CN113926489A - 一种重质油悬浮床加氢裂化催化剂的制备方法 - Google Patents
一种重质油悬浮床加氢裂化催化剂的制备方法 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/04—Oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种重质油悬浮床加氢裂化催化剂的制备方法。以焙烧处理累托土为载体材料，采用等体积浸渍法得到Mo负载型催化剂，将所制备Mo负载型催化剂进行有机表面修饰，获得具有亲油性Mo负载型催化剂。该催化剂在渣油悬浮床加氢裂化反应中表现出良好的的加氢裂化反应性能，有效地抑制焦炭和气体产生，提高液体馏分油收率。
Description
技术领域
本发明属于石油化工中的加氢裂化技术领域，涉及一种重质油悬浮床加氢裂化催化剂的制备方法。
背景技术
近年来，市场对汽油、柴油和航煤等轻质燃料油的需求不断增长，而常规原油储量持续下降，同时，原油重质化、劣质化的趋势加剧。为此，如何使重质油高效转化以满足市场对清洁燃料油需求成为当前石油化工领域亟需解决的问题。重质油（如减压渣油）组分结构复杂、分子量大、杂质（硫、氮、金属）含量高和粘度大，其加工转化为清洁燃料油难度极大。加氢处理、加氢裂化是当前重质油高效转化最有效的手段。对比以往的重质油处理工艺，悬浮床加氢技术具有原料适应性强，轻质产品收率高等优点，已成为炼油工业研究的热点和重点。催化剂作为悬浮床加氢裂化工艺的重要组成部分，已被研制出多种类型，其主要分类为：均相催化剂和非均相催化剂，其中均相催化剂分为水溶性和油溶性催化剂，非均相催化剂通常是固体粉末催化剂。
油溶性催化剂是一种有机金属盐，如环烷酸钼、乙酰丙酮钼等，其用量少活性高，生焦量少，但是该类催化剂因含有贵金属Mo和有机物导致生产成本高且回收难度大。水溶性催化剂主要有机物是与钼酸盐溶液混合形成的乳浊液。利用物理-化学分散相结合解决水溶性盐溶液的分散、乳化等问题，其前期处理十分复杂，同时脱水分离需要额外的能耗。
固体粉末催化剂主要包括负载型催化剂和天然矿物催化剂。负载型催化剂主要是由金属Mo、Co 、Ni等氧化物或盐的形式负载在氧化铝、无定型硅铝、分子筛和焦炭等载体上，其催化加氢活性较高，制备工艺简单，但反应大分子极易生焦沉积在催化剂活性位点上，堵塞孔道。天然矿物催化剂的加氢裂化反应活性低，气体和焦炭生成量大。
亲油疏水性固体粉末功能化制备已有大量的研究。Tsou等以三乙氧基(辛基)硅烷(OTS)为偶联剂，采用还原法制备疏水铜催化剂。将OTS接枝的还原CuPS催化剂应用于乙酰丙酸(LA)加氢合成γ-戊内酯(GVL)，疏在温和的反应条件(130 ℃、12 bar的H2压力)下，获得了高LA转化率(95.7%)、高GVL收率(85.2%)和稳定性。然而，新开发的Cu-O-SiO2-C8主要是界面作用，硅基化不可避免地会引起表面路易斯酸减弱，这表明OTS接枝CuPS制备的催化剂酸性是不稳定的。Tan等以脂肪酸改性修饰Cu/ZnO催化剂用于合成气(CO + H2)一步法合成二甲醚(DME)。疏水Cu/ZnO催化剂在水气存在下对甲醇合成的催化活性没有影响，对CO2选择性较低。CN103613078A，CN106540745A公开了水溶性无机氧化剂或无机盐表面进行亲油疏水改性的方法，该方法将无机氧化物或无机盐加入有机物混合物溶液中充分反应制备得到改性的氧化物或无机盐。CN105107479A公开了一种有机改性活性炭材料的制备方法，该制备过程是以活化后的活性碳与有机化合物反应制得接枝引发剂的活性碳，然后再与单体进行聚合反应，得到有机改性活性碳材料。但该制备过程较为繁琐，一定程度上限制了工业的生产和应用。CN102174278A公开一种无机纳米粉体表面亲油改性方法，该改性方法是将纳米粉体分散于水或水和乙醇混合液中，将改性剂吐温系或司班系按照一定的质量比加入混合液并加热搅拌，从而获得亲油性纳米粉体。CN107629471A公开了一种纳米二氧化钛改性制备得到亲油型纳米二氧化钛，其制备过程是将二氧化钛加入到一定状态下的水溶液，并将硅烷偶联剂加入到二氧化钛溶液中制得亲油型二氧化钛。将其应用于乳化沥青，使乳化后的沥青具有储存时间长，分散性好的优点。但所使用硅烷偶联剂暴露在水相体系中易发生水解反应。CN112624128A公开了一种亲油性纳米二氧化硅粉体的制备方法，该方法使用硅烷偶联剂在碱性条件下与纳米二氧化硅反应合成亲油性纳米SiO2。但是只适用于纳米级粉体的二氧化硅制备。CN109370265A公开了一种纳米二氧化硅的表面亲油改性方法，该方法以纳米二氧化硅为反应起始物，使用三甲基硅氧烷作为表面改性剂，采用溶胶-凝胶法，在碱性条件下制得改性纳米二氧化硅。然而，为实现二氧化硅的稳定分散，需要再次做接枝修饰，其制备过程较为繁琐，并不适用于工业化需求。CN112678807A公开了一种改性氧化亚硅/碳纳米管复合材料方法，其制备过程为：使用硅烷偶联剂水解处理后，同氧化亚硅和表面活性剂超声处理，惰性气体下加热合成改性氧化亚硅/碳纳米管复合材料。US2018029109A1公开了一种新型疏水型氧化铝的制备方法，该方法是将含长链羧酸的有机物加入到含有氧化铝化合物且pH值大于5.5泥浆混合液中，形成酸改性泥浆，经过水热后获得新型疏水氧化铝。EP3858900A1公开了一种基材的表面改性方法，该方法使用表面改性剂包括苯乙烯磺化硝基单体、聚合物或含有一个或多个硝基官能团的聚合物，通过插入反应在聚合物或纺织材料表面形成一个或多个碳氢键的化学反应，从而在聚合物或纺织材料表面上以化学方式附加特定或所需的化学功能。US20200263086A1公开了一种表面修饰的纳米颗粒，该方法是将纳米颗粒加入有机混合液中，在惰性气体条件下改性修饰获得表面修饰的纳米粒子。其制备过程包括：配体相互作用剂-纳米颗粒缔合复合物；具有特定的溶解性和/或相容性。配体相互作用剂-纳米颗粒缔合复合物链接/交联剂；连接/交联剂可以提供一个结合位点，使表面修饰配体与配体相互作用。
上述的制备方法都是通过利用特定的有机化合物与材料表面通过物理化学方式相互作用获得所需材料。其目的是降低材料的表面自由能，提高材料表面疏水性。本发明旨在通过有机修饰调控催化剂表界面性质，提高催化剂的亲油性，使其在重质油中高度分散，与原料油分子充分接触，实现催化剂的利用率最大化。
发明内容
本发明的目的在于提供一种重质油悬浮床加氢裂化催化剂的制备方法，以累托土负载Mo为基质，通过有机试剂表面修饰改性获得亲油性催化剂，该催化剂在渣油中高度分散，与渣油分子充分接触，提高催化剂悬浮床加氢裂化催化反应性能。
为实现上述目的，本发明采用如下技术方案：
一种重质油悬浮床加氢裂化催化剂制备方法，包括以下步骤：
（1）将天然矿物累托土进行焙烧改性处理；
（2）采用等体积浸渍法将金属钼盐负载在改性累托土；
（3）将步骤（2）所得累托土负载Mo催化剂超声分散于有机溶液中；
（4）将有机偶联剂与催化剂按照一定质量比加入到步骤（3）所得的悬浮液，超声处理；
（5）将步骤（4）所得的混合悬浮液转移至反应器，在一定温度下均相反应数小时；
（6）冷却后经过滤，固体样品干燥得到表面亲油性催化剂。
步骤（1）所述的累托土焙烧改性温度为400-1000 ℃，焙烧时间为1-8 h。
步骤（2）所述的Mo负载量为1-10 wt%，在50-200 ℃下干燥5-20 h，400-800 ℃下焙烧1-6 h。
步骤（3）所述的分散性溶液为异丙醇、去离子水、无水乙醇、甲苯、环己烷、正己烷、丙酮和二氯甲烷中的一种或者几种混合；无机粉末与溶液的质量比为1:5-1:30；超声处理不低于40 min。
步骤（4）所述的有机修饰剂为硅烷偶联剂，硅烷试剂，表面活性剂的任意一种或者两者混合。
所述的硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、3-氨基丙基三甲氧基硅烷和四乙氧基硅烷的任意一种或者两种混合；所述的硅烷化试剂为三甲基氯硅烷、三乙基氯硅烷、二甲基二氯硅烷、三甲基溴硅烷，三苯基氯硅烷的任意一种或者两种混合；所述的表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵，十二烷基苯磺酸钠，十二烷基硫酸钠中的任意一种；有机改性剂与无机固体粉末质量比为1:5-1:1。
步骤（5）所述的均相反应温度为100-400 ℃，反应时间为2-48 h。
步骤（6）所述固体样品经过滤、洗涤后，在20-150 ℃干燥8-24 h。
本发明的有益效果在于：
1）通过筛选有机物种类和调变有机物浓度制得具有亲油性催化剂，该催化剂在汽油、甲苯和渣油等有机体系中具有良好的分散性。
2）本发明制备的亲油性催化剂可高度分散在劣质渣油中，在悬浮床加氢裂化反应中表现出良好的抑制焦炭和气体的性能，同时提高液体馏分油收率。
3）本发明制备的具有亲油性催化剂所用材料和制备工艺绿色环保，原料价格低廉，工艺过程简单，可实现大规模生产。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
对比例
天然累托土在450 ℃下进行焙烧4 h，测出4g焙烧的累托土饱和吸水率，等体积水溶解 (NH4)6Mo7O24·4H2O得到Mo盐溶液，将Mo盐溶液均匀滴加在改性累托土表面，室温静置24 h，120 ℃干燥12 h，500 ℃下焙烧4 h得到固体粉末催化剂。
以减压渣油为原料进行催化剂的悬浮床加氢裂化反应评价，将40.0 g减压渣油、3wt%上述对比例催化剂和一定量CS2加入到250 mL高温高压反应器中， H2初始压力为11MPa。首先，催化剂在温度为350 ℃下硫化5 h，接着，在温度为430 ℃下反应3 h。催化剂的加氢裂化反应评价结果为：渣油的转化率是76.4%，汽油和柴油馏分油收率为50.2 wt%，液体收率为82.7 wt%，气体收率为14.7 wt%，焦炭产率是2.6 wt%。
实施例1
制备累托土负载Mo催化剂的步骤同对比例。
将2.0 g累托土负载Mo催化剂分散于30 mL甲苯中，超声处理40 min；将1.0 g的γ-氨丙基三乙氧基硅烷溶解至催化剂悬浮液中，超声处理20 min；在120 ℃下均相反应24h；自然冷却至室温，用无水乙醇离心洗涤后得到红褐色固体，将固体置于60 ℃干燥4 h，110 ℃干燥10 h得到亲油性累托土负载Mo催化剂。
催化剂悬浮床加氢裂化反应实验条件同对比例，反应评价结果是：渣油的转化率是81.6%，汽油和柴油馏分油收率为53.6 wt%，液体收率为87.0 wt%，气体收率为11.3 wt%，焦炭产率是1.7 wt%。
实施例2
制备累托土负载Mo催化剂的步骤同对比例。
将4.0 g累托土负载Mo催化剂分散于30 mL乙醇中，超声处理40 min；将1.6 g的γ-氨丙基三乙氧基硅烷溶解至催化剂悬浮液中，超声处理20 min；在120℃下均相反应24h；自然冷却至室温，用无水乙醇离心洗涤后得到红褐色固体，将固体置于60 ℃干燥4 h，110 ℃干燥10 h得到亲油性累托土负载Mo催化剂。
催化剂悬浮床加氢裂化反应实验条件同对比例，反应评价结果是：渣油的转化率是82.9%，汽油和柴油馏分油收率为54.3 wt%，液体收率为87.9 wt%，气体收率为10.6 wt%，焦炭产率是1.5 wt%。
实施例3
制备累托土负载Mo催化剂的步骤同对比例。
将4.0 g累托土负载Mo催化剂分散于30 mL水中，超声处理40 min；将1.6 g的γ-氨丙基三乙氧基硅烷溶解至催化剂悬浮液中，超声处理20 min；在120 ℃下均相反应24 h；自然冷却至室温，用无水乙醇离心洗涤后得到红褐色固体，将固体置于60 ℃干燥4 h，110℃干燥10 h得到亲油性累托土负载Mo催化剂。
催化剂悬浮床加氢裂化反应实验条件同对比例，反应评价结果是：渣油的转化率是84.2%，汽油和柴油馏分油收率为55.8 wt%，液体收率为88.5 wt%，气体收率为10.1 wt%，焦炭产率是1.4 wt%。
实施例4
制备累托土负载Mo催化剂的步骤同对比例。
将3.0 g累托土负载Mo催化剂分散于30 mL去离子水和乙醇中，超声处理40 min；将1.5 g十六烷基三甲基溴化铵溶解至催化剂悬浮液中，超声处理20 min；在120 ℃下均相反应24 h；自然冷却至室温，用无水乙醇离心洗涤后得到红褐色固体，将固体置于60 ℃干燥4 h，110 ℃干燥10 h得到亲油性累托土负载Mo催化剂。
催化剂悬浮床加氢裂化反应实验条件同对比例，反应评价结果是：渣油的转化率是85.3%，汽油和柴油馏分油收率为55.7 wt%，液体收率为88.4 wt%，气体收率为10.2 wt%，焦炭产率是1.4 wt%。
实施例5
制备累托土负载Mo催化剂的步骤同对比例。
将4.0 g累托土负载Mo催化剂分散于30 mL乙醇中，超声处理40 min；将2.0 g三甲基氯硅烷溶解至催化剂悬浮液中，超声处理20 min；在120 ℃下均相反应48 h；自然冷却至室温，用无水乙醇离心洗涤后得到红褐色固体，将固体置于60 ℃干燥4 h，110 ℃干燥10 h得到亲油性累托土负载Mo催化剂。
催化剂悬浮床加氢裂化反应实验条件同对比例，反应评价结果是：渣油的转化率是84.5%，汽油和柴油馏分油收率为55.4 wt%，液体收率为88.7 wt%，气体收率为9.8 wt%，焦炭产率是1.5 wt%。
实施例6
制备累托土负载Mo催化剂的步骤同对比例。
将3.0 g累托土负载Mo催化剂分散于30 mL乙醇中，超声处理40 min；将1.5 g 的γ-甲基丙烯酰氧基丙基三甲氧基硅烷溶解至催化剂悬浮液中，超声处理20 min；在120 ℃下均相反应48 h；自然冷却至室温，用无水乙醇离心洗涤后得到红褐色固体，将固体置于60℃干燥4 h，110 ℃干燥10 h得到亲油性累托土负载Mo催化剂。
催化剂悬浮床加氢裂化反应实验条件同对比例，反应评价结果是：渣油的转化率是84.7%，汽油和柴油馏分油收率为55.0 wt%，液体收率为88.5 wt%，气体收率为9.9 wt%，焦炭产率是1.6 wt%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (8)
1.一种重质油悬浮床加氢裂化催化剂的制备方法，其特征在于：以累托土负载Mo为催化活性组分，经过有机表面修饰，得到重质油悬浮床加氢裂化催化剂；采用的有机表面修饰剂为硅烷偶联剂、硅烷化试剂、表面活性剂中的至少一种。
2.根据权利要求1所述的方法，其特征在于：所述的硅烷偶联剂为γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、3-氨基丙基三甲氧基硅烷、四乙氧基硅烷中的至少一种；所述的硅烷化试剂为三甲基氯硅烷、三乙基氯硅烷、二甲基二氯硅烷、三甲基溴硅烷、三苯基氯硅烷中的至少一种；所述的表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基苯磺酸钠、十二烷基硫酸钠中的至少一种。
3.根据权利要求1所述的方法，其特征在于：包括以下步骤：
（1）将天然矿物累托土进行焙烧，得到改性累托土；
（2）采用等体积浸渍法将金属钼盐负载在改性累托土上，得到累托土负载Mo粉末；
（3）将累托土负载Mo粉末超声分散于溶剂中，加入有机表面修饰剂，超声处理；均相反应，冷却后过滤，干燥得到所述的重质油悬浮床加氢裂化催化剂。
4.根据权利要求3所述的方法，其特征在于：步骤（1）中焙烧温度为400-1000 ℃，时间为1-8 h。
5.根据权利要求3所述的方法，其特征在于：步骤（2）中Mo负载量为1-10 wt%，50-200℃干燥5-20 h，400-800 ℃焙烧1-6 h。
6.根据权利要求3所述的方法，其特征在于：步骤（3）中溶剂为异丙醇、去离子水、无水乙醇、甲苯、环己烷、正己烷、丙酮、二氯甲烷中的至少一种；累托土负载Mo粉末与溶剂的质量比为1:5-1:30；超声处理不低于40 min；有机表面修饰剂与累托土负载Mo粉末的质量比为1:5-1:1；均相反应温度为100-400 ℃，时间为2-48 h；干燥温度为20-150 ℃，时间为8-24 h。
7.一种如权利要求1所述的方法制得的重质油悬浮床加氢裂化催化剂。
8.一种如权利要求1所述的方法制得的催化剂在劣质重油悬浮床加氢裂化中的应用。
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