高品质润滑油基础油(简称基础油)的生产是炼油企业提升经济效益的重要途径,烷基化技术是生产基础油的重要方法之一。本研究选用安全环保的氯铝酸离子液体催化异丁烷与1-十六烯的烷基化反应,系统考察离子液体的组成以及烷基化反应温度、...高品质润滑油基础油(简称基础油)的生产是炼油企业提升经济效益的重要途径,烷基化技术是生产基础油的重要方法之一。本研究选用安全环保的氯铝酸离子液体催化异丁烷与1-十六烯的烷基化反应,系统考察离子液体的组成以及烷基化反应温度、离子液体与反应物体积比(酸烃体积比)、搅拌速率、异丁烷与1-十六烯摩尔比(烷烯摩尔比)等反应条件对其催化烷基化反应性能的影响。结果表明,以优化的复合离子液体[Et_(3)NH]Cl-1.6AlCl_(3)-0.3CuCl为催化剂,适宜的酸烃体积比、提高烷烯摩尔比、加快搅拌速率、降低反应温度,均可以有效提升1-十六烯的转化率,显著增加目标产物C 20组分的选择性。在反应温度为15℃、搅拌速率为1300 r min、酸烃体积比为1∶2.8、烷烯摩尔比为30∶1的最佳反应条件下,1-十六烯的转化率可达99.8%,C_(20)组分的选择性在92%以上,烷基化油满足Ⅲ+类润滑油基础油的质量要求。展开更多
轻烃异构化一般以C_(5)和C_(6)烃为原料,C_(7)及C_(7)以上烃类在异构化过程中由于存在较为剧烈的裂化反应,致使异构化油收率较低。作为一种新型低温轻烃异构化催化剂,离子液体对大分子烃类原料的适应性不佳。因此,在大分子烃类异构化过...轻烃异构化一般以C_(5)和C_(6)烃为原料,C_(7)及C_(7)以上烃类在异构化过程中由于存在较为剧烈的裂化反应,致使异构化油收率较低。作为一种新型低温轻烃异构化催化剂,离子液体对大分子烃类原料的适应性不佳。因此,在大分子烃类异构化过程中,抑制副反应、提高异构化油收率一直是研究的难点和重点。基于离子液体催化烷烃异构化反应机理,通过异丁烷循环抑制副反应、促进异构化反应的进行,进而降低异构化产物中C_(4)烷烃的含量,提高异构化油的收率。系统考察了异丁烷引入量、反应温度、反应时间、搅拌速率以及酸烃比等工艺条件对氯铝酸离子液体催化正庚烷异构化反应的影响规律。结果表明,体系中大量异丁烷的循环提高了氢转移速率,抑制了裂化、歧化等副反应,使副产物C 4组分的含量大幅降低。在异丁烷引入量为正庚烷体积的30%、反应温度为50℃、反应时间为1 h、搅拌速率为1500 r min和酸烃比(离子液体与正庚烷体积比)为1的条件下,正庚烷转化率达到91.0%,异构烷烃选择性和液体收率分别达到87.2%和93.5%;与未引入异丁烷体系相比,正庚烷转化率相近时,引入异丁烷体系的异构烷烃选择性和液体收率分别提高了16.0百分点和14.8百分点。展开更多
A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active pha...A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPR technique, with their HDS activity being investigated with thiophene as a model substrate. For the sulfided Mo 0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 K and attributed to the hydrogenation of the so called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mo x+ sites on the MoS 2 phase(MoS 2 slab). With the introduction of nickel into the active phase of the sulfided Mo 0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/ γ Al 2O 3 catalysts, the thiophene HDS rate and the quantity of hydrogen sulfide evolved during TPR process increase monotonously with the atomic ratio of molybdenum to nickel in the form of [ n (Ni)+ n (Mo)]/ n (Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni Mo S slab due to the loss of S during TPR process and vacancies or sites related to the H 2S evolution peak II should be regarded as the mainly active reaction centers of thiophene HDS.展开更多
文摘高品质润滑油基础油(简称基础油)的生产是炼油企业提升经济效益的重要途径,烷基化技术是生产基础油的重要方法之一。本研究选用安全环保的氯铝酸离子液体催化异丁烷与1-十六烯的烷基化反应,系统考察离子液体的组成以及烷基化反应温度、离子液体与反应物体积比(酸烃体积比)、搅拌速率、异丁烷与1-十六烯摩尔比(烷烯摩尔比)等反应条件对其催化烷基化反应性能的影响。结果表明,以优化的复合离子液体[Et_(3)NH]Cl-1.6AlCl_(3)-0.3CuCl为催化剂,适宜的酸烃体积比、提高烷烯摩尔比、加快搅拌速率、降低反应温度,均可以有效提升1-十六烯的转化率,显著增加目标产物C 20组分的选择性。在反应温度为15℃、搅拌速率为1300 r min、酸烃体积比为1∶2.8、烷烯摩尔比为30∶1的最佳反应条件下,1-十六烯的转化率可达99.8%,C_(20)组分的选择性在92%以上,烷基化油满足Ⅲ+类润滑油基础油的质量要求。
文摘轻烃异构化一般以C_(5)和C_(6)烃为原料,C_(7)及C_(7)以上烃类在异构化过程中由于存在较为剧烈的裂化反应,致使异构化油收率较低。作为一种新型低温轻烃异构化催化剂,离子液体对大分子烃类原料的适应性不佳。因此,在大分子烃类异构化过程中,抑制副反应、提高异构化油收率一直是研究的难点和重点。基于离子液体催化烷烃异构化反应机理,通过异丁烷循环抑制副反应、促进异构化反应的进行,进而降低异构化产物中C_(4)烷烃的含量,提高异构化油的收率。系统考察了异丁烷引入量、反应温度、反应时间、搅拌速率以及酸烃比等工艺条件对氯铝酸离子液体催化正庚烷异构化反应的影响规律。结果表明,体系中大量异丁烷的循环提高了氢转移速率,抑制了裂化、歧化等副反应,使副产物C 4组分的含量大幅降低。在异丁烷引入量为正庚烷体积的30%、反应温度为50℃、反应时间为1 h、搅拌速率为1500 r min和酸烃比(离子液体与正庚烷体积比)为1的条件下,正庚烷转化率达到91.0%,异构烷烃选择性和液体收率分别达到87.2%和93.5%;与未引入异丁烷体系相比,正庚烷转化率相近时,引入异丁烷体系的异构烷烃选择性和液体收率分别提高了16.0百分点和14.8百分点。
文摘A series of sulfided tertiary NiMoP/ γ Al 2O 3 catalysts with different contents of MoO 3 were prepared by using molybdophosphoric acid of Keggin structure(H 3PMo 12 O 40 ) and nickel nitrate as origins of active phase components of molybdenum, phosphorus and nickel, and characterized by TPR technique, with their HDS activity being investigated with thiophene as a model substrate. For the sulfided Mo 0 catalyst containing no nickel as promoter, the only hydrogen sulfide evolution peak Ⅰ is observed at 462 K and attributed to the hydrogenation of the so called edge sulfur atoms chemisorbed on coordinatively unsaturated(cus) Mo x+ sites on the MoS 2 phase(MoS 2 slab). With the introduction of nickel into the active phase of the sulfided Mo 0 catalyst and with the increase of the molybdenum loading, a new hydrogen sulfide evolution peak Ⅱ gradually develops at the low temperature side of the peak Ⅰ, at the same time accompanied by both the increase of the area ratio of the peak Ⅱ to the peak Ⅰ and the shift of the hydrogen sulfide evolution maximum rate to lower temperatures, which may imply the existence of two kinds of active centers related to molybdenum and nickel respectively and the synergic action between the two centers above. It should be noted that for the sulfided NiMoP/ γ Al 2O 3 catalysts, the thiophene HDS rate and the quantity of hydrogen sulfide evolved during TPR process increase monotonously with the atomic ratio of molybdenum to nickel in the form of [ n (Ni)+ n (Mo)]/ n (Ni). On the basis of the results here, the conclusion may be reached that the two kinds of vacancies can be formed on the edge of Ni Mo S slab due to the loss of S during TPR process and vacancies or sites related to the H 2S evolution peak II should be regarded as the mainly active reaction centers of thiophene HDS.
