CN102310003B - 一种加氢裂化催化剂及其制备方法 - Google Patents

一种加氢裂化催化剂及其制备方法 Download PDF

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Publication number
CN102310003B
CN102310003B CN2010102221551A CN201010222155A CN102310003B CN 102310003 B CN102310003 B CN 102310003B CN 2010102221551 A CN2010102221551 A CN 2010102221551A CN 201010222155 A CN201010222155 A CN 201010222155A CN 102310003 B CN102310003 B CN 102310003B
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China
Prior art keywords
catalyst
molecular sieve
hydrocracking catalyst
preparation
amorphous aluminum
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CN102310003A (zh
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杜艳泽
关明华
王凤来
刘昶
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Priority to CN2010102221551A priority Critical patent/CN102310003B/zh
Priority to EP11172823.4A priority patent/EP2404667B1/en
Priority to KR1020110066814A priority patent/KR101851542B1/ko
Priority to US13/177,364 priority patent/US20120006724A1/en
Priority to DK11172823.4T priority patent/DK2404667T3/da
Publication of CN102310003A publication Critical patent/CN102310003A/zh
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Priority to US15/335,586 priority patent/US9937485B2/en
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract

本发明公开了一种加氢裂化催化剂及其制备方法，以重量计，催化剂中酸性裂化组分包括分子筛0～20％和无定形硅铝20％～60％，以氧化物重量计，加氢金属总含量为35％～70％，加氢裂化催化剂具有如下性质，比表面积为150m2/g～350m2/g，孔容为0.20cm3/g～0.50cm3/g。本发明催化剂采用酸性组分粉末材料与浸渍溶液直接混合浸渍，然后过滤、干燥、成型、活化的方法制备。与现有加氢裂化催化剂相比，本发明催化剂在加氢活性金属含量较高的同时，具有更大的孔容和比表面积，适宜于更重质、更劣质减压馏分油的单段加氢处理过程。

Description

一种加氢裂化催化剂及其制备方法
技术领域
本发明涉及一种加氢裂化催化剂及其制备方法，特别是高金属含量的处理重质馏分油的单段高中油选择性加氢裂化催化剂及其制备方法。
技术背景
近年来，世界范围内加氢裂化能力持续增加，其中亚太地区增长最快。我国经济的持续增长也强劲拉动了国内成品油市场的不断走高，目前我国现有加氢裂化装置加工能力已超过30.0Mt/a。但由于原油质量逐年变差，进口的高硫原油大幅度增加，以及炼厂为提高经济效益，开始普遍采用原油减压深拔技术，使得减压馏分油的干点由原来的520℃提高到了600℃左右，其密度越来越大、馏程越来越高、所含烃分子的分子量越来越大、结构也越来越复杂、硫氮等杂质含量也越来越多，大大增加了加氢裂化处理的难度，这些对加氢裂化技术以及加氢裂化催化剂都提出了更高的要求。
由于柴油发动机性能上的优点及其广泛使用，因此市场对柴油的需求量一直非常旺盛。目前炼油厂生产的柴油主要有直馏柴油和二次加工柴油，生产二次加工柴油的主要途径有催化裂化、加氢裂化和延迟焦化。由于环保法规日益严格，清洁燃料的标准也大大提高，催化柴油和焦化柴油产品已不能满足指标要求，需要进一步处理才能出厂。加氢裂化技术作为重油轻质化的主要手段之一，具有原料适应性强、产品方案灵活、目的产品选择性高、产品质量好、附加值高等优点，可满足市场对清洁燃料的需求，已成为二十一世纪的主要炼油技术。
单段加氢裂化技术具有流程简单、操作容易、投资少、产品选择性和性质稳定、反应末期氢耗不增加等特点，适合于最大量生产中间馏分油，尤其是最大量生产柴油的加氢裂化装置。加氢裂化技术的核心是加氢裂化催化剂，其关键在于加氢裂化催化剂水平的提高。
在单段加氢裂化技术中，原料不经过预精处理或经过浅度的预精制而直接与单段加氢裂化催化剂接触，因此要求单段加氢裂化催化剂具有较强的加氢性能和较强的耐杂质能力。单段加氢裂化方面，国外比较有代表性的技术提供者主要有Chevron公司和UOP公司。Chevron公司的单段高中油催化剂品种较多，先后推出了ICR-106、ICR-120、ICR-126、ICR-142、ICR-150、ICR-155、ICR-162等催化剂。ICR-142催化剂的活性明显高于ICR-106无定形硅铝催化剂，中油选择性与其相当；ICR-162催化剂活性较ICR-142催化剂又有显著提高，但中油选择性比ICR-142催化剂低一些。UOP公司开发的单段高中油催化剂主要有HC-102、HC-22、DHC-8、DHC-32、DHC-100、DHC-200、HC-110、HC-115、HC-215等催化剂。除HC-102和DHC-8为无定形催化剂外，其它均为含分子筛催化剂。HC-115催化剂活性比DHC-8无定形催化剂高，反应温度降低8℃，中间馏分油选择性相当。HC-110催化剂活性同DHC-8催化剂相当，但中间馏分油收率高3.0％。HC-215的中油选择性和活性均有所提高。
国内各大科研院所也积极开发单段加氢裂化催化剂，如中国石化抚顺石油化工研究院先后开发了ZHC-01、ZHC-02、3973、ZHC-04、FC-14、FC-28、FC-30等催化剂。ZHC-01催化剂比ICR-126催化剂反应温度低3℃，中油选择性相当。ZHC-02和3973催化剂与国外无定形催化剂水平相当。FC-28催化剂活性高于ICR-142，中油选择性与无定形催化剂相当。FC-30催化剂与FC-28催化剂相比，反应温度低3℃以上，中油选择性相当。采用该催化剂生产的石脑油是优质的重整原料，航煤是优质的3#喷气燃料，柴油是优质的轻柴油，尾油可以作为蒸汽裂解的原料。FC-14催化剂不仅活性比无定形催化剂有较大幅度的提高(单程通过时反应温度降低10～15℃，全循环操作时反应温度降低20～30℃)，而且中油选择性也比无定形催化剂提高2个百分点以上，同时具有中间馏分油质量好、柴油和尾油低温流动性好等特点，特别适合用于最大量生产中间馏分油(尤其是低凝柴油)以及高质量润滑油基础油，性能达到或超过国际先进水平。
加氢裂化催化剂是加氢裂化技术的核心。加氢裂化催化剂是由加氢功能和裂化功能组成的双功能催化剂，其中加氢功能是由加氢活性金属提供，提高加氢裂化催化剂的加氢性能，有利于芳烃的饱和，可以使多环芳烃可以进一步开环转化，这不仅有利于处理更重质、劣质的加氢裂化原料油，提高液体产品收率及生产高质量的加氢裂化产品，还能进一步提高催化剂的抗有机氮中毒的能力，减少生焦、积碳，延长催化剂的使用寿命。单段加氢裂化催化剂由于没有加氢预精制催化剂的保护，大量有机硫化物和氮化物直接与催化剂接触，因此要求催化剂必须具有很高的加氢脱氮活性、加氢脱硫活性和加氢饱和性能，才能维持催化剂性能的充分发挥。提高单段加氢裂化催化剂的加氢性能是满足处理劣质原料油和生产高质量产品最重要的途径。随着减压深拔技术的不断推广，加氢裂化原料质量变重、变差，以及产品质量升级和装置扩能改造的需求日趋提升，炼厂对加氢裂化催化剂的性能提出了越来越高的要求，尤其是对加氢裂化催化剂的加氢性能提出了更高的要求。常规金属含量(以氧化物计加氢金属总含量一般低于30％)的加氢裂化催化剂的加氢性能已经不能完全满足当前的实际使用需求。
通常提高加氢裂化催化剂的加氢性能的方法主要有改进催化剂添加助剂和提高加氢金属含量等。添加助剂的方法主要是通过添加助剂来改善载体和加氢金属的作用力，以提高加氢金属在催化剂表面上的分散，专利CN01123767.8给出了一种含稀土的加氢裂化催化剂制备方法，该方法通过添加稀土助剂，来改善载体与加氢金属的分散状态，使得催化剂的加氢性能得到了一定的改善。专利US 6,527,945、CN00110016.5和专利CN00109747.4通过添加硼、磷和卤素(F、Cl)等助剂，使得加氢裂化催化剂的性能获得了进一步的提高。但添加助剂的方法只是最大限度的利用了有限的数目的加氢活性中心，不能使加氢裂化催化剂的加氢性能获得较大幅度的提高，提高加氢裂化催化剂加氢金属含量可以大幅度的提高加氢活性中心数目，在加氢处理催化剂方面已经获得了非常好的应用。如专利US5086032、US4820677和CN200410050730.9等专利介绍了采用共沉法制备高金属含量加氢处理催化剂，制备出金属含量高达50～95％加氢处理催化剂，催化剂的加氢性能获得了极大的提高，产品质量获得了极大的改善。虽然催化剂具有较高的加氢性能，但催化剂孔容和比表面积小，只能处理柴油以下较轻质的馏分，并且由于共沉法制备催化剂金属利用率低，金属分散性能不好，且制备工艺复杂，产品稳定性差，所以催化剂性价比不高。混捏法可以制备各种活性金属含量的催化剂，但混捏法制备的催化剂性能相对较差，活性金属有效利用率低，加氢催化剂较少采用混捏法制备。US 5,565,088介绍了一种含NZMS分子筛加氢裂化催化剂，采用浸渍法制备催化剂，其较高金属含量的催化剂比金属含量低的催化剂可以生产出质量更好的航煤和柴油产品，但其金属含量最高没有超过40％，产品质量提高受到了限制。
通过以上分析，采用浸渍法制备催化剂，可以充分发挥加氢金属的性能，但制备催化剂的金属含量受到很大的限制；共沉法虽然可以制备高金属含量的加氢处理催化剂，但金属的利用率不高，催化剂孔结构也受到一定的限制。即现有不能得到加氢活性金属含量高、同时孔容和比表面积大的加氢裂化催化剂。因此，采用浸渍法制备高金属，且具有大孔容、大比表面积单段加氢裂化催化剂，将具有很重要的实用意义。
发明内容
针对现有常规金属含量加氢裂化催化剂性能的不足和高金属含量加氢裂化催化剂制备方法的限制，本发明提供了一种使用具有专利浸渍法制备技术制备的大孔、大比表面积、高金属含量单段加氢裂化催化剂。
本发明的加氢裂化催化剂，以重量计，酸性裂化组分包括分子筛0～20％和无定形硅铝20％～60％，以氧化物重量计，加氢金属总含量为35％～70％，优选为40％～60％，加氢裂化催化剂具有如下性质，比表面积为150m2/g～350m2/g，优选为160m2/g～300m2/g；孔容为0.20cm3/g～0.50cm3/g，优选为0.30cm3/g～0.45cm3/g。
本发明加氢裂化催化剂中，还可以根据需要含有氧化铝、粘土、助剂等适宜组分，助剂一般为磷、氟、硼、钛、锆等中的一种或几种。
本发明加氢裂化催化剂中，分子筛可以是Y型分子筛、β分子筛、ZSM-5分子筛、SAPO分子筛和MCM-41介孔分子筛的一种或几种复合使用，优选为Y型分子筛或β分子筛。分子筛的含量优选为1％～10％。分子筛种类和含量可以根据原料性质及产品要求具体优化确定。
本发明加氢裂化催化剂中，无定形硅铝是主要的裂化组分，同时是分散大量加氢活性金属的场所，因此要求具有较大的孔容和比表面积及适宜的酸性质。具体要求为：无定形硅铝比表面积为400-650m2/g，优选为400～550m2/g；孔容为1.0～2.0cm3/g，优选为1.2～1.6cm3/g，氧化硅重量含量为20％～80％，优选为30％～65％。平均孔直径在10～20nm范围内，优选在10～15nm，红外酸量(160℃吡啶红外吸附光谱法测定)在0.3～0.8mmol/g之间。
本发明加氢裂化催化剂中，加氢活性组分为W、Mo、Ni、Co中的一种或几种，优选为W和Ni。
本发明加氢裂化催化剂的制备方法如下：
(1)将所需的分子筛粉末、无定形硅铝前身物粉末混合均匀；
(2)配制含加氢活性金属组分的浸渍溶液；
(3)用步骤(2)的浸渍溶液浸渍步骤(1)的混合粉末；
(4)浸渍后过滤、干燥、粉碎，加入适宜粘结剂或胶溶剂，经过成型、活化得到最终加氢裂化催化剂。
本发明加氢裂化催化剂制备方法中，无定形硅铝前身物为无定形硅铝干胶粉，具体制备过程如下：
(1)酸性铝盐溶液(如AlCl3、Al(NO3)3、Al2(SO4)3溶液中的一种或几种)与按比例配制的碱性硅酸钠和铝酸钠的混合溶液进行中和成胶反应，反应温度控制在20～80℃，pH值在4.0～9.5范围内。
(2)在成胶后加入有机硅源，硅源可以包括有机硅油或硅酯类等中的一种或几种，有机硅的加入量按最终产品所需总硅量的5％～40％，最好为10％～30％，调整pH值和温度进行老化温度控制在60～80℃，pH值在6.0～10.0范围，老化时间为60～300min。
(3)将(2)所得溶胶进行过滤、洗涤。
(4)将(3)所得滤饼进行干燥、粉碎，制得无定形硅铝干胶粉。
本发明加氢裂化催化剂制备方法中，其它制备过程和条件为本领域技术人员熟知的技术内容。
本发明采用特种大孔无定形硅铝作为主要酸性组分和活性组分的分散载体，同时采用固体粉末浸渍的方法，得到的加氢催化剂在具有更高加氢活性组分含量的同时，具有更大的孔容和比表面积。本发明加氢裂化催化剂具有更高的加氢性能，特别是加氢脱氮性能，保证了单段加氢裂化催化剂裂化性能的正常发挥。
本发明加氢裂化催化剂制备过程采用粉体浸渍，与常规的成型后载体浸渍相比，粉体浸渍可以吸收更多的浸渍液，吸液率高达500％以上，而常规成型后载体浸渍时的吸液率只有100％左右。因此浸渍液不需要较高金属浓度，溶液配制简单，性质稳定，适合工业规模使用。较稀的金属盐浸渍液可以降低溶液的粘度，降低溶液表面张力，这样可以减弱浸渍过程中毛细阻力现象的影响。不仅可以保证催化剂中金属组分具有较高的含量，还能进一步提高金属在载体表面的分散度。
本发明的加氢处理催化剂采用改性分子筛和大孔无定形硅铝载体，浸渍方式采用的是粉体打浆添加，不仅能保证催化剂具有较高的金属含量和较好金属组分分布的均匀度，还能保证催化剂具有较大的孔容与表面积。
本发明加氢处理催化剂的制备过程中，浸渍液循环使用。因此该方法具有制备工艺简单、成本低、污染小等特点，适合工业规模推广使用。
本发明采用特种硅改性大孔氧化铝作为载体，这种专利产品具有超大的孔容和比表面积，可以担载更多的金属组分，并且可以保证金属组分能够很好的在载体上分散。本发明方法可以采用单一大孔氧化铝载体，不仅能保证催化剂具有较高的金属含量和较好金属组分分布的均匀度，还能保证催化剂具有较大的孔容与表面积。
本发明催化剂载体中使用的无定形硅铝采用硅铝同时沉淀方式制备，在成胶结束后引入有机硅源作为改性扩孔剂，这样不仅可以获得硅铝分布均匀的无定形硅铝，还能提高无定形硅铝的硅铝比，增大无定形硅铝孔容和比表面积，可以制备出满足催化剂性能需要的大孔、大比表面积、高硅铝比的无定形硅铝。由于氧化铝和氧化硅的均匀分布，使得无定形硅铝的酸性中心也能够均匀分布。无定形硅铝的制备过程中引入有机硅后，在干燥和焙烧过程中，有机物膨胀挥发，使无定形硅铝获得较大的孔容与比表面积，并且可以根据实际使用要求调整有机硅的加入量来调整产品的孔容和比表面积。无定形的硅铝制备过程中，未使用氨水等污染物，没有氨氮排放。硅源采用廉价水玻璃和少量的有机硅源相结合，使得制备成本得到有效的控制。因此该方法具有制备工艺简单、成本低、无污染等特点，适合工业规模推广使用。无定形硅铝在制备过程中可以通过调整碱性溶液中硅酸钠和铝酸钠的比例，以及调整硅酸钠与有机硅的比例，来灵活控制无定形硅铝产品的硅铝比，可以获得二氧化硅含量在20％～80％较宽范围的无定形硅铝，无定形硅铝中二氧化硅的含量又与酸性有着直接的关系，因此可以进一步来调变其酸性，来针对不同的使用要求，制备具有不同酸性的无定形硅铝材料。
具体实施方式
本发明催化剂一种具体过程如下：
(1)以钨镍为例，非贵加氢金属盐溶液配制：取一定量的去离子水在搅拌状态下，逐渐加入硝酸镍和偏钨酸铵晶体，待全部溶解后，静止，过滤，得到金属浸渍溶液，其中WO3含量10.0～50.0gWO3/100ml，NiO含量2.0～15.0gNiO/100ml。钼镍、钼钴和三组元金属组分溶液的配制属于成熟技术，请参考相关文献。
(2)测定所需改性分子筛、氧化铝和无定形硅铝干基。按比例称取一定量上述组分，置于搅拌金属浸渍溶液中，固液体积比为1∶5～1∶20，打浆时间为30～120min。混合浆液进行抽滤，滤饼干基控制在15％～30％，在100～150℃条件下干燥2～6小时，含金属粉体干基为40％～80％，然后进行粉碎，颗粒度控制100～200目。所需的分子筛可以按照本领域现有方法制备或使用市售产品。所需的助剂等其它组分可以加入固体粉末中，也可以加入浸渍溶液中。
(3)将(2)步骤得到的担载加氢金属的粉状物进行碾压，20～60min后加入浓度为2～10gHNO3/100ml稀硝酸溶液，继续碾压形成可挤糊膏状，然后挤条成型，催化剂形状可以是柱状、三叶草、四叶草和其它异性条等，长度控制3～8mm。
(4)将步骤(3)获得的条形物活化，首先在100～150℃条件下干燥2～6小时，然后进行焙烧，焙烧温度400～600℃，时间为3～10小时，制备出催化剂成品。
本发明加氢裂化催化剂载体中所用的改性分子筛，可以改性Y型分子筛、β分子筛、ZSM-5分子筛、SAPO分子筛和MCM-41介孔分子筛的一种或几种复合使用。分子筛的改性方法可以是水热处理或EDTA、SiCl4、(NH4)2SiF6、光气或草酸等化学脱铝改性法，以及使用酸、碱、盐式络合剂的水热与化学脱铝相结合等改性方法处理的分子筛。所用改性分子筛的性质为：硅铝摩尔比为3～100，优选为10～60，Na2O含量≤0.5wt％，红外酸量为0.1～1.2mmol/g，优选0.2～0.6mmol/g。
本发明一般选用超大孔改性氧化铝，优选CN200510047483.1制备的大孔改性氧化铝，孔容高达1.4mL/g～1.8mL/g，比表面积为500m2/g～550m2/g。
本发明使用的大孔无定形硅铝，孔容高达1.0mL/g～2.0mL/g，比表面积为400m2/g～650m2/g。一种具体制备方法如下：
(1)酸性溶液的配制，以AlCl3溶液的制备为例：将一般氧化铝与盐酸在90～120℃下进行反应，用活性炭脱铁，使得以重量计Fe/Al2O3值小于0.005％，制得精AlCl3溶液，再进行稀释，浓度为10～60g Al2O3/L可以作为成胶时的工作液。
(2)碱性溶液的配制，先配制出NaAlO2溶液，在搅拌条件下加入硅酸钠溶液，制备出透明的混合溶液，混合溶液中以Al2O3计含5～80g Al2O3/L，以SiO2计含5～120g SiO2/L。
(3)成胶过程：将酸性溶液与碱性溶液同时以一定的流速加入到成胶罐中，并进行搅拌，成胶时间控制在60～100min，成胶反应温度控制在20～80℃，最好控制在50～70℃，成胶反应过程的pH值控制在4.0～9.5范围内。成胶反应后加入有机硅溶剂，然后对浆液进行老化，老化pH值为6.0～10.0，温度控制在60～80℃，老化时间为60～300min。
(4)过滤、洗涤：将老化浆液进行过滤，将母液分离，得到的滤饼用去离子水进行洗涤，洗涤浆化时控制温度在60～80℃之间，洗涤时间为20～50min，洗涤次数为3～5次。
(5)干燥：将(4)所得的滤饼在100～150℃下进行干燥1～20小时。
本发明选用金属盐类溶液，一般为VIB族和VIII族金属盐类，如W、Mo、Ni、Co等金属的盐类溶液的一种或几种，金属溶液浓度一般为5.0～50.0g金属/100mL。
本发明中，比表面和孔容采用低温液氮物理吸附法，红外酸量、B酸和L酸采用吡啶吸附红外光谱法，其中B酸和L酸的总和即为红外酸量，微量元素采用等离子发射光谱法。
下面的实施例用于更详细地说明本发明载体的制备方法，但本发明的范围不只限于这些实施例的范围，涉及的百分含量为重量百分含量。
实例1(比较例)
取578g大孔氧化铝(天津天久公司生产，孔容0.82ml/g，比表面积323m2/g，干基71.1％)，386g小孔氧化铝(德国生产SB粉)制备粘合剂(干基26.2％)，加入6g田菁粉，碾压30分钟，加入适量的蒸馏水，使混合物成可挤糊膏状，挤条，挤条机孔板直径为1.5mm三叶草。湿条在120℃下干燥4小时，然后进行焙烧，温度550℃，时间3小时，编号HF-1S。取两份HF-1S载体，各120g分别浸渍在钨镍溶液(WO3含量43.1g/100ml，NiO含量7.2g/100ml)和钼镍溶液中(MoO3含量40.7g/100ml，NiO含量6.5g/100ml)进行过饱和浸渍，浸渍后催化剂在480℃进行焙烧，制备出催化剂成品分别编号为HF-1A和HF-1B。
实例2(比较例)
只是将实例1中的大孔氧化铝改用专利CN200510047483.1提供的硅改性大孔氧化铝，其它同实例1，制备载体编号为HF-2S，催化剂编号为HF-2A和HF-2B。
实例3(比较例)
只是将实例2中的浸渍液浓度进行调整，钨镍溶液为WO3含量51.5g/100ml，NiO含量11.4g/100ml，钼镍溶液MoO3含量50.3g/100ml，NiO含量12.4g/100ml。其它同实例2。制备载体编号为HF-3S，催化剂编号为HF-3A和HF-3B。
实例4(比较例)
取578g天久大孔氧化铝进行水热处理，水热处理温度为560℃，蒸气压力0.1MPa，时间40min。取三种金属盐浸渍液800ml，分别为钨镍溶液(WO3含量12.1g/100ml，NiO含量2.1g/100ml)、钼镍溶液(MoO3含量11.7g/100ml，NiO含量1.8g/100ml)和钨钼镍溶液(WO3含量6.3g/100ml，MoO3含量7.7g/100ml，NiO含量2.6g/100ml)，将水热处理后氧化铝加入搅拌的金属浸渍液中，浸渍时间120min，抽滤，120℃下干燥4小时，然后粉碎，用180目过筛。将粉状物与适量田菁粉混合，加入浓度为4gHNO3/100ml的稀硝酸进行成型，挤条孔板为直径为1.5mm三叶草。湿条在120℃下干燥4小时，然后将进行焙烧，焙烧温度480℃，时间3小时，催化剂编号分别为HF-4A、HF-4B、HF-4C。
实例5
只是将实例4中的大孔氧化铝改用大孔无定形硅铝干胶粉(孔容1.32mL/g，比表面积485m2/g，干基75.4％，平均孔直径为12.7nm)，成型时添加适量小孔氧化铝粘结剂，其它同实例4，制备催化剂编号分别为HF-5A、HF-5B和HF-5C。
大孔无定形硅铝干胶粉制备过程如下：将6000mL含Al2O3 5g/100mL的AlCl3溶液与含Al2O3 5g/100mL和SiO2 15g/100mL的铝酸钠和硅酸钠混合溶液并流滴加到温度为65℃搅拌的成胶反应灌中，保持pH值为8.0，反应接触时间40min.，以AlCl3溶液滴完为准。继续搅拌10min，滴加正硅酸乙酯120mL，滴加时间为20min。然后使用5％的氢氧化钠溶液将浆液pH值调整为9.0进行老化。老化时间为1.5小时。对产物进行过滤，然后用固液比为1∶20的去离子水洗涤，洗涤温度70℃，洗涤次数3次。对所得滤饼在120℃下干燥3h。
实例6
只是将实例5中大孔无定形硅铝与实例4中的大孔氧化铝重量比为4∶1。浸渍液浓度进行如下调整，钨镍溶液为WO3含量18.0g/100ml，NiO含量2.8g/100ml；钼镍溶液MoO3含量17.8g/100ml，NiO含量2.9g/100ml；钨钼镍溶液WO3含量8.7g/100ml，MoO3含量9.9g/100ml，NiO含量3.5g/100ml，其它同实例4，制备催化剂编号分别为HF-6A、HF-6B和HF-6C。
其中大孔无定形硅铝(性质：孔容1.40mL/g，比表面积550m2/g，干基74.3％，平均孔直径为13.6nm)制备法如下：将8000mL含Al2O3 5g/100mL的AlCl3溶液与含Al2O3 5g/100mL和SiO215g/100mL的铝酸钠和硅酸钠混合溶液并流滴加到温度为65℃搅拌的成胶反应灌中，保持pH值为8.0，反应接触时间40min.，以AlCl3溶液滴完为准。继续搅拌10min，滴加含SiO2 10g/100mL有机硅油(牌号5001)1400mL，滴加时间为40min。然后使用5％的氢氧化钠溶液将浆液pH值调整为9.0进行老化。老化时间为1.5小时。对产物进行过滤，然后用固液比为1∶20的去离子水洗涤，洗涤温度70℃，洗涤次数3次。对所得滤饼在120℃下干燥3h。
实例7
只是将实例5中的浸渍液浓度进行调整，钨镍溶液为WO3含量20.8g/100ml，NiO含量3.4g/100ml；钼镍溶液MoO3含量21.3g/100ml，NiO含量4.1g/100ml；钨钼镍溶液WO3含量8.4g/100ml，MoO3含量12.1g/100ml，NiO含量4.3g/100ml其它同实例4，制备催化剂编号分别为HF-7A、HF-7B和HF-7C。
同时使用占最终催化剂重量为5％的改性Y分子筛(性质：硅铝摩尔比为13，Na2O含量≤0.1wt％，红外酸量为0.8mmol/g)。
实例8
只是将实例5中的浸渍液浓度进行调整，钨镍溶液为WO3含量24.3g/100ml，NiO含量4.0g/100ml；钼镍溶液MoO3含量25.3g/100ml，NiO含量5.4g/100ml；钨钼镍溶液WO3含量8.9g/100ml，MoO3含量15.4g/100ml，NiO含量4.9g/100ml其它同实例4，制备催化剂编号分别为HF-8A、HF-8B和HF-8C。
本实施例中，对以上各例催化剂进行物化分析和活性评价。各例催化剂物化性质见表1所示。
表1.催化剂物化性质
Figure BSA00000180560100131
R为平均孔直径。
评价装置采用200ml小型加氢装置上进行，活性评价前对催化剂进行预硫化。评价催化剂活性所用原料油性质及反应工艺条件见表2和表3，催化剂脱氮相对活性对比结果见表4。
表2.原料油性质
Figure BSA00000180560100141
表3.催化剂评价工艺条件
Figure BSA00000180560100142
表4.催化剂脱氮相对活性对比结果
Figure BSA00000180560100143
表5.催化剂(HF-7A与商品催化剂FC30)加氢裂化反应结果
Figure BSA00000180560100151
*其它条件同表3

Claims (9)

1.一种加氢裂化催化剂，以重量计，催化剂中酸性裂化组分包括分子筛0～20％和无定形硅铝20％～60％，以氧化物重量计，加氢金属总含量为40％～70％，加氢裂化催化剂具有如下性质，比表面积为150m2/g～350m2/g，孔容为0.30cm3/g～0.50cm3/g；其中无定形硅铝比表面积为400-650m2/g，孔容为1.0～2.0cm3/g，氧化硅重量含量为20％～80％，平均孔直径在10～20nm范围内，红外酸量在0.3～0.8mmol/g之间；
催化剂的制备方法，包括如下过程：
(1)将所需的分子筛粉末、无定形硅铝前身物粉末混合均匀；
(2)配制含加氢活性金属组分的浸渍溶液；
(3)用步骤(2)的浸渍溶液浸渍步骤(1)的混合粉末；
(4)浸渍后过滤、干燥、粉碎，加入适宜粘结剂或胶溶剂，经过成型、活化得到最终加氢裂化催化剂。
2.按照权利要求1所述的催化剂，其特征在于：加氢裂化催化剂中，以氧化物重量计，加氢金属总含量为40％～60％。
3.按照权利要求1或2所述的催化剂，其特征在于：加氢裂化催化剂比表面积为160m2/g～300m2/g，孔容为0.30cm3/g～0.45cm3/g。
4.按照权利要求1所述的催化剂，其特征在于：加氢裂化催化剂中，还含有氧化铝、粘土或助剂，助剂为磷、氟、硼、钛、锆中的一种或几种。
5.按照权利要求1所述的催化剂，其特征在于：加氢裂化催化剂中，分子筛是Y型分子筛、β分子筛、ZSM-5分子筛、SAPO分子筛和MCM-41介孔分子筛的一种或几种复合使用。
6.按照权利要求1或5所述的催化剂，其特征在于：分子筛的含量为1％～10％。
7.按照权利要求1所述的催化剂，其特征在于：无定形硅铝比表面积为400～550m2/g，孔容为1.2～1.6cm3/g，氧化硅重量含量为30％～65％，平均孔直径在10～15nm范围内。
8.一种权利要求1至7任一权利要求所述催化剂的制备方法，包括如下过程：
(1)将所需的分子筛粉末、无定形硅铝前身物粉末混合均匀；
(2)配制含加氢活性金属组分的浸渍溶液；
(3)用步骤(2)的浸渍溶液浸渍步骤(1)的混合粉末；
(4)浸渍后过滤、干燥、粉碎，加入适宜粘结剂或胶溶剂，经过成型、活化得到最终加氢裂化催化剂。
9.按照权利要求8所述的方法，其特征在于：无定形硅铝前身物为无定形硅铝干胶粉，具体制备过程如下：
(1)酸性铝盐溶液与碱性硅酸钠和铝酸钠的混合溶液进行中和成胶反应，反应温度控制在20～80℃，pH值在4.0～9.5范围内；
(2)在成胶后加入有机硅源，硅源为有机硅油或硅酯类中的一种或几种，有机硅的加入量按最终产品所需总硅量的5％～40％，调整pH值和温度进行老化温度控制在60～80℃，pH值在6.0～10.0范围，老化时间为60～300min；
(3)将(2)所得溶胶进行过滤、洗涤；
(4)将(3)所得滤饼进行干燥、粉碎，制得无定形硅铝干胶粉。
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