟武.环己酮酸催化合成环己烯环己酮的研究[J].襄樊学院学报,2001,22(5):45-48
[32]李瑞硕,王心葵.环己酮双聚合成环己烯环己酮新型催化剂的研究[J].石油化工,1995(24):95-99
[33]陈劲松,王海南,王虹.2-(1-环己烯基)环己酮的合成[J].化工时刊,2006,20(4):45-46
[34]金东元,陶建伟,姜荫,等.离子交换树脂催化合成2-(1-环己烯基)环己酮[J]
[35]李彦鹏,刘大鹏,刘晨光.环己酮自缩合固体催化剂的研究[J].工业催化,2007,15(1):38-42
[36]冯望烟,陈诩,缪雪茹.环己酮二聚物脱氢制邻苯基苯酚反应及催化剂研究[J].石油化工,1990,19:238.
[37]Imamura J.Process for the Production of O-Phenylphenol.US:4080390,1978-3-21
[38]清水一男等,日本特许公报.昭81,46,801
[39]日本特许公报,昭61,20,181
[40]蔡春,吕春绪.催化脱氢合成邻苯基苯酚工艺研究[J].染料工业.2001(4):27-28
[41]HeithG.PrearationofUnsaturatedCyelieKetones[P].Brit1480326,1977-07-20
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