B型银催化剂乙烯环氧化工艺条件的优化
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摘要
采用微型等温固定床积分反应器,对B型银催化剂上乙烯环氧化制环氧乙烷的工艺条件进行研究,考察了原料气中乙烯、氧气、二氧化碳和1,2-二氯乙烷的含量,以及反应温度等5个因素对环氧化过程的影响;并以环氧乙烷收率和反应选择性为目标,采用正交实验考察上述5个因素对环氧化过程的综合影响。实验结果表明,反应温度对环氧乙烷收率和反应选择性的影响最显著,其对B型银催化剂性能的发挥起着决定性的作用;综合考虑环氧乙烷收率和选择性两个指标,确定的相对适宜工艺条件为:反应温度240℃,原料气中1,2-二氯乙烷含量0.7×10~(-6)(x)、乙烯含量22.00%(x)、二氧化碳含量1.00%(x)、氧气含量6.50%(x),在此条件下环氧乙烷的收率和选择性可分别达到38.87%和86.70%。
Ethylene epoxidation over B-type silver catalyst was studied in a micro constant temperature fixed bed integral reactor.The effects of reaction temperature,ethylene concentration,oxygen concentration,carbon dioxide concentration and 1,2-C_2H_4Cl_2 inhibitor concentration on the ethylene epoxidation process were investigated through orthogonal experiments.It was found that the effect of the reaction temperature was the most prominent.Under the optimized operating conditions of reaction temperature 240 ℃,1,2-C_2H_4Cl_2 concentration 0.7× 10~(-6)(x),ethylene concentration22.00%(x),oxygen concentration 6.50%(x),and carbon dioxide concentration 1.00%(x),the yield and selectivity of ethylene oxide in the ethylene epoxidation were 38.87%and 86.70%,respectively.
Ethylene epoxidation over B-type silver catalyst was studied in a micro constant temperature fixed bed integral reactor.The effects of reaction temperature,ethylene concentration,oxygen concentration,carbon dioxide concentration and 1,2-C_2H_4Cl_2 inhibitor concentration on the ethylene epoxidation process were investigated through orthogonal experiments.It was found that the effect of the reaction temperature was the most prominent.Under the optimized operating conditions of reaction temperature 240 ℃,1,2-C_2H_4Cl_2 concentration 0.7× 10~(-6)(x),ethylene concentration22.00%(x),oxygen concentration 6.50%(x),and carbon dioxide concentration 1.00%(x),the yield and selectivity of ethylene oxide in the ethylene epoxidation were 38.87%and 86.70%,respectively.
引文
[1]朱建民.环氧乙烷产业的发展[J].日用化学品科学,2009,32(11):9-11.
[2]李文臣,贾力威,刘焱楠.国内外环氧乙烷生产和市场分析[J].化学工业,2014,32(5):37-40.
[3]王海蔷,刘昱.环氧乙烷生产技术进展[J].化工科技,2012,20(3):67-70.
[4]李金兵,张志祥,陈建设,等.YS银催化剂的研制及工业应用[C]//第八届全国工业催化技术及应用年会论文集.西安:工业催化杂志社,2011:300-301.
[5]梁汝军,李建伟.B型银催化剂上乙烯环氧化宏观动力学研究[J].石油化工,2015,44(1):29-35.
[6]梁汝军,李建伟,李金兵,等.Y型银催化剂宏观动力学研究[J].化学工程,2015,43(1):51-54.
[7]Metcalf P L,Harriot P.Kinetics of Silver-Catalyzed Ethylene Oxidation[J].Ind Eng Chem Process Des Develop,1972,11(4):478-484.
[8]Borman P C,Westerterp K R.An Experimental Study of the Kinetics of the Selective Oxidation of Ethene over a Silver onα-Alumina Catalyst[J].Ind Eng Chem Res,1995,34(1):49-58.
[9]高政,谷彦丽,金积铨.乙烯在银催化剂上氧化本征动力学的研究[J].乙烯工业,2003,15(1):30-34.
[10]张丽萍,李晋鲁,朱起明.乙烯催化氧化制环氧乙烷反应动力学[J].石油化工,1986,15(3):160-166.
[11]梁汝军,李建伟,陈标华,等.YS-7型银催化剂上乙烯环氧化宏观动力学[J].河南大学学报,2007,37(2):141-146.
[12]张旭之,王松汉,戚以政.乙烯衍生物工学[M].北京:化学工业出版社,1995:174-175.
[13]李基涛,蔡丽芬.微量1,2-二氯乙烷在乙烯环氧化中的作用及其吸附态表征[J].分子催化,1992,6(2):114-119.
[14]Berty J M.Ethylene Oxide Synthesis[J].Appl Ind Catal,1983,1:207-238.
[15]Campbell C T.Chlorine Promoters in Selective Ethylene Epoxidation over Ag(111):A Comparison with Ag(110)[J].J Catal,1986,99(1):28-38.
[16]Kestenbaum H,de Oliveira A L,Schmidt W,et al.Silver-Catalyzed Oxidation of Ethylene to Ethylene Oxide in a Microreaction System[J].Ind Eng Chem Res,2002,41(4):710-719.
[17]Bowker M,Waugh K C.The Adsorption of Chlorine and Chloridation of Ag(111)[J].Surf Sci,1983,134(3):639-664.
[18]曹立礼,朱启明.银催化剂表面氧吸附特性及乙烯选择氧化机理模型[J].石油化工,1982,11(11):719-724.
[2]李文臣,贾力威,刘焱楠.国内外环氧乙烷生产和市场分析[J].化学工业,2014,32(5):37-40.
[3]王海蔷,刘昱.环氧乙烷生产技术进展[J].化工科技,2012,20(3):67-70.
[4]李金兵,张志祥,陈建设,等.YS银催化剂的研制及工业应用[C]//第八届全国工业催化技术及应用年会论文集.西安:工业催化杂志社,2011:300-301.
[5]梁汝军,李建伟.B型银催化剂上乙烯环氧化宏观动力学研究[J].石油化工,2015,44(1):29-35.
[6]梁汝军,李建伟,李金兵,等.Y型银催化剂宏观动力学研究[J].化学工程,2015,43(1):51-54.
[7]Metcalf P L,Harriot P.Kinetics of Silver-Catalyzed Ethylene Oxidation[J].Ind Eng Chem Process Des Develop,1972,11(4):478-484.
[8]Borman P C,Westerterp K R.An Experimental Study of the Kinetics of the Selective Oxidation of Ethene over a Silver onα-Alumina Catalyst[J].Ind Eng Chem Res,1995,34(1):49-58.
[9]高政,谷彦丽,金积铨.乙烯在银催化剂上氧化本征动力学的研究[J].乙烯工业,2003,15(1):30-34.
[10]张丽萍,李晋鲁,朱起明.乙烯催化氧化制环氧乙烷反应动力学[J].石油化工,1986,15(3):160-166.
[11]梁汝军,李建伟,陈标华,等.YS-7型银催化剂上乙烯环氧化宏观动力学[J].河南大学学报,2007,37(2):141-146.
[12]张旭之,王松汉,戚以政.乙烯衍生物工学[M].北京:化学工业出版社,1995:174-175.
[13]李基涛,蔡丽芬.微量1,2-二氯乙烷在乙烯环氧化中的作用及其吸附态表征[J].分子催化,1992,6(2):114-119.
[14]Berty J M.Ethylene Oxide Synthesis[J].Appl Ind Catal,1983,1:207-238.
[15]Campbell C T.Chlorine Promoters in Selective Ethylene Epoxidation over Ag(111):A Comparison with Ag(110)[J].J Catal,1986,99(1):28-38.
[16]Kestenbaum H,de Oliveira A L,Schmidt W,et al.Silver-Catalyzed Oxidation of Ethylene to Ethylene Oxide in a Microreaction System[J].Ind Eng Chem Res,2002,41(4):710-719.
[17]Bowker M,Waugh K C.The Adsorption of Chlorine and Chloridation of Ag(111)[J].Surf Sci,1983,134(3):639-664.
[18]曹立礼,朱启明.银催化剂表面氧吸附特性及乙烯选择氧化机理模型[J].石油化工,1982,11(11):719-724.