CN108452843B - 一种柴油加氢精制催化剂及其制备方法和应用 - Google Patents
一种柴油加氢精制催化剂及其制备方法和应用 Download PDFInfo
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- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
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- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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Abstract
本发明公开了一种柴油加氢精制催化剂及其制备方法和应用。该催化剂以催化剂质量为100％计，包含TS‑1分子筛1～30％，γ‑Al2O3 20～50％，氧化锆0.01～10％，石墨烯0.01～5％，以金属氧化物计的杂多酸10～40％；催化剂比表面积为250～500m2/g，孔容0.5～0.8mL/g。该催化剂具备特定孔径、较大孔容，较高加氢脱硫活性等特点，可作为柴油加氢精制催化剂使用。
Description
技术领域
本发明涉及一种柴油加氢精制催化剂及其制备方法和应用，适用于石油炼制领域中柴油加氢精制过程。
背景技术
目前，加氢脱硫是降低柴油原料中硫含量的主要方法，可以同时进行加氢脱硫、加氢脱氮、烯烃饱和等反应，生产国Ⅴ柴油或其调和组分。
2017年我国全面实行国Ⅴ车用柴油标准，计划2019年实行国Ⅵ车用柴油标准。柴油原料中催化柴油、焦化柴油与直馏柴油相比，具有更高的硫、氮、烯烃含量，更难于加工。为了满足更严格标准的要求，同时应对原油劣质化趋势，新型高活性柴油加氢催化剂的研发势在必行。
目前柴油加氢精制催化剂一般是以氧化铝为载体，以VIll族和VIB族金属元素为活性组分，也有为了提高催化剂的活性和稳定性，对载体进行改进，例如以氧化铝氧化硅为载体的，或者是加入助剂，一般是P、F、B、Si、Ti、Zr等。大多以改性氧化铝为载体，以Mo、W为主活性金属，Co、Ni为助活性组分。
中国专利CN1123765.1公开了一种柴油加氢处理催化剂，该催化剂含有一种载体和负载在载体上的钼和/或钨及镍和/或钴，其特征在于，所述载体由氧化铝和沸石组成，氧化铝与沸石的重量比为90:10～50:50，所述氧化铝是由小孔氧化铝和大孔氧化铝按照75:25～50:50的重量比复合而成的氧化铝。
中国专利CN96120988.7公开了一种柴油加氢转化催化剂，以氧化铝和Y型分子筛为载体，含有至少一种VIB族金属和至少一种VIll族金属，其特征在于催化剂载体组成为氧化铝40～90w％、无定形硅铝0～20w％，分子筛5～40w％。
发明内容
本发明的目的在于提供一种柴油加氢精制催化剂及其制备方法和应用。
为实现上述目的，本发明提供一种柴油加氢精制催化剂，以催化剂质量为100％计，包含TS-1分子筛1～30％，γ-Al2O3 20～50％，氧化锆0.01～10％，石墨烯0.01～5％，以金属氧化物计的杂多酸10～40％；催化剂比表面积为250～500m2/g，孔容0.5～0.8mL/g。。
本发明所述的柴油加氢精制催化剂，所述杂多酸为M6[WM3(H2O)2(ZnW9O34)2]，其中，M为Mn、Co、Ni和Cu中的一种或几种。
为实现上述目的，本发明还提供一种所述的柴油加氢精制催化剂的制备方法，包括以下步骤：
(1)将氧化铝粉、TS-1分子筛、氧化锆混合均匀，然后加入石墨烯，混合均匀后再加入助挤剂和粘合剂，再次混合均匀，挤条成型，冷冻干燥或真空干燥后，焙烧制得Al2O3-TS-1-ZrO2-石墨烯复合氧化物载体；
(2)用含有活性金属的杂多酸配成浸渍液，将制得的载体进行等体积浸渍，冷冻干燥或真空干燥后，焙烧制得柴油加氢精制催化剂。
本发明所述的柴油加氢精制催化剂的制备方法，所述杂多酸为M6[WM3(H2O)2(ZnW9O34)2]，其中，M为Mn、Co、Ni和Cu中的一种或几种。
本发明所述的柴油加氢精制催化剂的制备方法，其特征在于，所制得的催化剂包含活性金属W及Mn、Co、Ni和Cu中的一种或几种和载体Al2O3-TS-1-ZrO2-石墨烯复合氧化物，以活性金属氧化物计，活性金属占催化剂重量的10～40％。
本发明所述的柴油加氢精制催化剂的制备方法，所制得的催化剂直径为0.8mm～2.0mm或大于2.5mm。
本发明所述的柴油加氢精制催化剂的制备方法，所制得的催化剂直径为1.0mm～1.8mm。
本发明所述的柴油加氢精制催化剂的制备方法，所制得的催化剂外形为条形、三叶草形、颗粒状或齿球形。
本发明所述的柴油加氢精制催化剂的制备方法，步骤(2)中载体浸渍时间为0.5～5小时，焙烧温度为400～550℃，焙烧时间为2～6小时。
为实现上述目的，本发明还提供一种所述的柴油加氢精制催化剂的应用，催化剂经硫化后用作柴油加氢精制催化剂，反应条件为反应温度为280～380℃，氢分压为6.0～9.0MPa，氢油体积比300:1～600:1，体积空速为0.5～3.0h-1。
本发明所述的催化剂，通过TS-1、氧化锆含量调整载体酸性，采用含杂多酸为浸渍液，减弱载体与活性组分的相互作用，制备活性组分高度分散的柴油加氢精制催化剂，显著提高催化剂的加氢脱硫活性，适用于直馏柴油、催化柴油、焦化柴油或其混合油的加氢精制
本发明的有益效果：
本发明柴油加氢精制催化剂具有比表面积大、活性金属利用率高等特点，拥有较高的加氢脱硫活性，具有良好的应用前景。
具体实施方式
本发明柴油加氢精制催化剂以杂多酸溶液为浸渍液，Al2O3-TS-1-ZrO2-石墨烯复合氧化物为载体。催化剂比表面积为250～500m2/g，孔容0.5～0.8mL/g。
本发明柴油加氢精制催化剂，按催化剂的重量百分比计，TS-1分子筛含量为1～30％，γ-Al2O3含量为20～50％，氧化锆含量为0.01～10％，石墨烯含量为0.01～5％，杂多酸含量为10～40％。
本发明柴油加氢精制催化剂，所采用的浸渍液中含有的杂多酸为M6[WM3(H2O)2(ZnW9O34)2]，(M＝Mn、Co、Ni、Cu)的一种或几种。
本发明柴油加氢精制催化剂，活性金属为W、Mn、Co、Ni、Cu等，以氧化物计活性组分含量10～40％。
本发明柴油加氢精制催化剂的外形可以是片状、球形、圆柱条或异形条(三叶草、四叶草、蝶形)、颗粒状或齿球形，最好是圆柱条和异形条。
本发明柴油加氢精制催化剂制备过程如下：将氧化铝粉、TS-1分子筛、氧化锆混合均匀，添加适量石墨烯，混合均匀后添加适量助挤剂和粘合剂，再次混合均匀。挤条成型，外形可以是条形、三叶草形、颗粒状或齿球形。冷冻干燥或真空干燥后，焙烧制得载体。用含有活性金属的杂多酸配成浸渍液。将制得的载体进行等体积浸渍，冷冻干燥或真空干燥后，焙烧制得柴油加氢精制催化剂。
上述石墨烯可以为氧化石墨烯、石墨烯或其混合物。
上述助挤剂可以为淀粉、田菁粉、聚乙烯醇、甲基纤维素、聚乙二醇中的一种或几种，以各组分总重量为准，其添加量为1％～5％，优选为2％～4％。
上述粘合剂可以为硝酸、柠檬酸、乙二酸、酒石酸中的一种或几种，以各组分总重量为准，其添加量为1％～10％，优选为4％～8％。
本发明中载体浸渍时间为0.5～5小时，优选为1～3小时。浸渍后载体进行冷冻干燥，载体在300～550℃下焙烧2～6小时，优选为3～5小时，制得柴油加氢精制催化剂。
本发明柴油加氢精制催化剂经硫化后可用于直馏柴油、催化柴油、焦化柴油或其混合油的加氢精制。反应条件为反应温度为280～380℃，氢分压为6.0～9.0MPa，氢油体积比300:1～600:1，体积空速为0.5～3.0h-1。
本发明的柴油加氢精制催化剂可以用于直馏柴油、催化柴油、焦化柴油或其混合油的加氢精制。
下面的实施例将对本发明提供的一种柴油加氢精制催化剂予以进一步的说明，但并不因此而限制本发明。
实施例1
取100g拟薄水铝石，20gTS-1分子筛，1g氧化锆，石墨烯1g，混合均匀。加入4g田菁粉，混合均匀，滴加含4g硝酸、4g柠檬酸的水溶液混捏，挤条成1.5mm的三叶草形，冷冻干燥，然后550℃焙烧4h，制成载体。再用Ni6[WNi3(H2O)2(ZnW9O34)2]配制的浸渍液等体积浸渍，冷冻干燥，400℃焙烧4h，制得催化剂A。
实施例2
取100g拟薄水铝石，20gTS-1分子筛，1g氧化锆，石墨烯1g，混合均匀。加入4g田菁粉，混合均匀，滴加含4g硝酸、4g柠檬酸的水溶液混捏，挤条成1.5mm的三叶草形，冷冻干燥，然后550℃焙烧4h，制成载体。再用Co6[WCo3(H2O)2(ZnW9O34)2]配制的浸渍液等体积浸渍，冷冻干燥，400℃焙烧4h，制得催化剂B。
实施例3
取100g拟薄水铝石，105gTS-1分子筛，17.5g氧化锆，17.5g石墨烯，混合均匀。加入17.5g田菁粉，混合均匀，滴加含17.5g硝酸、17.5g柠檬酸的水溶液混捏，挤条成1.5mm的圆柱条，冷冻干燥，然后550℃焙烧4h，制成载体。再用Ni6[WNi3(H2O)2(ZnW9O34)2]配制的浸渍液等体积浸渍，冷冻干燥，400℃焙烧6h，制得催化剂C。
实施例4
取100g拟薄水铝石，1.4gTS-1分子筛，14g氧化锆，0.14g石墨烯，混合均匀。加入1.4g田菁粉，混合均匀，滴加含1.4g硝酸、1.4g柠檬酸的水溶液混捏，挤条成1.5mm的齿球形，冷冻干燥，然后550℃焙烧4h，制成载体。再用Cu6[WCu3(H2O)2(ZnW9O34)2]配制的浸渍液等体积浸渍，冷冻干燥，550℃焙烧2h，制得催化剂D。
实施例5
取100g拟薄水铝石，42gTS-1分子筛，7g氧化锆，7g石墨烯，混合均匀。加入4g田菁粉，混合均匀，滴加含4g硝酸、4g柠檬酸的水溶液混捏，挤条成1.5mm的三叶草形，冷冻干燥，然后550℃焙烧4h，制成载体。再用Mn6[WMn3(H2O)2(ZnW9O34)2]配制的浸渍液等体积浸渍，冷冻干燥，400℃焙烧4h，制得催化剂E。
比较例1
一种常规柴油加氢精制催化剂F，加氢活性金属为钼、镍。此催化剂以氧化铝为载体，用硝酸镍和钼酸铵配制的共浸液浸渍，100℃～120℃干燥4h，500℃～600℃焙烧4h而制得。
表1催化剂的物理化学性质
实施例6
本实例介绍上述催化剂的微反评价结果。
10mL微反评价使用的催化剂量为8g，以硫含量为1260ppm、氮含量为1178ppm的二次柴油为评价原料，进行加氢脱硫活性对比试验，反应条件为反应温度340℃，氢分压为6.4MPa，氢油体积比500:1，体积空速为2.0h-1。催化剂的微反评价结果见表2。
表2微反加氢评价结果
由表2可以看出，以二次柴油为原料，所研制催化剂均具有较高加氢脱硫活性且高于参比剂。本发明柴油加氢精制催化剂具有比表面积大、加氢脱硫活性高等特点，特别适用于高氮原料，具有良好的应用前景。
当然，本发明还可有其它多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (8)
1.一种柴油加氢精制催化剂，其特征在于，以催化剂质量为100％计，包含TS-1分子筛1～30％，γ-Al2O3 20～50％，氧化锆0.01～10％，石墨烯0.01～5％，以金属氧化物计的杂多酸10～40％；催化剂比表面积为250～500m2/g，孔容0.5～0.8mL/g；
所述杂多酸为M6[WM3(H2O)2(ZnW9O34)2]，其中，M为Mn、Co、Ni和Cu中的一种或几种；W及Mn、Co、Ni和Cu中的一种或几种为活性金属。
2.权利要求1所述的柴油加氢精制催化剂的制备方法，其特征在于，包括以下步骤：
(1)将氧化铝粉、TS-1分子筛、氧化锆混合均匀，然后加入石墨烯，混合均匀后再加入助挤剂和粘合剂，再次混合均匀，挤条成型，冷冻干燥或真空干燥后，焙烧制得Al2O3-TS-1-ZrO2-石墨烯复合氧化物载体；
(2)用含有活性金属的杂多酸配成浸渍液，将制得的载体进行等体积浸渍，冷冻干燥或真空干燥后，焙烧制得柴油加氢精制催化剂。
3.根据权利要求2所述的柴油加氢精制催化剂的制备方法，其特征在于，所制得的催化剂包含活性金属W及Mn、Co、Ni和Cu中的一种或几种和载体Al2O3-TS-1-ZrO2-石墨烯复合氧化物，以活性金属氧化物计，活性金属占催化剂重量的10～40％。
4.根据权利要求2所述的柴油加氢精制催化剂的制备方法，其特征在于，所制得的催化剂直径为0.8mm～2.0mm或大于2.5mm。
5.根据权利要求4所述的柴油加氢精制催化剂的制备方法，其特征在于，所制得的催化剂直径为1.0mm～1.8mm。
6.根据权利要求2所述的柴油加氢精制催化剂的制备方法，其特征在于，所制得的催化剂外形为条形、三叶草形、颗粒状或齿球形。
7.根据权利要求2所述的柴油加氢精制催化剂的制备方法，其特征在于，步骤(2)中载体浸渍时间为0.5～5小时，焙烧温度为400～550℃，焙烧时间为2～6小时。
8.权利要求1所述的柴油加氢精制催化剂的应用，其特征在于：催化剂经硫化后用作柴油加氢精制催化剂，反应条件为反应温度为280～380℃，氢分压为6.0～9.0MPa，氢油体积比300:1～600:1，体积空速为0.5～3.0h-1。
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