乙烯—硫化氢催化加成合成乙硫醇
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摘要
以γ-Al2O3为载体、以钼酸铵和硝酸钴为浸渍组分,采用等体积浸渍法制备了一系列Co-Mo/γ-Al2O3催化剂,采用XRD、XPS和NH3-TPD等技术对制备的催化剂进行了表征。
采用固定床反应器考察了反应温度、反应压力、原料的进料组成和乙烯的气时空速等反应条件对乙烯和硫化氢合成乙硫醇反应的影响,初步确定了适宜的催化剂评价条件为:反应温度240°C,反应压力1.4MPa,H2S/C2H4(摩尔比)为3:1,乙烯的气时空速300h-1。
在选定的评价条件下,评价了Co-Mo/γ-Al2O3催化剂对乙烯和硫化氢合成乙硫醇反应的催化性能,考察了催化剂的组成和制备条件对催化剂性能的影响。结果表明,MoO3和CoO的适宜负载量均为10wt%,在500°C下焙烧的催化剂活性较好。
采用正交实验,对反应温度、反应压力、原料的进料组成和乙烯的气时空速等反应条件做了进一步研究,结果表明,适宜的反应条件为:反应温度265°C,反应压力1.6MPa,H2S/C2H4(摩尔比)为2:1,乙烯的气时空速为240h-1。
Usingγ-alumina as support, ammonium molybdate and cobalt nitrate as impregnated precursor components, a series of Co-Mo/γ-Al2O3 samples were prepared by incipient-wetness impregnation method, and their physico-chemical performances were characterized by XRD, XPS and NH3-TPD techniques.
The fixed bed reactor was used to test the effect of reaction temperature, reaction pressure, gas hourly space velocity of ethylene and molar ratio of reactants on the catalytic activity for the addition of hydrogen sulfide to ethylene. The reaction condition of temperature of 240°C, pressure of 1.4MPa, GHSV of ethylene of 300h-1 and molar ratio of hydrogen sulfide to ethylene of 3:1 was estimated as the proper evaluation condition.
The activity of Co-Mo/γ-Al2O3 catalyst for ethyl mercaptan synthesis from hydrogen sulfide and ethylene was evaluated, and the influence of the composition and the preparation condition of the catalysts on the catalyst performences were investigated under above evaluation conditions. The result showed that the catalyst calcined at 500°C was better, the optimal content of MoO3 and CoO loading on the catalyst were both 10wt%.
Orthogonal experiment was designed to optimize the reaction condition and the result showed that the optimal reaction conditions were temperature of 265°C, pressure of 1.6MPa, GHSV of ethylene of 240h-1 and molar ratio of hydrogen sulfide to ethylene of 2:1.
采用固定床反应器考察了反应温度、反应压力、原料的进料组成和乙烯的气时空速等反应条件对乙烯和硫化氢合成乙硫醇反应的影响,初步确定了适宜的催化剂评价条件为:反应温度240°C,反应压力1.4MPa,H2S/C2H4(摩尔比)为3:1,乙烯的气时空速300h-1。
在选定的评价条件下,评价了Co-Mo/γ-Al2O3催化剂对乙烯和硫化氢合成乙硫醇反应的催化性能,考察了催化剂的组成和制备条件对催化剂性能的影响。结果表明,MoO3和CoO的适宜负载量均为10wt%,在500°C下焙烧的催化剂活性较好。
采用正交实验,对反应温度、反应压力、原料的进料组成和乙烯的气时空速等反应条件做了进一步研究,结果表明,适宜的反应条件为:反应温度265°C,反应压力1.6MPa,H2S/C2H4(摩尔比)为2:1,乙烯的气时空速为240h-1。
Usingγ-alumina as support, ammonium molybdate and cobalt nitrate as impregnated precursor components, a series of Co-Mo/γ-Al2O3 samples were prepared by incipient-wetness impregnation method, and their physico-chemical performances were characterized by XRD, XPS and NH3-TPD techniques.
The fixed bed reactor was used to test the effect of reaction temperature, reaction pressure, gas hourly space velocity of ethylene and molar ratio of reactants on the catalytic activity for the addition of hydrogen sulfide to ethylene. The reaction condition of temperature of 240°C, pressure of 1.4MPa, GHSV of ethylene of 300h-1 and molar ratio of hydrogen sulfide to ethylene of 3:1 was estimated as the proper evaluation condition.
The activity of Co-Mo/γ-Al2O3 catalyst for ethyl mercaptan synthesis from hydrogen sulfide and ethylene was evaluated, and the influence of the composition and the preparation condition of the catalysts on the catalyst performences were investigated under above evaluation conditions. The result showed that the catalyst calcined at 500°C was better, the optimal content of MoO3 and CoO loading on the catalyst were both 10wt%.
Orthogonal experiment was designed to optimize the reaction condition and the result showed that the optimal reaction conditions were temperature of 265°C, pressure of 1.6MPa, GHSV of ethylene of 240h-1 and molar ratio of hydrogen sulfide to ethylene of 2:1.
引文
[1]徐寿昌,有机化学,北京:高等教育出版社,1993, 233~234
[2] Wiezevich P. J., Turner L. B., Frolich P. K., Sulfur compounds derived from petroleum, Industrial and engineering chemistry, 1993, 25(3): 295~296
[3] Roy K. M., Thiols and organic sulfides, Ullmann's Encyclopedia of Industrial Chemistry, 2000, 1~15
[4]张镜吾,化工百科全书-第10卷,北京:化学工业出版社,1996, 739~744
[5]史卫国,黄清臻,徐之明,甲拌磷的合成研究,河北化工,1996, 4: 22~24
[6]郝立勇,陈玲,王玉民等,乙烷磺酰氯的合成,泰山医学院学报,2004, 25(4): 270~272
[7]霍竹林,苏红维,高淑捧等,氯甲酸乙硫醇酯的合成,河北化工,2004, 6: 48
[8]郝立勇,朱晓慧,齐永秀等,乙硫醇氯化法合成乙烷磺酰胺,精细化工,2002, 19(7): 421~423
[9]刘红霞,胡卫兵,张云才,二乙基四硫的合成研究,精细化工中间体,2004, 34(2): 49~50
[10]何磊,硫化氢下游产品开发与应用,化工中间体,2003, 8: 10~14
[11]张珍明,高纯度对叔丁基苄硫醇的合成,化工时刊,2000, 7: 42
[12] Fields E. K., Production of mercaptans, US4347384, 1982-8-31
[13] Hilliso F., Miller E., Synthesis of mercaptans, I&EC Process Design and Development, 1962, 1(4): 271~276
[14]杨秋华,傅希贤,浅谈原子经济,《化学通报》网络版,2001, 9
[15] Sharipov A. K., Mercaptans from gas condensates and crude oils, Chemistry and Technology of Fuels and Oils, 2002, 38(4): 280~285
[16]徐琼,尹笃林,硫化氢加成直接合成硫醇的催化剂研究进展,精细化工中间体,2005, 35(1): 17~19
[17] Eaton J. L., Trenton, Condensation of olefinic compounds with hydrogen sulfide, US2443852, 1948-06-22
[18] Fried H. E., Secondary thiols, EP122654, 1984-10-24
[19] Buchholz B., Tertiary mercaptans using zeolite catalysts, US4102931, 1978-07-25
[20] Giacobbe T. J., Process for making tertiary-thiols, US5453544, 1995-09-26
[21] Arretz E., Mirassou A., Process of synthesis of mercaptans from olefins and hydrogen sulphide by heterogeneous catalysis, US4565893, 1986-01-21
[22] Kubicek D. H., Mercaptans by addition of hydrogen sulfide to olefins in presence of carbon disulfide, US3963785, 1976-06-15
[23] Sattich W. E., Selective production of ethyl mercaptan, US5352838, 1994-10-04
[24] Buchholz B., Goshorn R. H., Process for the preparation of ethyl mercaptan and diethyl sulfide, US3257464, 1966-06-21
[25] Standard Oil Development Co, Organic mercaptans and sulfide, Brit 602238, 1948-05-24
[26] Devaux J. F., Precess for manufacturing sulphurized olefins, US6544936, 2003-04-08
[27] Perozzi E. F., Papay. G.., Mercaptan production, US4582939, 1986-04-15
[28]宋丽娟,杜桐林,分子筛醚化催化剂的发展动态,石油炼制与化工,1994, 25(4): 31~35
[29]丛浦珠,苏克曼,分析化学手册,北京:化学工业出版社,2000, 630
[30] Bian Guo-zhu, Fu Yi-lu, Ma Yun-sheng, Structure of Co-K-Mo/γ-Al2O3 catalysts and their catalytic activity for mixed alcohols synthesis. Catalysis Today, 51(1999): 187~193
[31]李玉敏,工业催化原理,天津:天津大学出版社,1992, 114
[32]林仁存,杨意泉,袁友珠等,钾促进钻钼耐硫CO变换催化剂的XPS和TPR表征,应用化学,2001, 18(1): 25~28
[33] Moon H. K., Choo K. H., Low-temperature continuous wet oxidation of trichloroethylene over CoOx/TiO2 catalysts, Catalysis Communications, 2007, 8(3): 462~466
[34]陈泳,张凯锋,景欢旺,一种制备掺杂纳米VO2的新方法,甘肃科学学报,2006, 18(2): 38~40
[35] Weber T., Muijsers J. C., Niemantsverdriet J.W., Physical Chemical, 1995, 99(22): 9194
[36] Patterson T. A., Carver J. C., Leyden D. E. et al., Physical Chemical, 1976, 80(15): 1700
[37] Cook C. M., Albright D. E., Savidakis M. C., Production of mercaptans using heterogeneous acidic catalysts, US6162952, 2000-12-19
[38]黄仲涛,工业催化,北京:化学工业出版社,1994, 37
[39]李小定,陈劲松,Co-Mo系宽温耐硫变换催化剂,小氮肥设计技术,2005, 26(2): 12~17
[40]王法强,丙烯腈常压气相加氢氧化铝负载钯、镍催化剂及动力学研究:[硕士学位论文],上海,上海师范大学,2003
[41] Al-Zeghayer Y. S., Sunderland P., Masry W. A., Activity of Co-Mo/γ-Al2O3 as a catalyst in hydrodesulfurization: effects of Co/Mo ratio and drying condition. Applied Catalysis A: General, 2005, 282(1): 163-171
[42] Al-Zeghayer Y. S., Jibril B. Y., On the effects of calcination conditions on the surface and catalytic properties ofγ-Al2O3-supported Co-Mo hydrodesulfurization catalysts. Applied Catalysis A: General, 2005, 292: 287~294
[43]黄玉媛,杜上鉴,精细化工配方研究与产品配置技术,广州:广东科技出版社,2003, 227~242
[2] Wiezevich P. J., Turner L. B., Frolich P. K., Sulfur compounds derived from petroleum, Industrial and engineering chemistry, 1993, 25(3): 295~296
[3] Roy K. M., Thiols and organic sulfides, Ullmann's Encyclopedia of Industrial Chemistry, 2000, 1~15
[4]张镜吾,化工百科全书-第10卷,北京:化学工业出版社,1996, 739~744
[5]史卫国,黄清臻,徐之明,甲拌磷的合成研究,河北化工,1996, 4: 22~24
[6]郝立勇,陈玲,王玉民等,乙烷磺酰氯的合成,泰山医学院学报,2004, 25(4): 270~272
[7]霍竹林,苏红维,高淑捧等,氯甲酸乙硫醇酯的合成,河北化工,2004, 6: 48
[8]郝立勇,朱晓慧,齐永秀等,乙硫醇氯化法合成乙烷磺酰胺,精细化工,2002, 19(7): 421~423
[9]刘红霞,胡卫兵,张云才,二乙基四硫的合成研究,精细化工中间体,2004, 34(2): 49~50
[10]何磊,硫化氢下游产品开发与应用,化工中间体,2003, 8: 10~14
[11]张珍明,高纯度对叔丁基苄硫醇的合成,化工时刊,2000, 7: 42
[12] Fields E. K., Production of mercaptans, US4347384, 1982-8-31
[13] Hilliso F., Miller E., Synthesis of mercaptans, I&EC Process Design and Development, 1962, 1(4): 271~276
[14]杨秋华,傅希贤,浅谈原子经济,《化学通报》网络版,2001, 9
[15] Sharipov A. K., Mercaptans from gas condensates and crude oils, Chemistry and Technology of Fuels and Oils, 2002, 38(4): 280~285
[16]徐琼,尹笃林,硫化氢加成直接合成硫醇的催化剂研究进展,精细化工中间体,2005, 35(1): 17~19
[17] Eaton J. L., Trenton, Condensation of olefinic compounds with hydrogen sulfide, US2443852, 1948-06-22
[18] Fried H. E., Secondary thiols, EP122654, 1984-10-24
[19] Buchholz B., Tertiary mercaptans using zeolite catalysts, US4102931, 1978-07-25
[20] Giacobbe T. J., Process for making tertiary-thiols, US5453544, 1995-09-26
[21] Arretz E., Mirassou A., Process of synthesis of mercaptans from olefins and hydrogen sulphide by heterogeneous catalysis, US4565893, 1986-01-21
[22] Kubicek D. H., Mercaptans by addition of hydrogen sulfide to olefins in presence of carbon disulfide, US3963785, 1976-06-15
[23] Sattich W. E., Selective production of ethyl mercaptan, US5352838, 1994-10-04
[24] Buchholz B., Goshorn R. H., Process for the preparation of ethyl mercaptan and diethyl sulfide, US3257464, 1966-06-21
[25] Standard Oil Development Co, Organic mercaptans and sulfide, Brit 602238, 1948-05-24
[26] Devaux J. F., Precess for manufacturing sulphurized olefins, US6544936, 2003-04-08
[27] Perozzi E. F., Papay. G.., Mercaptan production, US4582939, 1986-04-15
[28]宋丽娟,杜桐林,分子筛醚化催化剂的发展动态,石油炼制与化工,1994, 25(4): 31~35
[29]丛浦珠,苏克曼,分析化学手册,北京:化学工业出版社,2000, 630
[30] Bian Guo-zhu, Fu Yi-lu, Ma Yun-sheng, Structure of Co-K-Mo/γ-Al2O3 catalysts and their catalytic activity for mixed alcohols synthesis. Catalysis Today, 51(1999): 187~193
[31]李玉敏,工业催化原理,天津:天津大学出版社,1992, 114
[32]林仁存,杨意泉,袁友珠等,钾促进钻钼耐硫CO变换催化剂的XPS和TPR表征,应用化学,2001, 18(1): 25~28
[33] Moon H. K., Choo K. H., Low-temperature continuous wet oxidation of trichloroethylene over CoOx/TiO2 catalysts, Catalysis Communications, 2007, 8(3): 462~466
[34]陈泳,张凯锋,景欢旺,一种制备掺杂纳米VO2的新方法,甘肃科学学报,2006, 18(2): 38~40
[35] Weber T., Muijsers J. C., Niemantsverdriet J.W., Physical Chemical, 1995, 99(22): 9194
[36] Patterson T. A., Carver J. C., Leyden D. E. et al., Physical Chemical, 1976, 80(15): 1700
[37] Cook C. M., Albright D. E., Savidakis M. C., Production of mercaptans using heterogeneous acidic catalysts, US6162952, 2000-12-19
[38]黄仲涛,工业催化,北京:化学工业出版社,1994, 37
[39]李小定,陈劲松,Co-Mo系宽温耐硫变换催化剂,小氮肥设计技术,2005, 26(2): 12~17
[40]王法强,丙烯腈常压气相加氢氧化铝负载钯、镍催化剂及动力学研究:[硕士学位论文],上海,上海师范大学,2003
[41] Al-Zeghayer Y. S., Sunderland P., Masry W. A., Activity of Co-Mo/γ-Al2O3 as a catalyst in hydrodesulfurization: effects of Co/Mo ratio and drying condition. Applied Catalysis A: General, 2005, 282(1): 163-171
[42] Al-Zeghayer Y. S., Jibril B. Y., On the effects of calcination conditions on the surface and catalytic properties ofγ-Al2O3-supported Co-Mo hydrodesulfurization catalysts. Applied Catalysis A: General, 2005, 292: 287~294
[43]黄玉媛,杜上鉴,精细化工配方研究与产品配置技术,广州:广东科技出版社,2003, 227~242