CN109097096B - 一种催化裂化汽油预加氢方法 - Google Patents

一种催化裂化汽油预加氢方法 Download PDF

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CN109097096B
CN109097096B CN201811058042.5A CN201811058042A CN109097096B CN 109097096 B CN109097096 B CN 109097096B CN 201811058042 A CN201811058042 A CN 201811058042A CN 109097096 B CN109097096 B CN 109097096B
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tungsten
carrier
doped lanthanum
lanthanum ferrite
alumina
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CN109097096A (zh
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王廷海
鲍晓军
岳源源
王学丽
刘杰
朱海波
袁珮
白正帅
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Fuzhou University
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Fuzhou University
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Priority to PCT/CN2018/122104 priority patent/WO2020052144A1/zh
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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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    • C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
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    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

本发明涉及一种催化裂化汽油预加氢方法，催化裂化汽油经过预加氢反应器，进行硫醇醚化、双键异构反应，反应条件如下：反应温度80‑160℃，反应压力1‑5 MPa，液体体积空速1‑10 h‑1，氢油体积比3‑8:1；预加氢催化剂包括载体和活性组分，载体包含具有大孔结构的氧化铝复合载体和选自ZSM‑5、ZSM‑11、ZSM‑12、ZSM‑35、丝光沸石、无定型硅铝、SAPO‑11、MCM‑22、Y分子筛或beta分子筛中的一种或几种，载体表面负载活性组分钴，钼，镍，钨中的一种或几种，以氧化物记，活性组分含量为0.1~15.5%，用于进一步生产低烯烃、超低硫含量，高辛烷值的汽油。

Description

一种催化裂化汽油预加氢方法
技术领域
本发明涉及一种催化裂化汽油预加氢方法，用于生产低烯烃、超低硫含量，高辛烷值的清洁汽油。
背景技术
FCC汽油是由C4-C12的烃类以及微量的硫化物、氧化物和金属砷化物等组成的混合物，根据各炼油企业的原油性质和加工路线的差异，FCC汽油是由18-55v％的烯烃、12-20v％的芳烃和烷烃组成的混合物，各组分的辛烷值特性是芳烃>烯烃≈异构烷烃>烷烃。我国高硫、高烯烃含量和较低辛烷值的FCC汽油约占70％，而低硫含量、低烯烃含量、高辛烷值的烷基化油、异构化油和重整油的比例较低，这使得我国FCC汽油的清洁化需要同时承载着脱硫、降烯烃和保持辛烷值的三重任务目标。
氧化铝载体广泛用于多相催化剂、催化剂载体等领域，载体氧化铝的热稳定性、水热稳定性、抗结焦性能等不理想。通常添加助剂进行改性，提高载体性能。改性氧化铝载体专利技术有很多，CN201310429334.6公开一种高性能催化剂载体及其制备方法，用于多相催化反应的催化剂载体材料。这种高性能催化剂载体的主要成分为Al、Zr、Mg、Ti、Si氧化物的混合物，以稀土元素或铬改性，制备方法包括载体颗粒的制备和载体颗粒的改性，制备的高温载体的比表面积在80m2/g以上，孔容在0.3ml/g以上，高温水蒸汽处理比表面积保留率在90％以上。该催化剂载体可用于高温反应催化剂的制备，能够承受600℃以上的高温，可以在400～650℃下使用。在高温反应时，活性组分金属或金属氧化物颗粒不易烧结，性能稳定，催化剂具有较长的寿命。CN200780024779.9提供一种废气净化催化剂，其具有由具有细孔结构的二氧化硅构成的多孔二氧化硅载体、以及担载于该多孔二氧化硅载体的细孔结构内的钙钛矿型复合氧化物的粒子。这里，在该多孔二氧化硅载体中，在其细孔分布中，源于一次粒子间的间隙的峰处于3～100nm的范围。
汽油加氢脱硫催化剂最常用的载体是氧化铝，为提高催化剂的活性和稳定性，用硅、钛、镁、硼、磷等改性氧化铝制备复合载体，可以调变催化剂的孔结构、表面酸性以及活性组分与载体之间的相互作用。此外，调变载体的孔结构也会增大载体的比表面，其性能比目前使用的同类产品性能要优越数倍以上。
CN201610561945.X涉及一种硫醇醚化催化剂及其制备方法与应用。75％～85％的NiO-SiO2粉体，5％～10％的NiO，余量为Al2O3，加入稀硝酸溶液混合均匀，挤条成型后干燥，焙烧，制得所述催化剂，其中NiO-SiO2粉体是通过溶胶-凝胶法制得。本发明的硫醇醚化催化剂具有丰富的弱酸性位，具有高硫醇醚化活性和高活性稳定性，并具有高选择性。CN201611056044.1提供了一种低温硫醇醚化催化剂及其制备方法与应用，该催化剂以碱性助剂改性的氧化铝为载体，以NiO、MoO3及WO3为活性组分；其中，以该低温硫醇醚化催化剂的总重量为100％计，所述催化剂包含6～15wt％的NiO、0.1～10wt％的MoO3、0.1～10wt％的WO3、0.1～5wt％的碱性助剂的氧化物，及余量为氧化铝载体。还提供了上述催化剂的制备方法及其在催化汽油或液化石油气所含硫醇与烯烃或二烯烃的硫醚化反应中的应用。该发明所提供的该催化剂反应条件缓和，反应活性高，脱硫醇效率高且价格低廉，可用于汽油和液化石油气的深度脱硫工艺过程中。
目前，国内炼油企业普遍选用的汽油质量升级技术中，以Prime-G技术为代表的高选择性脱硫工艺，采用预加氢-轻重汽油切割-重汽油选择性加氢脱硫-重汽油补充脱硫工艺原理。但由于具体汽油原料组成及含量不同，以及汽油产品标准不同，汽油改质工艺及所用催化剂差异也较大。
发明内容
本发明提供一种催化裂化汽油预加氢方法，用于脱除二烯烃及硫醇、硫醚，同时双键异构端烯烃转化为内烯烃；并饱和剩余二烯烃。反应产物再经过脱硫、辛烷值恢复等反应单元生产低烯烃、超低硫含量，高辛烷值的清洁汽油。
一种催化裂化汽油预加氢方法，催化裂化汽油经过预加氢反应器，进行硫醇醚化、双键异构反应，反应条件如下：反应温度80-160℃，反应压力1-5MPa，液体体积空速1-10h-1，氢油体积比3-8:1；反应使用的预加氢催化剂包括载体和活性组分，载体包含具有大孔结构的氧化铝复合载体和选自ZSM-5、ZSM-11、ZSM-12、ZSM-35、丝光沸石、无定型硅铝、SAPO-11、MCM-22、Y分子筛或beta分子筛中的一种或几种，具有大孔结构的氧化铝复合载体含有0.1～12wt％的钨掺杂铁酸镧，氧化铝复合载体介孔占总孔的1～85％，氧化铝复合载体大孔占总孔的1～70％。优选地，介孔占总孔的5～70％，优选大孔占总孔的5～45％。载体表面负载活性组分钴，钼，镍，钨中的一种或几种，以氧化物记，活性组分含量为0.1～15.5％。
进一步优选，反应条件如下：反应温度90-145℃，反应压力1-4MPa，液体体积空速1-8h-1，氢油体积比3-6:1；
本发明所述预加氢反应主要是小分子硫醇、硫醚在预加氢催化剂的作用下，与二烯烃发生硫醚化反应，同时双键异构(即端烯烃转化为内烯烃)，并将剩余的二烯烃饱和。在硫醇醚化、双键异构反应的同时抑制烯烃聚合、过度裂化等副反应，以提高催化剂活性和选择性，提高液体收率。
上述钴，钼，镍，钨活性组分可以是它们的各种盐类或者它们各自的氧化物，硫化物，氮化物，磷化物中的一种或几种。
所述催化剂的制备方法，包括如下步骤：将含钴，钼，镍，钨的活性组分物质配成浸渍液，浸渍载体，在120-180℃下干燥4-8小时，450-800℃下焙烧3-9小时，得到预加氢催化剂。
所述氧化铝载体中包含0.1～12wt％的钨掺杂铁酸镧，载体介孔占总孔的1～85％，大孔占总孔的1～70％。优选地，介孔占总孔的5～70％，优选大孔占总孔的5～45％。
一种氧化铝复合载体的制备方法，将铝源和田菁粉加入到捏合机中混合均匀，加入无机酸溶液和有机聚合物，捏合均匀，然后再加入钨掺杂铁酸镧，捏合均匀后，经过挤条、成型、干燥、焙烧，得到氧化铝复合载体。
上述氧化铝复合载体粉末与ZSM-5、ZSM-11、ZSM-12、ZSM-35、丝光沸石、SAPO-11、MCM-22、Y分子筛或beta分子筛粉末中的一种或几种混合均匀，再加入田菁粉去离子水混和，加入无机酸，搅拌，干燥，焙烧处理得到混合载体。再负载活性组分钴，钼，镍，钨中的一种或几种，催化剂中钴，钼，镍，钨以氧化物记，含量为0.1～15.5％。
上述制备氧化铝复合载体所述铝源为拟薄水铝石、氧化铝、硫酸铝中的一种或几种。铝源也可以是高岭土、累托土、珍珠岩、蒙脱土中的一种或几种。
对载体的进一步改进，一种改进氧化铝复合载体，载体中包含0.1～12wt％的氧化硅，钨掺杂铁酸镧0.1～10wt％，载体介孔占总孔的1～80％，大孔占总孔的1～55％。优选地，介孔占总孔的1～65％，更优选5～55％，优选大孔占总孔的1～40％或5～45％，更优选10～35％，载体微孔、介孔、大孔不均匀分布。
优选地，上述氧化铝复合载体中钨掺杂铁酸镧为0.3～9wt％，更优选0.3～5wt％，钨掺杂铁酸镧中钨占钨掺杂铁酸镧的0.1～8wt％。
所述有机聚合物为聚乙烯醇、聚丙烯酸钠、聚乙二醇、聚丙烯酸酯中的一种或几种，优选聚丙烯酸或聚丙烯酸钠。
氧化铝载体中加入钨掺杂铁酸镧，相比加入铁酸镧(LaFeO3)，氧化铝载体中加入钨掺杂铁酸镧，再引入选自ZSM-5、ZSM-11、ZSM-12、ZSM-35、丝光沸石、无定型硅铝、SAPO-11、MCM-22、Y分子筛或beta分子筛中的一种或几种制备复合载体，负载钴、钼、镍、钨活性组分，催化剂有效促进硫醚化反应，同时双键异构(即端烯烃转化为内烯烃)，并将剩余的二烯烃饱和。尤其是双键异构选择性比较高。
对载体进一步改进，氧化铝复合载体中优选加入氧化硅，该氧化铝复合载体的制备方法，将铝源(如拟薄水铝石)和田菁粉加入到捏合机中混合均匀，加入无机酸或有机酸溶液和有机聚合物，捏合均匀，然后再加入钨掺杂铁酸镧，混合均匀得到氧化铝前驱体备用；有机聚合物的酸液中加入硅源，混合均匀后，与氧化铝前驱体混合，氧化铝前驱体中单位含量的有机聚合物比硅源中有机聚合物的含量高1.5倍以上,经挤条、成型、干燥、焙烧，得到氧化铝载体。所述硅源可以是硅酸钠或硅微粉。所述无机酸为硝酸、盐酸、硫酸，有机酸为草酸、柠檬酸、氨三乙酸、酒石酸、醋酸或苹果酸。
上述氧化铝载体的进一步改进，所述硅源可以是硅酸钠或硅微粉，也可以是硅藻土、蛋白石中的一种或两种，铝源也可以是高岭土、累托土、珍珠岩、蒙脱土中的一种或几种。
高岭土、累托土、珍珠岩、蒙脱土粉末活化过程的亚熔盐介质为NaOH-H2O，将铝土矿粉末与亚熔盐介质按质量比为1:0.2～2混合均匀，在100～400℃温度下，活化时间为0.5～4h。硅藻土、蛋白石的活化过程是将硅藻土在500～1000℃温度下，焙烧1～10h。上述氧化铝载体中的钨掺杂铁酸镧最好具有微介孔，引入具有微介孔钨掺杂铁酸镧，制备的催化剂有利于抑制烃类裂化等副反应发生，提高目的产物选择性。
一种具有微介孔的钨掺杂铁酸镧的制备方法，柠檬酸溶于去离子水中搅拌溶解，然后将硝酸镧与硝酸铁加入柠檬酸中，搅拌溶解，加入聚丙烯酸钠或聚丙烯酸，聚丙烯酸钠或聚丙烯酸的加入量为钨掺杂铁酸镧的0.1～9wt％，优选0.1～6.0wt％。再加入含钨化合物，以氧化物记，钨占钨掺杂铁酸镧的0.1～8wt％，搅拌，反应后，经干燥、焙烧、研磨得到成品。含钨化合物包括钨酸铵、偏钨酸铵、仲钨酸铵等。
氧化铝前驱体中单位含量的有机聚合物比硅源中有机聚合物的含量高1.5倍以上。可以有效改善载体的孔结构，一方面使载体微孔、介孔、大孔不均匀分布，减少烯烃聚合、过度裂化等副反应发生、提高选择性，汽油收率高，有利于装置长周期运转；另一方面有利于载体表面产生出更多的活性位负载中心，提高催化剂活性。
本发明所述预加氢催化剂载体包含具有大孔结构的氧化铝复合载体和选自ZSM-5、ZSM-11、ZSM-12、ZSM-35、丝光沸石、无定型硅铝、SAPO-11、MCM-22、Y分子筛或beta分子筛中的一种或几种，负载钴，钼，镍，钨中的一种或几种，用于汽油脱除二烯烃及硫醇、硫醚，同时双键异构端烯烃转化为内烯烃；并饱和剩余二烯烃。不但有效促进单支链异构，提高辛烷值，而且有利于减少低碳异构烃的再裂化反应，减少烯烃聚合、过度裂化等副反应发生，提高活性选择性，汽油收率高。
本发明催化裂化汽油预加氢方法，对不同催化裂化汽油适应性强，通过硫醇醚化、双键异构反应脱除二烯烃、硫醇硫醚，并饱和剩余烷烃，辛烷值损失小。适用于催化裂化汽油预加氢生产满足国五、国六标准的清洁汽油。
具体实施方式
以下通过实施例进一步详细描述本发明，但这些实施例不应认为是对本发明的限制。本发明所用的原料试剂均为市售产品。
实施例1
1、制备具有微介孔的钨掺杂铁酸镧
搅拌条件下，将2.2mol La(NO3)3溶于100mL水中，加入柠檬酸搅拌溶解；再加入4.2mol Fe(NO3)3，然后再加入160g聚丙烯酸钠，再加入含10g偏钨酸铵的水溶液，继续搅拌30min，经烘干、焙烧、研磨得到微介孔钨掺杂铁酸镧。
2、制备氧化铝载体
2.2g微介孔钨掺杂铁酸镧中加入柠檬酸备用，将300g拟薄水铝石粉子和20.0g田菁粉加入到捏合机中，并混合均匀，再加入硝酸、8g聚丙烯酸钠，捏合均匀，然后加入微介孔钨掺杂铁酸镧，混合均匀，经过捏合-挤条成型为三叶草形状。在120℃干燥8小时，700℃焙烧4小时，得到含微介孔钨掺杂铁酸镧的氧化铝载体1。载体孔结构如表1所示。
3、制备催化剂
氧化铝载体1与田菁粉、酸化无定型硅铝、去离子水捏合搅拌，经干燥焙烧得到复合载体1-1，将七钼酸铵和硝酸镍加入到蒸馏水中，配成浸渍液浸渍上述复合载体1-1，得到的催化剂前躯体在140℃烘干后，在500℃焙烧6h，得到催化剂1。催化剂1主要组成：含微介孔钨掺杂铁酸镧的氧化铝载体为73.2wt％，氧化铝含量为4.8wt％，氧化硅含量为5.2wt％，氧化镍含量为7.7wt％，氧化钼含量为9.1wt％。
实施例2
1、制备钨掺杂铁酸镧
搅拌条件下，将2.2mol La(NO3)3溶于100mL水中，加入柠檬酸搅拌溶解；再加入4.2mol Fe(NO3)3，再加入含10g偏钨酸铵的水溶液，继续搅拌30min，经烘干、焙烧、研磨得到钨掺杂铁酸镧。
2、制备氧化铝载体
2.2g钨掺杂铁酸镧中加入柠檬酸，将300g拟薄水铝石粉子和20.0g田菁粉加入到捏合机中，并混合均匀，再加入硝酸、8g聚丙烯酸钠，捏合均匀，然后加入钨掺杂铁酸镧，混合均匀，经过捏合-挤条成型为三叶草形状。在120℃干燥8小时，700℃焙烧4小时，得到含钨掺杂铁酸镧的氧化铝载体2。载体孔结构如表1。
3、制备催化剂
同实施例1，载体中引入zsm-5，得到复合载体2-1，将含钼、钴的浸渍液浸渍复合载体2-1，得到的催化剂前躯体在140℃烘干后，在530℃焙烧5h，得到催化剂2。催化剂2主要组成：含钨掺杂铁酸镧的氧化铝载体为71.5WT％，zsm-5含量7WT％，钼氧化物10.8wt％，钴氧化物10.7wt％。
实施例3
载体的制备同实施例1，所不同的是微介孔钨掺杂铁酸镧占载体6wt％。载催化剂的制备同实施例1，用活化后的蒙脱土为铝源。所不同的是活性组分为钼、钨，催化剂3主要组成：微介孔钨掺杂铁酸镧的氧化铝载体为75.6wt％，氧化铝含量为4.0wt％，氧化硅含量为4.0wt％，钼氧化物10.1wt％，钨氧化物6.3wt％。
实施例4
制备改进型氧化铝载体
2g聚丙烯酸钠溶于硝酸中，再加入28g硅微粉，搅拌均匀，得到硅微粉-聚丙烯酸钠混合物，取1/10的量备用，2.0g微介孔钨掺杂铁酸镧中加入柠檬酸备用。将310g拟薄水铝石粉子和22.0g田菁粉加入到捏合机中，加入硝酸，再加入28g聚丙烯酸钠硝酸溶液，并混合均匀，再加入上述硅微粉-聚丙烯酸钠混合物，捏合均匀，然后加入微介孔钨掺杂铁酸镧，混合均匀，经过捏合-挤条成型为三叶草形状。在130℃干燥7小时，650℃焙烧5小时，得到微介孔钨掺杂铁酸镧和氧化硅的氧化铝载体4。
催化剂的制备同实施例2，所不同的是活性组分为钨、镍、钼，催化剂4主要组成：含微介孔钨掺杂铁酸镧的氧化铝载体为71.7wt％，zsm-5含量5WT％，钨氧化物7.8wt％，镍氧化物3.2wt％，钼氧化物12.3wt％。
实施例5
搅拌条件下，将2.0mol La(NO3)3溶于100mL水中，加入柠檬酸搅拌溶解；再加入4.0mol Fe(NO3)3，再加入含12g偏钨酸铵的水溶液，继续搅拌30min，经烘干、焙烧、研磨得到钨掺杂铁酸镧。
载体的制备同实施例4，所不同的是钨掺杂铁酸镧占载体3wt％，用活化后的硅藻土和高岭土为硅源铝源。催化剂5主要组成：含钨掺杂铁酸镧和氧化硅的氧化铝载体为74.0wt％，zsm-5含量4WT％，钼氧化物12.9wt％、钨氧化物9.1wt％。
实施例6
催化剂制备同实施例4，所不同的是催化剂中加入丝光沸石，催化剂6主要组成：含微介孔钨掺杂铁酸镧和氧化硅的氧化铝载体4含量80.1wt％、丝光沸石含量6.8wt％，钼氧化物10.4wt％，钨氧化物2.7wt％。用活化后的硅藻土和高岭土为硅源铝源。
实施例7
催化剂制备同实施例6，所不同的是催化剂中加入beta分子筛，催化剂7主要组成：含微介孔钨掺杂铁酸镧和氧化硅的氧化铝载体4含量72.8wt％，beta分子筛含量6.7wt％，钼氧化物10.4wt％，镍氧化物10.1wt％。用活化后的硅藻土和高岭土为硅源铝源。
对比例1
载体制备同实施例4，只是加入的是铁酸镧，催化剂的制备同实施例4，反应条件同实施例4，反应结果见表2。
表1大孔的氧化铝载体比表面积与孔径分布
Figure BDA0001796316730000081
表2催化剂预加氢反应结果
Figure BDA0001796316730000082
Figure BDA0001796316730000091
FCC汽油通过预加氢反应器在预加氢催化剂1、3、4、7的作用下进行加氢，脱除二烯烃及硫醇、硫醚，同时双键异构(即端烯烃转化为内烯烃)，并将剩余的二烯烃饱和。反应温度为115℃，反应压力为1.8MPa，液体体积空速为5h-1，氢油体积比为4:1，反应结果见表2。
预加氢催化剂2、5、6反应为108℃，反应压力为1.4MPa，液体体积空速为4h-1，氢油体积比为3:1，反应结果见表2。
预加氢催化剂1-7辛烷值损失低，汽油收率高，硫醇脱除率高，活性好，催化剂能够有效抑制烯烃聚合、过度裂化等副反应发生，抑制低碳烃类的裂化反应，汽油收率高，有利于装置长周期运转；催化剂的载体表面产生出更多的活性位负载中心，有效提高催化剂脱除二烯烃及硫醇、硫醚，双键异构活性，催化剂具有良好的活性和选择性。反应运行600h，预加氢催化剂4和7产品硫醇脱除率为98.2％、98.6％，辛烷值损失为0.2个单位、0.3个单位，积碳率0.3、0.2，液体收率99.6％、99.0％。内烯烃增量0.37％、0.42％，二烯烃含量脱除率100％、100％，催化剂反应性能稳定。
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的保护范围。

Claims (10)

1.一种催化裂化汽油预加氢方法，其特征在于：催化裂化汽油经过预加氢反应器，在预加氢催化剂的参与下进行硫醇醚化、双键异构反应，反应条件如下：反应温度80-160℃，反应压力1-5 MPa，液体体积空速1-10 h-1，氢油体积比3-8:1；预加氢催化剂包括载体和活性组分，载体包含具有大孔结构的氧化铝复合载体和选自ZSM-5、ZSM-11、ZSM-12、ZSM-35、丝光沸石、无定型硅铝、SAPO-11、MCM-22、Y分子筛或beta分子筛中的一种或几种，氧化铝复合载体含有0.1~12wt%的钨掺杂铁酸镧，氧化铝复合载体介孔占总孔的1~85%，氧化铝复合载体大孔占总孔的1~70%；载体表面负载活性组分钴，钼，镍，钨中的一种或几种，以氧化物记，活性组分含量为0.1~15.5%；所述钨掺杂铁酸镧为具有微介孔的钨掺杂铁酸镧，具有微介孔的钨掺杂铁酸镧的制备方法如下：柠檬酸溶于水中搅拌溶解，然后将硝酸镧与硝酸铁加入柠檬酸中，搅拌溶解，加入聚丙烯酸钠或聚丙烯酸，聚丙烯酸钠或聚丙烯酸的加入量为钨掺杂铁酸镧的0.1~9wt%，再加入含钨化合物，以氧化物计，钨占钨掺杂铁酸镧的0.1~8 wt%，搅拌，反应后，经干燥、焙烧、研磨得到成品。
2.根据权利要求1所述的催化裂化汽油预加氢方法，其特征在于：反应条件如下：反应温度90-145oC，反应压力1-4 MPa，液体体积空速1-8 h-1，氢油体积比3-6:1。
3.根据权利要求1所述的催化裂化汽油预加氢方法，其特征在于：所述氧化铝复合载体中钨掺杂铁酸镧为0.3~9 wt%，钨掺杂铁酸镧中钨占钨掺杂铁酸镧的0.1~8 wt%。
4.根据权利要求1所述的催化裂化汽油预加氢方法，其特征在于：所述具有大孔结构的氧化铝复合载体介孔占总孔的5~70%，大孔占总孔的5~45%。
5.根据权利要求1或2所述的催化裂化汽油预加氢方法，其特征在于：所述氧化铝复合载体包含0.1~12 wt%的氧化硅，0.1~10 wt%的钨掺杂铁酸镧，介孔占总孔的1~80%，大孔占总孔的1~40%，载体中微孔、介孔、大孔不均匀分布。
6.根据权利要求1或2所述的催化裂化汽油预加氢方法，其特征在于：所述氧化铝复合载体的制备方法如下：将铝源和田菁粉加入到捏合机中混合均匀，加入无机酸溶液和有机聚合物，捏合均匀，然后再加入钨掺杂铁酸镧，捏合均匀后，经过挤条、成型、干燥、焙烧，得到氧化铝载体。
7.根据权利要求5所述的催化裂化汽油预加氢方法，其特征在于：所述氧化铝复合载体的制备方法如下：将铝源和田菁粉加入到捏合机中混合均匀，加入无机酸或有机酸溶液和有机聚合物，捏合均匀，然后再加入钨掺杂铁酸镧，混合均匀得到氧化铝前驱体备用；有机聚合物的酸液中加入硅源，混合均匀后，与氧化铝前驱体混合，氧化铝前驱体中单位含量的有机聚合物比硅源中有机聚合物的含量高1.5倍以上，经挤条、成型、干燥、焙烧，得到氧化铝载体。
8.根据权利要求7所述的催化裂化汽油预加氢方法，其特征在于：所述硅源是硅藻土、蛋白石中的一种或两种，所述铝源是高岭土、累托土、珍珠岩、蒙脱土中的一种或几种。
9.根据权利要求6所述的催化裂化汽油预加氢方法，其特征在于：所述有机聚合物为聚乙烯醇、聚丙烯酸钠、聚乙二醇、聚丙烯酸酯中的一种或几种。
10.根据权利要求1~3任一项所述的催化裂化汽油预加氢方法，其特征在于：所述预加氢催化剂的制备方法包括如下步骤：将含钴，钼，镍，钨的活性组分物质配成浸渍液，浸渍载体，在120-180℃下干燥4-8小时，450-800℃下焙烧3-9小时，得到预加氢催化剂。
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