2-丁烯合成有机硫化剂的研究
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摘要
采用2-丁烯为主要成分的混合烯烃和单质硫为原料,利用高压间歇釜反应器在催化剂存在条件下制备有机硫化剂。实验过程中,考察了反应时间、反应温度、硫烯比、催化剂用量等工艺条件对有机硫化剂硫含量的影响,重点考察了胺类催化剂、秋兰姆催化体系和噻唑催化体系等几类催化剂对硫含量的影响,并利用固定床反应器考察了不同种类催化剂对有机硫化剂分解温度的影响。实验还用不同烯烃代替2-丁烯为原料合成有机硫化剂并进行了硫含量比较,通过正交实验优化了反应工艺条件。用浸渍法将有机硫化剂浸渍到加氢催化剂上,在间歇釜反应器中通氢气活化加氢催化剂,利用燃烧-中和滴定法测量加氢催化剂硫化度,并在高压微反装置中对加氢催化剂进行实际原料反应活性评价。活化过程中考察了活化升温速率、活化终温及活化终温恒温时间对加氢催化剂硫化度和活性的影响。
实验结果表明,采用2-丁烯为主要成分的混合烯烃和单质硫为原料合成的有机硫化剂硫含量高、分解温度范围宽,优于以C_9、C_(12)、C_(16)烯烃为原料合成的有机硫化剂。用于预硫化加氢催化剂时,加氢催化剂硫化度高、活性好。在使用2-硫醇基苯并噻唑、氧化锌和三乙胺复合体系为催化剂时,硫含量高于传统合成方法中不使用催化剂或以氢氧化钠为催化剂时有机硫化剂的硫含量。酸性物质不宜作催化剂使用。反应最佳工艺条件为:在反应温度170℃、反应时间2h、硫烯比1.9、二乙胺催化剂用量为烯烃摩尔量的0.4倍时,有机硫化剂硫含量可以达到26%以上。在浸渍实验中,采用混合硫化剂方式浸渍效果最好,且用二乙胺催化剂和噻唑催化体系合成的有机硫化剂预硫化加氢催化剂时,加氢催化剂硫化度最高、活性最好。确定的最佳活化工艺条件为:以10℃/min从室温升至150℃,恒温0.5h,再以2℃/min从150℃升至320℃,恒温2.5h,此时催化剂的硫化度为94.97%。
A kind of organic sulfurizing agent was synthesized by elemental sulfur and mixed olefins mainly composed of 2-butene in the high-pressure batch reactor in exist of catalysts. The effect of reaction time, reaction temperature, mol ratio of sulfur and catalyst amount on the sulfur content of the organic sulfurizing agent were investigated, especially the effect of different catalysts like amine catalyst, thiuram catalyst and thiazole catalyst on the sulfur content and on the decomposition temperature by fixed bed reactor. In addition, another organic sulfurizing agent was synthesized by other olefins instead of 2-butene, the sulfur content compared, optimum reaction conditions obtained by orthogonal experiment. The organic sulfurizing agent was added on the hydrogenation catalyst by means of impregnation, the sulfidity of catalysts measured by firing-correcting determination, the reactivity of practical materials evaluated in a high pressure micro-reactor. In the process, the effect of elevating rate of activation, final time of activation and constant temperature time on the sulfidity of the hydrogenation catalyst and its activity were studied.
The experimental results indicated that the sulfur content of the organic sulfurizing agent was high synthesized by elemental sulfur and mixed olefins mainly composed of 2-butene, and the range of decomposition temperature was wide, which was superior to the organic sulfurizing agent synthesized by C9、C12、C16 olefins. When the sulphurizing hydrogenation catalyst used, the sulfur content of hydrogenation catalyst was high, and the activity was good. When 2-hydrosulfobenzothiazol, zinc oxide and triethylamine were used as catalyst, the sulfur content was higher than that of traditional method without catalysts or taking sodium hydroxide as catalyst. Acid materials were not suitable for catalysts.The optimum process conditions was reaction temperature170℃, reaction time 2h, the amount of which was 0.4 times of mol amount of olefin, on the condition of which the sulfur content of the organic sulfurizing agent could reach a higher value above 26%. In the experiment of impregnation, the impregnating effect adopting mixing sulfurizing agent was best, moreover when the hydrogenation catalyst was sulfurized by the organic sulfurizing agent synthesized by diethylamine catalyst and thiazole catalyst, the sulfidity of the catalyst was high, and the activity was best. The optimum activation conditions were determined as follows: the temperature increasing from room temperature to 150℃at the speed of 10℃/min, then from 150℃to 320℃,constant temperature being 2.5h,in this time the sulfidity of the catalyst was 94.97%.
实验结果表明,采用2-丁烯为主要成分的混合烯烃和单质硫为原料合成的有机硫化剂硫含量高、分解温度范围宽,优于以C_9、C_(12)、C_(16)烯烃为原料合成的有机硫化剂。用于预硫化加氢催化剂时,加氢催化剂硫化度高、活性好。在使用2-硫醇基苯并噻唑、氧化锌和三乙胺复合体系为催化剂时,硫含量高于传统合成方法中不使用催化剂或以氢氧化钠为催化剂时有机硫化剂的硫含量。酸性物质不宜作催化剂使用。反应最佳工艺条件为:在反应温度170℃、反应时间2h、硫烯比1.9、二乙胺催化剂用量为烯烃摩尔量的0.4倍时,有机硫化剂硫含量可以达到26%以上。在浸渍实验中,采用混合硫化剂方式浸渍效果最好,且用二乙胺催化剂和噻唑催化体系合成的有机硫化剂预硫化加氢催化剂时,加氢催化剂硫化度最高、活性最好。确定的最佳活化工艺条件为:以10℃/min从室温升至150℃,恒温0.5h,再以2℃/min从150℃升至320℃,恒温2.5h,此时催化剂的硫化度为94.97%。
A kind of organic sulfurizing agent was synthesized by elemental sulfur and mixed olefins mainly composed of 2-butene in the high-pressure batch reactor in exist of catalysts. The effect of reaction time, reaction temperature, mol ratio of sulfur and catalyst amount on the sulfur content of the organic sulfurizing agent were investigated, especially the effect of different catalysts like amine catalyst, thiuram catalyst and thiazole catalyst on the sulfur content and on the decomposition temperature by fixed bed reactor. In addition, another organic sulfurizing agent was synthesized by other olefins instead of 2-butene, the sulfur content compared, optimum reaction conditions obtained by orthogonal experiment. The organic sulfurizing agent was added on the hydrogenation catalyst by means of impregnation, the sulfidity of catalysts measured by firing-correcting determination, the reactivity of practical materials evaluated in a high pressure micro-reactor. In the process, the effect of elevating rate of activation, final time of activation and constant temperature time on the sulfidity of the hydrogenation catalyst and its activity were studied.
The experimental results indicated that the sulfur content of the organic sulfurizing agent was high synthesized by elemental sulfur and mixed olefins mainly composed of 2-butene, and the range of decomposition temperature was wide, which was superior to the organic sulfurizing agent synthesized by C9、C12、C16 olefins. When the sulphurizing hydrogenation catalyst used, the sulfur content of hydrogenation catalyst was high, and the activity was good. When 2-hydrosulfobenzothiazol, zinc oxide and triethylamine were used as catalyst, the sulfur content was higher than that of traditional method without catalysts or taking sodium hydroxide as catalyst. Acid materials were not suitable for catalysts.The optimum process conditions was reaction temperature170℃, reaction time 2h, the amount of which was 0.4 times of mol amount of olefin, on the condition of which the sulfur content of the organic sulfurizing agent could reach a higher value above 26%. In the experiment of impregnation, the impregnating effect adopting mixing sulfurizing agent was best, moreover when the hydrogenation catalyst was sulfurized by the organic sulfurizing agent synthesized by diethylamine catalyst and thiazole catalyst, the sulfidity of the catalyst was high, and the activity was best. The optimum activation conditions were determined as follows: the temperature increasing from room temperature to 150℃at the speed of 10℃/min, then from 150℃to 320℃,constant temperature being 2.5h,in this time the sulfidity of the catalyst was 94.97%.
引文
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[3] Emmanuel Arretz.Process for the preparation of organic disulphides and polysulphides [P].US5068445,1991-11-26.
[4]王月霞.加氢催化剂的器外预硫化[J].炼油设计,2000,30(7):57～58.
[5]蒲延芳,张志华.加氢催化剂预硫化技术探讨[J].化学工程师,1996,3(54):29～31.
[6]黄锦霞.硫化异丁烯的合成[J].精细化工,1985,(5):25～27.
[7]贺英.硫化异丁烯的生产工艺研究[J].甘肃化工,1999,(1):14～18.
[8]杨景培,马先贵.闭路无污染工艺制备硫化极压剂的研究[J].润滑油,1997,12(3):17～30.
[9]冯铱,张白玲,苏刚.高压硫化异丁烯的研制[J].润滑油,2001,16(1):37～40.
[10]张白玲,伏喜胜.国外硫化烯烃的生成工艺改进及其代用品[J].润滑油,1997,12(6):44～49.
[11]亨利.贡戈拉,伊夫.达次.有机多硫化物的制备方法[P].CN1009925B,1990-10-10.
[12]于守智,高晓东,陈若雷.一种加氢催化剂的预硫化方法[P].CN1417299A,2003-5-14.
[13]于守智,高晓冬,陈若雷.一种加氢催化剂预硫化方法[P].CN1262305A,2000-8-9.
[14]刘雪玲,兰玲,蒋广安,等.一种加氢催化剂的预硫化方法[P].CN1611577A,2005-5-4.
[15] Joseph A Arvizzigno,et al.Sulfurized olefins[P].US005338468A,1994-8-14.
[16] Micael Gerald Romanelli,Brooklyn,N.Y.Sulfurized olefin composition and its method of preparation[P].US005849677A,1998-12-15.
[17] Eika W.Qian,Shigeru Yamada,Jeayoung Lee,et al.Synthesis of polysulfides using diisobutylene,sulfur,and hydrogen sulfide over solid base catalysts.Applied Catalysis A:General.2003,(253):15～27.
[18]赵野,胡胜,于春梅.加氢催化剂预硫化技术评述[J].精细石油化工进展,2005,6(8):49～52.
[19] Menno de Wind,J Heinerman,Seck leong Lee,et al.Air quality and economics spur use of presulfided catalysts[J].Oil&Gas Journal,1992,90(8):49～53.
[20] W.霍夫曼著,王梦蛟,曾泽新,等译.橡胶硫化与硫化配合剂[M].1975:88～236.
[21]赵光辉,任敦泾,李建忠,等.我国橡胶助剂工业的现状及发展[J].世界橡胶工业,2007,34(4):32～37.
[22]李汉堂.国内外橡胶助剂工业的发展[J].现代橡胶技术,2006,32(5):1～8.
[23]郭炳,魏清林.我国橡胶助剂发展近况[J].山西化工,2004,24(1):59～61.
[24]姚莹.国内橡胶助剂研究开发情况及发展趋势[P].SCI/TECH INFORMATION DEVELOPMENT﹠ ECONOMY,2003,13(8):74～75.
[25] James E.Shaw,ea al.Preparation of high purity polysulfides[P].US5206439,1993-4-27.
[26] Shaw,Jame E.Stable polysulfides and process therefor[P].US5218147,1993-6-8.
[27] J.F.德沃,G.弗雷米.稳定和脱臭的有机多硫化物的生产[P].CN1228418A,1999-9-15.
[28] Shaw,Jame E.Production of polysulfides[P].US5403961,1995-4-4.
[29] Shaw,Jame E.Preparation of high purity polysulfides[P].US5155275,1992-10-13.
[30] Shaw,Jame E.Process producing organic polysulfide compounds[P].US5530163,1996-6-25.
[31]陈日初.燃烧中和滴定法连续测定锌精矿、锌焙砂等物质中的硫[J].有色冶金,2001,(5):94～95.
[32] C.布伦,T.肖莱,G.弗雷米.加氢处理催化剂的预硫化方法[P].CN1270988A,2000-10-25.
[33] P.杜弗雷斯内,B.勒戈尔,G.贝力比.处理烃的催化剂预硫化方法[P].CN1082591A,1994-2-23.
[34]孙万付,张喜文,马波,等.硫化条件对加氢裂化催化剂金属硫化度的影响[J].燃料化学学报,2000,28(5):406～408.
[35]李彦鹏,刘大鹏,柴永明,等.器外预硫化型MoNiP/γ-Al2O3催化剂的加氢脱硫性能研究[J].石油炼制与化工,2006,37(5):15～19.
[36] Samuel Texier,Gilles Berhault,Guy Perot et al.Activation of alumina-supported hydrotreating catalysts by prganosylfides:comparison with H2S and effect of differentsolvents[J].Journal of Catalysis,2004,(223):404～418.
[37] Kirk E.Davis,Euclid,Ohio.Sulfurized Compositions[P].US4191659,1980-4-4.
[38]李高峰,王文婷.预硫化加氢催化剂在加氢改质装置上的工业应用[J].工业催化,2005,13:148～152.
[39]莫里斯.博尔恩,吕西安娜.布里葵,雅克.拉勒芒,等.多硫烯烃组合物,其制法和作为润滑油添加剂的应用[P].CN87107001A,1988-4-27.
[40]周宏标.微量硫化氢和硫醇的汞量测定法[J].湖北化工,2000,(5):47～48.
[41] Andrew G.Horodysky,Cherry Hill,Phillip S.Landis,et al.Process for making sulfurized olefins[P].US4225488,1980-9-30.
[42]薛全康,郭慎远,马步勇,等.用于钴钼系催化剂硫化的固体硫化剂及制备[P].CN1048175A,1991-1-2.
[43]王群,文尚军.采用固体硫化剂的加氢催化剂器内预硫化新技术[J].天然气化工,2004,29(4):58～61.
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