CN114602484B - 一种加氢脱残炭催化剂的制备方法 - Google Patents
一种加氢脱残炭催化剂的制备方法 Download PDFInfo
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- CN114602484B CN114602484B CN202011393713.0A CN202011393713A CN114602484B CN 114602484 B CN114602484 B CN 114602484B CN 202011393713 A CN202011393713 A CN 202011393713A CN 114602484 B CN114602484 B CN 114602484B
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Classifications
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
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- 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
- 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
- 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
- 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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- 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
- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
本发明公开了一种加氢脱残炭催化剂的制备方法，包括：（1）脱碳处理后废催化剂进行水热活化处理，经液固分离，分离后溶液经浓缩处理获得浓缩液，固体物料经干燥处理获得活化物料；（2）将偏高岭土水热晶化处理，改性处理后获得改性物料；（3）将活化物料和改性物料混合，用浓缩液浸渍，经液固分离，获得活性金属改性物料；（4）将活性金属改性物料与拟薄水铝石混合均匀，混捏成型，负载活性金属组分得到加氢脱残炭催化剂。该方法以废催化剂和改性处理后的高岭土为部分原料，回收利用废催化剂中金属，降低生产成本的同时得到较高的大孔含量及适宜的表面酸性的催化剂，该催化剂具有较高的脱残炭活性及加氢脱硫、脱氮活性。
Description
技术领域
本发明涉及催化剂制备领域，具体地说涉及一种加氢脱残炭催化剂的制备方法。
背景技术
渣油包含了原油中最重的组分，其中包括有多种复杂的烃类，以及高浓度的硫、氮和金属（主要是镍和钒），并具有高粘度、高残炭值等特点。因为生成油的残炭值是影响下游FCC装置进料配比的关键指标之一，同时也是催化剂失活的重要原因，所以对渣油进行加氢脱残炭是加氢处理过程中很重要的一个环节。渣油残炭的前驱物主要是由其沥青质或胶质中较大的稠环芳烃所构成，想要尽可能地脱除这些杂质，就必须提高催化剂对此类物质的加氢转化的能力。因此选择的催化剂必须具有较大的孔径和孔容、适宜的比表面积以及合适的表面酸度。
CN1321726A公开一种渣油加氢处理催化剂及其制备方法，特别是渣油加氢脱氮和加氢脱残炭催化剂及其制备方法。该发明催化剂制备方法为在一水氢氧化铝混捏过程中混入含镍金属盐类以提供催化剂所需含镍量，然后加入一种中性溶液混合，再加入酸性溶液混捏，制备成含镍和硅的Al2O3载体，然后再以浸渍的方法一次负载上含钼的化合物。该方法制备的催化剂6-8nm孔道含量较高，大孔含量相对较少，不利于大分子反应物的扩散。
CN106622261A公开一种加氢脱残炭催化剂及其制备方法和应用，该催化剂含有活性金属组分和改性加氢催化剂载体，所述改性加氢催化剂载体是由以下方法制得，该方法包括：将经过水热处理的载体重复地依次进行浸渍和干燥，并将最后一次得到的干燥产物进行焙烧，其中，每次浸渍过程中所用的浸渍液含有提供相同或不同酸性助剂化合物。该方法对氧化铝载体进行水热处理并加入酸性助剂调变氧化铝载体的表面酸性质，但该方法水热处理条件温和，提高氧化铝载体大孔含量的效果不明显。
CN106622264A公开一种加氢脱残炭催化剂及其制备方法和应用，本发明涉及一种加氢脱残炭催化剂，该催化剂含有活性金属组分和改性加氢催化剂载体，所述改性加氢催化剂载体包括载体和负载在所述载体上的金属助剂和酸性助剂，所述金属助剂和酸性助剂在所述载体上呈分层分布，壳层为金属助剂，核层为酸性助剂，所述金属助剂为第IA族金属组分和/或第IIA族金属组分，所述酸性助剂选自F、P和B中的至少一种组分。该方法对氧化铝载体进行水热处理并加入金属助剂和酸性助剂调变氧化铝载体的性质，该方法同样存在对氧化铝载体进行水热处理时处理条件温和，使最终氧化铝载体大孔含量有待进一步提高的缺点。
发明内容
针对现有技术中的不足，本发明提供了一种加氢脱残炭催化剂的制备方法。该方法以活化处理后的废催化剂和改性处理后的高岭土为部分原料，并利用废催化剂中金属为部分活性金属组分，降低催化剂生产成本的同时制备的催化剂具有较高的大孔含量及适宜的表面酸性，该加氢脱残炭催化剂具有较高的脱残炭活性的同时具有较高的加氢脱硫、脱氮活性。
本发明的加氢脱残炭催化剂的制备方法，包括如下内容：
（1）将含钼的废催化剂粉末进行脱碳处理，脱碳处理后废催化剂进行水热活化处理，处理后物料经液固分离，分离后溶液经浓缩处理获得浓缩液Y，固体物料经干燥处理获得活化物料H；
（2）将偏高岭土水热晶化处理，处理后物料经干燥、焙烧、改性处理后获得改性物料G；
（3）将步骤（1）活化物料H和步骤（2）改性物料G混合均匀，用步骤（1）浓缩液Y浸渍混合物料，浸渍后物料经液固分离及干燥处理后获得活性金属改性物料W；
（4）将步骤（3）活性金属改性物料W与拟薄水铝石混合均匀，混捏成型，成型物经干燥、焙烧后得到载体，负载活性金属组分后经干燥、焙烧，得到加氢脱残炭催化剂。
本发明方法中，步骤（1）所述的含钼的废催化剂指的是已经达不到反应要求，或者由于级配原因而没有完全失活的蜡油及渣油加氢脱金属、加氢脱硫、脱氮等加氢处理催化剂。该废催化剂除含钼外，还含有钨、镍、钴等加氢活性组分中的一种或多种，废催化剂中除了活性金属的硫化物和氧化铝载体外，还包括其它氧化物如氧化钛、氧化硅、氧化硼、分子筛等及积碳、重金属等杂质，重金属如钒等。废催化剂上的活性金属含量一般占催化剂重量的1wt%-30wt%，进一步优选钼含量占催化剂重量的0.5wt%-25wt%，金属杂质的含量一般占0.1wt%-40wt%。形状一般是圆柱形、球形或多叶形。
本发明方法中，步骤（1）所述的废催化剂粉末的粒度为200目以上，优选为400-800目。所述的脱碳处理是指去除废催化剂中的积碳，优选采用焙烧的方法去除，焙烧时的焙烧温度为700-950℃，焙烧时间为6-12小时，焙烧可以在空气气氛下进行，优选在氧气气氛下进行。
本发明方法中，步骤（1）所述的废催化剂水热活化处理是指将废催化剂置于碳酸氢铵溶液中进行的活化处理。碳酸氢铵的用量与废催化剂的质量比为4:1-8:1，水的用量与碳酸氢铵和废催化剂总和的质量比为2:1-4:1；所述废催化剂、碳酸氢铵及水可以采用任意顺序加入进行混合，比如可以是将水加入废催化剂和碳酸氢铵的混合物中，也可以是将废催化剂浸入碳酸氢铵的水溶液中。
本发明方法中，步骤（1）所述的水热活化处理温度为120-160℃，处理时间为4-8小时。
本发明方法中，步骤（1）所述的浓缩一般采用蒸发浓缩，浓缩至溶液中钼浓度以氧化物计为0.5-1g/100mL。
本发明方法中，步骤（1）所述的干燥温度为60-160℃，干燥时间为4-8小时。
本发明方法中，步骤（2）所述的偏高岭土是指高岭土经高温焙烧得到的，一般的焙烧温度为750-900℃，焙烧时间为3-6小时。
本发明方法中，步骤（2）所述的水热晶化处理是指将偏高岭土置于碳酸氢铵溶液中进行的水热晶化处理。碳酸氢铵与偏高岭土的质量比为1.5:1-3.0:1，水与偏高岭土和碳酸氢铵总和的质量比为2:1-4:1；所述偏高岭土、碳酸氢铵及水可以采用任意顺序加入进行混合，比如可以是将水加入偏高岭土和碳酸氢铵的混合物中，也可以是将偏高岭土浸入碳酸氢铵的水溶液中。
本发明方法中，步骤（2）所述的水热晶化处理温度为120-160℃，水热晶化处理时间为4-8小时；该水热晶化处理一般在高压反应釜中进行。
本发明方法中，步骤（2）所述的干燥温度为100-160℃，干燥时间为6-10小时，所述的焙烧温度为600-850℃，焙烧时间为4-8小时。
本发明方法中，步骤（2）所述的改性处理为将水热晶化后的偏高岭土进行脱硅或脱铝处理，所述的脱铝处理一般在酸性溶液中进行，酸性溶液为硝酸、盐酸或磷酸水溶液，优选为盐酸溶液，溶液的质量百分比浓度为15%-30%，液固质量比为20:1-40:1，处理时间为60-120分钟；所述的脱硅处理一般在碱性溶液中进行，碱性溶液为氢氧化钠、氢氧化钾或氨水溶液，溶液的质量百分比浓度为10%-20%，液固质量比为5:1-10:1，处理时间为30-90分钟。所述的脱硅及脱铝处理进一步优选在超声条件下进行，超声处理温度为30-90℃，超声处理时的频率为40-80kHz。脱硅或脱铝处理结束后物料经液固分离及干燥处理，干燥温度为100-160℃，干燥时间为6-10小时。
本发明方法中，步骤（3）所述的混合物料中活化物料H与改性物料G的质量比为1:2-1:5，浓缩液Y的用量为使混合物料完全浸没，浸渍时间为0.5-1小时。所述的干燥温度为100-160℃，干燥时间为6-10小时。
本发明方法中，步骤（4）所述拟薄水铝石可以是任意方法制备的拟薄水铝石，拟薄水铝石质量与活性金属改性物料W的质量比为1:1-5:1。
本发明方法中，步骤（4）所述的混捏成型采用本领域常规方法进行，成型过程中，可根据需要加入助挤剂，所述的助挤剂为田菁粉。所述的胶溶剂为盐酸、硝酸、硫酸、乙酸、草酸等中一种或几种，胶溶剂的浓度为0.1%-3%；所述的干燥温度为100-160℃，干燥时间为6-10小时；所述的焙烧温度为600-750℃，焙烧时间为4-6小时；焙烧在含氧气氛中，优选空气气氛中进行。
本发明方法中，步骤（4）所述加氢活性金属组分为第VIB族和/或第VIII族金属，第VIB族金属选自W、Mo中的一种或多种，第VIII族金属选自Co、Ni中的一种或多种，负载时用活性组分浸渍液以体积浸渍或过饱和浸渍等方式将活性组分负载到氧化铝载体上，活性组分浸渍液可以是含加氢活性组分的酸溶液、碱溶液或水溶液，浸渍液中第VIB族金属的含量以金属氧化物计为5.0-20.5g/100mL，第VIII族金属的含量以金属氧化物计为2.0-8.5g/100mL。所述的干燥温度为80-160℃，干燥时间为6-10小时，所述的焙烧为450-550℃下焙烧4-8小时。
与现有技术相比，本发明具有以下优点：
（1）本发明将废催化剂脱碳后进行活化处理，活化过程中，一方面废催化剂中活性金属钼和反应过程中沉积的钒发生溶解反应，另一方面废催化剂中的氧化铝在密闭、弱碱性的水热条件下发生水热晶化反应，由于金属钼、钒的溶解及氧化铝的晶化，使活化后废催化剂的孔结构得到很好的改善，尤其是比表面积得到大大的提升。
（2）偏高岭土经碳酸氢铵溶液水热晶化处理，处理后明显提高偏高岭土的比表面及孔容，晶化处理后物料在酸性溶液或碱性溶液中改性处理时，由于改性溶液的溶硅或溶铝作用，使偏高岭土晶粒表面形成蚀点，提高材料10-20nm的孔道含量。
（3）将活化后废催化剂及改性高岭土的混合物料作为氧化铝载体的部分原料，由于混合物料经过水热晶化处理，使物料晶粒较大，提高氧化铝载体的大孔含量，另一方面，由于高岭土中硅元素的存在，有效调变氧化铝载体的表面性质，改善活性金属与载体的作用，提高了催化剂的催化活性。
（4）废催化剂经活化后进行液固分离，分离后溶液中含有钼、钒等金属离子，溶液经浓缩并浸渍活化废催化剂物料及高岭土改性物料的混合物料，首先，废催化剂中的钼、钒等金属作为活性组分被二次利用，其次，使混合物料中金属含量增加，使最终催化剂中相应位置的大孔处活性金属含量增加，提高大孔处催化活性的同时提高催化剂的容金属及容积碳能力。
具体实施方式
下面结合实施例来进一步说明本发明的技术方案和技术效果，但并不局限于以下实施例。本发明中wt%代表质量分数。
BET法：应用N2物理吸-脱附表征实施例与对比例载体孔结构，具体操作如下：采用ASAP-2420型N2物理吸-脱附仪对样品孔结构进行表征。取少量样品在300℃下真空处理3-4小时，最后将产品置于液氮低温（-200℃）条件下进行氮气吸-脱附测试。其中比表面积根据BET方程得到，孔容和孔直径在30nm以下的分布率根据BJH模型得到。
压汞法：应用压汞仪表征实施例与对比例载体孔直径分布，具体操作如下：采用美国麦克AutoPore9500型全自动压汞仪对样品孔分布进行表征。样品烘干后称重装入膨胀计内，并在维持仪器给定的真空条件下脱气30分钟，装汞。随后将膨胀计放入高压釜内，排气。然后进行升压、降压测试。汞接触角度130º，汞界面张力0.485N.cm-1，孔直径100nm以上的分布率用压汞法测得的。
采用NB/SH/T 0704-2010标准方法测定油品中氮含量。
采用SH/T 0689-2000标准方法测定油品中硫含量。
采用SH/T 0266-92标准方法测定油品中残炭含量。
采用GB/T 34099-2017标准方法测定油品中Ni、V含量。
实施例中采用的废催化剂为固定床渣油加氢工业装置的废催化剂（含MoO3：6.4%，NiO：10.8%，V2O5：21.4%，Al2O3：49.7%，C：10.1%），经过抽提去除催化剂表面上的油和干燥处理。
实施例1
（1）活化物料H的制备
将200克粉碎至500目以上的废催化剂于800℃焙烧9小时，称取焙烧后废催化剂100克、碳酸氢铵650克，加入2000克蒸馏水搅拌20分钟，将混合物料转入高压釜中于135℃加热6.5小时，水热处理后物料经过滤处理，滤液经蒸发浓缩，浓缩至溶液Y中氧化钼浓度为0.75g/100mL，滤饼于120℃干燥6小时，制得活化物料H。
（2）改性物料G的制备
将200克高岭土原粉置于高温马弗炉中于850℃高温焙烧3.5小时。称取上述焙烧后的高岭土100克，碳酸氢铵200克，向上述物料中加入1000克蒸馏水搅拌20分钟，将混合物料转入高压釜中升温至140℃恒温6小时，然后将物料于110℃干燥6小时，800℃焙烧5小时。称取上述物料100克，置于烧杯中，向烧杯中加入3500克质量百分比浓度为20%的盐酸溶液，将烧杯置于超声容器中超声处理，超声频率为70kHz，处理温度为35℃，处理时间为80分钟，处理后物料经液固分离后于110℃干燥6小时，制得改性物料G。
（3）活性金属改性物料W的制备
称取步骤（1）活化物料H质量20克，步骤（2）改性物料G质量60克混合均匀，用步骤（1）浓缩溶液Y完全浸没混合物料并浸渍1小时，浸渍后物料经液固分离，固体物料于120℃干燥6小时，获得活性金属改性物料W。
（4）加氢脱残炭催化剂Cat的制备
称取拟薄水铝石100克，活性金属改性物料W质量40克，田菁粉2克，将上述物料混合均匀，然后加入适量溶有3克醋酸的水溶液混捏，挤条成型，成型物于140℃干燥6小时，700℃在空气中焙烧5小时，制得氧化铝载体。称取上述氧化铝载体30克置于喷浸滚锅中，用氧化钼浓度为15.7g/100ml，氧化镍浓度为3.8g/100ml的Mo-Ni-P溶液以饱和浸渍的方式喷浸上述氧化铝载体，浸渍后的催化剂于120℃烘干，再在450℃温度下焙烧5小时，制得加氢脱残炭催化剂Cat-1，催化剂性质见表1。
实施例2
同实施例1，只是步骤（1）制备活化物料H时，废催化剂的焙烧温度为850℃，焙烧为8小时，碳酸氢铵加入量为550克，水热处理温度为145℃，处理时间为5.5小时，溶液Y浓缩至氧化钼浓度为0.85g/100mL。步骤（2）制备改性物料G时，高岭土的焙烧温度为800℃，焙烧时间为4.5小时，碳酸氢铵的加入量为250克，水热处理温度为130℃，处理时间为7小时，盐酸换成质量浓度为17.5%的氢氧化钠，溶液加入量为600克，超声处理45分钟。步骤（3）活性金属改性物料W制备时，改性物料G的加入量为80克。步骤（4）加氢脱残炭催化剂制备时，活性金属改性物料W的加入量为28.5克，制得加氢脱残炭催化剂Cat-2，催化剂性质见表1。
实施例3
同实施例1，只是步骤（1）制备活化物料H时，废催化剂的焙烧温度为900℃，焙烧为7小时，碳酸氢铵加入量为750克，水热处理温度为125℃，处理时间为7.5小时，溶液Y浓缩至氧化钼浓度为0.65g/100mL。步骤（2）制备改性物料G时，高岭土的焙烧温度为750℃，焙烧时间为5.5小时，碳酸氢铵的加入量为150克，水热处理温度为150℃，处理时间为5小时，盐酸质量浓度为25%，加入量为2500克，超声处理100分钟。步骤（3）活性金属改性物料W制备时，改性物料G的加入量为100克。步骤（4）加氢脱残炭催化剂制备时，活性金属改性物料W的加入量为65克，制得加氢脱残炭催化剂Cat-3，催化剂性质见表1。
实施例4
同实施例1，只是步骤（1）制备活化物料H时，废催化剂的焙烧温度为750℃，焙烧为10小时，碳酸氢铵加入量为450克，水热处理温度为155℃，处理时间为4.5小时，溶液Y浓缩至氧化钼浓度为0.95g/100mL。步骤（2）制备改性物料G时，碳酸氢铵的加入量为300克，水热处理温度为120℃，处理时间为8小时，盐酸换成质量浓度为12.5%的氢氧化钠，溶液加入量为800克，超声处理60分钟。步骤（3）活性金属改性物料W制备时，改性物料G的加入量为40克。步骤（4）加氢脱残炭催化剂制备时，活性金属改性物料W的加入量为22克，制得加氢脱残炭催化剂Cat-4，催化剂性质见表1。
对比例1
同实施例1，只是废催化剂未经活化处理，高岭土未经改性处理，而是将相同量的废催化剂和高岭土的混合物与拟薄水铝石混捏成型制得氧化铝载体，然后制得对比催化剂Cat-5，催化剂性质见表1。
对比例2
同实施例1，只是废催化剂未经活化处理，而是将相同量废催化剂和改性高岭土的混合物与拟薄水铝石混捏成型制得氧化铝载体，然后制得对比催化剂Cat-6，催化剂性质见表1。
对比例3
同实施例1，只是高岭土未经改性处理，而是将相同量的活化后的废催化剂与高岭土混合，用废催化剂活化处理后的浓缩溶液浸渍混合物，浸渍后的混合物经干燥与拟薄水铝石混捏成型制得氧化铝载体，然后制得对比催化剂Cat-7，催化剂性质见表1。
表1催化剂性质
催化性能评价：
将上述实施例和对比例制备得到的加氢脱残炭催化剂（Cat-1-Cat-7）进行催化性能评价，分别将催化剂Cat-1- Cat-7颗粒装入反应器中，反应条件为：反应温度380℃、氢分压14兆帕，液时体积空速为0.6小时-1，氢油体积比为1000，原料油中镍含量为13.1ppm、钒含量为29.5ppm、硫含量为3.9%、氮含量为0.38%、残碳为11.9%，反应1000小时后测定生成油中各杂质的含量，计算杂质脱除率，评价结果见表2。
表 2 催化剂加氢性能对比
由表2数据可以看出，以本发明方法制备的加氢脱残炭催化剂具有较高的脱残炭活性的同时具有较高的脱硫、脱氮活性。
Claims (11)
1.一种加氢脱残炭催化剂的制备方法，其特征在于包括如下内容：（1）将含钼废催化剂粉末进行脱碳处理，脱碳处理后废催化剂进行水热活化处理，处理后物料经液固分离，分离后溶液经浓缩处理获得浓缩液Y，固体物料经干燥，得到活化物料H；（2）将偏高岭土水热晶化处理，处理后物料经干燥、焙烧、改性处理后获得改性物料G；（3）将步骤（1）活化物料H和步骤（2）改性物料G混合均匀，用步骤（1）浓缩液Y浸渍混合物料，浸渍后物料经液固分离及干燥处理后获得活性金属改性物料W；（4）将步骤（3）活性金属改性物料W与拟薄水铝石混合均匀，混捏成型，成型物经干燥、焙烧后得到载体，负载活性金属组分后经干燥、焙烧，得到加氢脱残炭催化剂；步骤（1）所述的废催化剂粉末的粒度为200目以上；所述的废催化剂除含钼外，还含有钨、镍、钴加氢活性组分中的一种或多种；所述的脱碳处理是指去除废催化剂中的积碳，采用焙烧的方法去除，焙烧时的焙烧温度为700-950℃，焙烧时间为6-12小时；步骤（2）所述的改性处理为将水热晶化后的偏高岭土进行脱硅或脱铝处理；所述的脱铝处理在酸性溶液中进行，酸性溶液为硝酸、盐酸或磷酸水溶液，溶液的质量百分比浓度为15%-30%，液固质量比为20:1-40:1，处理时间为60-120分钟；所述的脱硅处理在碱性溶液中进行，碱性溶液为氢氧化钠、氢氧化钾或氨水溶液，溶液的质量百分比浓度为10%-20%，液固质量比为5:1-10:1，处理时间为30-90分钟。
2.根据权利要求1所述的方法，其特征在于：步骤（1）所述的废催化剂水热活化处理是指将废催化剂置于碳酸氢铵溶液中进行的活化处理。
3.根据权利要求1所述的方法，其特征在于：碳酸氢铵的用量与废催化剂的质量比为4:1-8:1，水的用量与碳酸氢铵和废催化剂总和的质量比为2:1-4:1。
4.根据权利要求1所述的方法，其特征在于：所述的水热活化处理温度为120-160℃，处理时间为4-8小时。
5.根据权利要求1所述的方法，其特征在于：步骤（1）所述的浓缩采用蒸发浓缩，浓缩至溶液中钼浓度以氧化物计为0.5-1g/100mL。
6.根据权利要求1所述的方法，其特征在于：步骤（2）所述的水热晶化处理是指将偏高岭土置于碳酸氢铵溶液中进行的水热晶化处理；碳酸氢铵与偏高岭土的质量比为1.5:1-3.0:1，水与偏高岭土和碳酸氢铵总和的质量比为2:1-4:1；所述的水热晶化处理温度为120-160℃，水热晶化处理时间为4-8小时；该水热晶化处理在高压反应釜中进行。
7.根据权利要求1所述的方法，其特征在于：步骤（2）所述的干燥温度为100-160℃，干燥时间为6-10小时，所述的焙烧温度为600-850℃，焙烧时间为4-8小时。
8.根据权利要求1所述的方法，其特征在于：所述的脱硅及脱铝处理在超声条件下进行，超声处理温度为30-90℃，超声处理时的频率为40-80kHz。
9.根据权利要求1所述的方法，其特征在于：步骤（3）所述的混合物料中活化物料H与改性物料G的质量比为1:2-1:5，浓缩液Y的用量为使混合物料完全浸没，浸渍时间为0.5-1小时。
10.根据权利要求1所述的方法，其特征在于：步骤（4）所述拟薄水铝石与活性金属改性物料W的质量比为1:1-5:1。
11.根据权利要求1所述的方法，其特征在于：步骤（4）所述活性金属组分为第VIB族和/或第VIII族金属，第VIB族金属选自W、Mo中的一种或多种，第VIII族金属选自Co、Ni中的一种或多种。
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