CN108554441A - 一种高活性加氢裂化预处理催化剂、制备方法及其应用 - Google Patents
一种高活性加氢裂化预处理催化剂、制备方法及其应用 Download PDFInfo
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- CN108554441A CN108554441A CN201810230882.9A CN201810230882A CN108554441A CN 108554441 A CN108554441 A CN 108554441A CN 201810230882 A CN201810230882 A CN 201810230882A CN 108554441 A CN108554441 A CN 108554441A
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- Prior art keywords
- catalyst
- carrier
- acid
- hydrocracking
- dipping
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- 238000007598 dipping method Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 29
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Classifications
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本发明提供一种高活性加氢裂化预处理催化剂、制备方法及其应用。本发明催化剂由活性组分、载体与助剂组成,比表面积为160~300m2/g,孔容为0.38~0.60cm3/g;所述的活性组分为Ni、Mo、W中的一种或几种,所述的载体由大孔氧化铝、改性氧化铝、改性分子筛,所述的助剂为B、F、P中的一种或者几种,所述加氢裂化预处理催化剂采用真空有机络合浸渍‑‑微波低温活化方法制备,将载体放置于浸渍双锥中进行抽真空处理,再采用等体积浸渍法负载活性金属,最后通过微波加热快速低温活化后制得。本发明高活性加氢裂化预处理催化剂具有活性高、生产成本低的特点。
Description
技术领域
本发明涉及加氢催化剂技术领域,涉及一种高活性加氢裂化预处理催化剂的制备方法。
背景技术
随着世界石油资源的日趋重质化、劣质化,石油燃料产品的日趋优质化、清洁化,因而发展重质原油高效转化与清洁油品生产技术成为当今石油加工业的首屈之重。加氢裂化技术是将重油轻质化与清洁油品生产集于一体的综合加工技术,已成为未来石油加工的核心技术,亦是炼化企业大力发展的主要趋势。加氢裂化技术的核心在于加氢裂化催化剂,而催化剂中含有分子筛,易吸附原料油中的氮化物,使其中毒失去活性。因此,通常在加氢裂化工艺中装填加氢裂化预处理催化剂,使原料油在与加氢裂化催化剂接触之前,先进行加氢脱氮、脱硫等杂质与多环芳烃加氢饱和,其目的是为加氢裂化催化剂提供优质原料(特别是低氮原料油),保护加氢裂化催化剂能够充分且稳定的发挥裂化活性。
随着加氢裂化技术的持续发展,加氢裂化预处理技术越来越受到重视且得到快速发展。加氢裂化预处理技术的核心在于加氢裂化预处理催化剂。加氢预处理催化剂通常采用氧化铝为载体,但是由于氧化铝本身孔径与表面酸性的局限,单一作为载体制备的催化剂不能够实现深度的多环芳烃饱和与杂环氮化物的脱除,需要进行氧化铝的改性。
CN103285914A公开了一种含硅铝-磷铝复合分子筛的加氢预处理催化剂的制法。该方法通过引入硅铝-磷铝复合分子筛,调节催化剂的酸分布,通过调变浸渍液的pH值削弱载体与金属之间的作用力,增加活性中心的密度,合理的匹配催化剂的加氢活性中心与酸中心。该方法所制备的催化剂在劣质蜡油加氢处理过程中表现出优异的芳环加氢饱和性能与C-N键的裂解能力,从而提高了催化剂的加氢脱芳与加氢脱氮性能。
CN103191753A公开了一种加氢处理催化剂的制备方法。该方法先用含氨水蒸汽对粉状加氢处理催化剂载体材料进行水热处理,然后再浸渍加氢活性金属,经干燥、成型、干燥、焙烧,得到加氢处理催化剂。本发明方法将成型前加氢处理催化剂载体材料粉体用含氨气水蒸汽进行水热处理,改善催化剂的酸性质,并采用一次浸渍法获得较高活性金属含量的加氢处理催化剂,并且催化剂具有优良的使用性能。本发明方法过程简单,可以制备各种加氢处理催化剂,特别适宜于制备重质馏分油加氢处理催化剂。
CN102309971A公开了一种加氢处理催化剂的制备方法,使用粉状加氢处理催化剂载体材料进行浸渍,然后干燥、成型、焙烧,得到最终加氢处理催化剂。加氢处理催化剂载体材料在浸渍活性金属前优选进行水热处理,催化剂载体材料优选大孔氧化铝或改性大孔氧化铝。本发明方法利用成型前加氢处理催化剂载体材料粉体吸液量大的特点,采用一次浸渍法获得较高活性金属含量的加氢处理催化剂,并且催化剂具有优良的使用性能。
CN102019201A公开了一种含分子筛的重质馏分油加氢精制催化剂的制备方法,其特征在于以氧化铝、磷铝分子筛AlPO4-5和钛硅分子筛ETS-10共同作为载体,通过两种分子筛的协同作用,提高催化剂的加氢精制性能,使其在较缓和工艺条件下加工劣质重馏分油,达到深度脱硫、脱氮效果。中国发明专利CN100556994C公开一种加氢处理催化剂,其载体由二氧化钛与二氧化硅复合氧化物与HY分子筛或酸改性HY分子筛共同作为载体,负载活性组分,制备成催化剂,Y分子筛的引入,增加了催化剂的酸性,提高了加氢反应性能。
现有的加氢裂化预处理催化剂制备技术均采用传统湿法进行活性组分的浸渍负载,电烘箱或回转炉进行活化。传统湿法负载活性组分,金属浸渍量大时浸渍易造成金属在多孔材料孔道内外分布不均匀;催化剂采用电烘箱或回转炉传统干燥活化,其加热方式为热传导,加热效率低,耗时时间长、温控难,此方式加热干燥活化催化剂易造成活性金属组分的聚集,降低催化剂的反应活性。
发明内容
针对现有技术的不足,本发明提供了一种高活性加氢裂化预处理催化剂及其制备方法。
一种高活性加氢裂化预处理催化剂,包括:
所述的加氢裂化预处理催化剂由活性组分、载体与助剂组成;所述的活性组分为Ni、Mo、W中的一种或几种,所述的载体由大孔氧化铝、改性氧化铝、改性分子筛组成,所述的助剂为B、F、P中的一种或者几种;
所述的加氢预处理催化剂组分质量百分含量为:改性氧化铝20~40%,改性分子筛10~20%,金属总量18~30%,助剂2~8%,其余组分为大孔氧化铝;
所述的加氢预处理催化剂载体比表面积为300~480m2/g,孔容为0.68~0.90cm3/g,中强B酸含量为0.20~0.50mmol/g;催化剂比表面积为160~300m2/g,孔容为0.38~0.60cm3/g;
所述的大孔氧化铝为一步水热法制备所得,BET比表面积为280~400m2/g,孔容为0.90~1.4cm3/g,最可几孔径12.0~18.0nm;
所述的改性氧化铝为溶胶凝胶法制备所得,改性元素为Si、Ti、Zr、P中的一种或几种元素,改性元素氧化物总含量占改性氧化铝粉体的2~12wt%;BET比表面积为320~450m2/g,孔容为0.80~1.2cm3/g,最可几孔径8.0~12.0nm;
所述的改性分子筛为十二元环的USY分子筛、H-Beta分子筛与H-SAPO-5分子筛中的一种或几种;
所述的加氢裂化预处理催化剂是将载体放置于浸渍双锥中进行抽真空处理0.5-12.0h后,在真空下采用等体积浸渍法负载活性金属,再经养生后置于微波干燥箱中进行脱水,脱水温度60~90℃,脱水时间10~60min,最后在微波加热至150~250℃下活化10~120min后制得。
根据本发明所述的加氢裂化预处理催化剂,优选:
所述的USY分子筛的骨架SiO2/Al2O3摩尔比25.0~40.0,氧化钠含量<0.08wt%,晶粒大小为100~400nm,吡啶-红外酸量0.50~1.0mmol/g,中强B酸含量占总酸量的30~50%,比表面积为500~800m2/g,孔容为0.30~0.70mL/g;
所述的H-Beta分子筛的整体SiO2/Al2O3摩尔比25.0~100.0,氧化钠含量<0.05wt%,晶粒大小为50~200nm,吡啶-红外酸量0.40~0.85mmol/g,中强B酸含量占总酸量的30~60%,比表面积为400~750m2/g,孔容为0.30~0.70mL/g;
所述的H-SAPO-5分子筛SiO2/Al2O3摩尔比0.10~0.40,氧化钠含量<0.05wt%,颗粒大小为2.0~8.0μm,吡啶-红外酸量0.20~0.60mmol/g,中强B酸含量占总酸量的40~60%,比表面积为360~600m2/g,孔容为0.28~0.50mL/g。
本发明还进一步提供了上述加氢裂化预处理催化剂的制备方法,包括以下步骤:
1)加氢裂化预处理催化剂载体的制备:将大孔氧化铝、改性氧化铝、改性分子筛、助挤助剂混合均匀,加入酸性溶液混捏、挤压成型,干燥、焙烧后得到载体;
2)络和浸渍液的配制:在浸渍槽中去离子水,再依次加入络合剂、活性组分前驱物种和助剂,均匀搅拌至溶解,定容后得到稳定的浸渍液;
3)催化剂的真空浸渍:将所制备的载体放入浸渍双锥中,进行载体的抽真空处理,在真空条件下对载体进行处理0.5~12.0h,喷入浸渍液,然后进行真空状态下浸渍0.5~4.0h,浸渍结束后养生2~12h;
4)将养生后的催化剂放置于微波干燥箱中进行脱水,脱水温度60~90℃,脱水时间10~60min,然后再放置于微波活化炉中进行活化,控制活化温度150~250℃,活化时间10~120min,活化结束后得到加氢裂化预处理催化剂;
所述的粘结剂为田菁粉、甲基纤维素与可溶性淀粉中的一种或几种,所述的酸性溶液为醋酸与柠檬酸的混合溶液;所述的络合剂为柠檬酸、乙二醇、聚乙二醇、乙醇胺、二乙醇胺、三乙醇胺、氨基三乙酸、乙二胺、乙二胺四乙酸中的一种或者几种;
所述的活性组分前驱物种为镍活性金属前驱物种、钨活性金属前驱物种、钼活性金属前驱物种;其中镍活性金属前驱物种为硝酸镍、碱式碳酸镍、乙酸镍一种或几种,钨活性金属前驱物种为偏钨酸铵,钼活性金属前驱物为七钼酸铵、三氧化钼中的一种或二种。
本发明还进一步提供了一种加氢裂化预处理催化剂经硫化后在加氢裂化工艺中的应用。
本发明加氢裂化预处理催化剂是以一步水热法合成的大孔氧化铝、溶胶凝胶法合成的改性氧化铝与十二元环改性分子筛共同作为载体原料,并首创以真空浸渍-微波低温干燥活化法制备得到的,本发明加氢预处理催化剂具有活性高、生产成本低的特点。本发明催化剂的制备方法与现有技术相比,其有益效果是:(1)能够使得活性组分在氧化铝与分子筛上均匀分布,并使得活性金属可进入分子筛微孔孔道内,增近活性组分与酸中心的距离;(2)缩短活性组分的干燥活化时间,防止活性组分的团聚,提高催化剂II类中心活性相的数量;(3)提高催化剂的干燥活化效率,降低催化剂生产能耗,进而降低催化剂生产成本。
具体实施方式
下面结合具体实施例对本发明技术方案作进一步描述。
实施例-1
催化剂设计:NiO:4.0wt%,MoO3:4.0wt%,WO3:20.0wt%,P2O5:2.0wt%,硅改性氧化铝28.0wt%,改性USY分子筛12.0wt%,大孔氧化铝30.0wt%。
将238.0g大孔氧化铝(干基含量72%)、222.0g硅改性氧化铝(SiO2含量4wt%,干基含量74%),78.0g改性Y分子筛(SiO2/Al2O3=25.0,干基含量88%)与8.0g甲基纤维素混合后投入混捏机混碾20min,将500g由水、醋酸、柠檬酸配制的酸性溶液逐次加入干粉中,先混捏至可挤膏状物,再经过空板、直径为8mm圆柱型孔板各挤压一次,最后成型为直径1.5mm蝶形条形物;将所得湿条于120℃烘箱中干燥8h,最后放置在马弗炉中程序升温至500℃焙烧3h,即得到载体ZT-1。
在100mL去离子水中依次溶解6.0g柠檬酸4.0g乙二醇、31.4g六水硝酸镍、46.0g偏钨酸铵、10.0g七钼酸铵、6.5g磷酸(浓度为85wt%),溶解澄清后将浸渍液定容至135mL。取140g载体ZT-1放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理1.0h后喷入浸渍液,真空状态下滚动浸渍2.0h,将浸渍后的载体养生4h,再于80℃微波干燥箱中脱水30min,最后放置微波活化炉中升温至200℃活化60min,即得到催化剂TC-1。
实施例-2
催化剂设计:NiO:4.0wt%,MoO3:4.0wt%,WO3:20.0wt%,P2O5:2.0wt%,硅锆改性氧化铝24.0wt%,H-Beta分子筛14.0wt%,大孔氧化铝32.0wt%。
将256.0g大孔氧化铝(干基含量72%)、183.0g硅锆改性氧化铝(SiO2、ZrO2总含量8wt%,干基含量75%),94.0g H-Beta分子筛(SiO2/Al2O3=40.0,干基含量85%)、8.0g田菁粉与4.0g甲基纤维素混合后投入混捏机混碾20min,将490g由水、醋酸、柠檬酸配制的酸性溶液逐次加入干粉中,先混捏至可挤膏状物,再经过空板、直径为8mm圆柱型孔板各挤压一次,最后成型为直径1.5mm蝶形条形物;将所得湿条于120℃烘箱中干燥8h,最后放置在马弗炉中程序升温至500℃焙烧3h,即得到载体ZT-2。
在100mL去离子水中依次溶解6.0g柠檬酸、4.0g聚乙二醇、31.4g六水硝酸镍、46.0g偏钨酸铵、10.0g七钼酸铵、6.5g磷酸(浓度为85wt%),溶解澄清后将浸渍液定容至130mL。取140g载体ZT-2放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理1.0h后喷入浸渍液,真空状态下滚动浸渍2.0h,将浸渍后的载体养生4h,再于80℃微波干燥箱中脱水30min,最后放置微波活化炉中升温至180℃活化90min,即得到催化剂TC-2。
实施例-3
催化剂设计:NiO:4.0wt%,MoO3:4.0wt%,WO3:20.0wt%,P2O5:2.0wt%,硅磷改性氧化铝28.0wt%,H-SAPO-5分子筛14.0wt%,大孔氧化铝28.0wt%。
将222.0g大孔氧化铝(干基含量72%)、222.0g硅磷改性氧化铝(SiO2、P2O5总含量6wt%,干基含量72%),89.0g H-Beta分子筛(SiO2/Al2O3=0.3,干基含量90%)、8.0g田菁粉与4.0g可溶性淀粉混合后投入混捏机混碾20min,将490g由水、醋酸、柠檬酸配制的酸性溶液逐次加入干粉中,先混捏至可挤膏状物,通过齿球形孔板挤出,经皮带传输设备拉伸、断条后,最后经切粒得到粒径2.0mm的齿球形载体;将所得湿球于120℃烘箱中干燥6h,最后放置在马弗炉中程序升温至520℃焙烧3h,即得到载体ZT-3。
在100mL去离子水中依次溶解6.0g柠檬酸4.0g乙二醇、31.4g六水硝酸镍、46.0g偏钨酸铵、10.0g七钼酸铵、6.5g磷酸(浓度为85wt%),溶解澄清后将浸渍液定容至130mL。取140g载体ZT-3放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理1.0h后喷入浸渍液,真空状态下滚动浸渍2.0h,将浸渍后的载体养生4h,再于80℃微波干燥箱中脱水30min,最后放置微波活化炉中升温至200℃活化60min,即得到催化剂TC-3。
实施例-4
催化剂设计:NiO:4.0wt%,MoO3:4.0wt%,WO3:20.0wt%,P2O5:2.0wt%,钛改性氧化铝28.0wt%,改性Y分子筛7.0wt%,H-Beta分子筛7.0wt%,大孔氧化铝28.0wt%。
将222.0g大孔氧化铝(干基含量72%)、222.0g钛改性氧化铝(TiO2含量4wt%,干基含量75%)、45.0g改性Y分子筛(SiO2/Al2O3=40.0,干基含量90%)、47.0g H-Beta分子筛(SiO2/Al2O3=60,干基含量85%)、8.0g田菁粉与4.0g可溶性淀粉混合后投入混捏机混碾20min,将490g由水、醋酸、柠檬酸配制的酸性溶液逐次加入干粉中,先混捏至可挤膏状物,通过齿球形孔板挤出,经皮带传输设备拉伸、断条后,最后经切粒得到粒径2.0mm的齿球形载体;将所得湿球于120℃烘箱中干燥6h,最后放置在马弗炉中程序升温至520℃焙烧3h,即得到载体ZT-4。
在100mL去离子水中依次溶解6.0g、柠檬酸4.0g乙二醇、31.4g六水硝酸镍、46.0g偏钨酸铵、10.0g七钼酸铵、6.5g磷酸(浓度为85wt%),溶解澄清后将浸渍液定容至135mL。取140g载体ZT-4放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理1.0h后喷入浸渍液,真空状态下滚动浸渍2.0h,将浸渍后的载体养生4h,再于90℃微波干燥箱中脱水20min,最后放置微波活化炉中升温至200℃活化60min,即得到催化剂TC-4。
对比实施例-1
催化剂设计:NiO:4.0wt%,MoO3:4.0wt%,WO3:20.0wt%,P2O5:2.0wt%,硅改性氧化铝28.0wt%,改性USY分子筛12.0wt%,大孔氧化铝30.0wt%。
在100mL去离子水中依次溶解6.0g柠檬酸4.0g乙二醇、31.4g六水硝酸镍、46.0g偏钨酸铵、10.0g七钼酸铵、6.5g磷酸(浓度为85wt%),溶解澄清后将浸渍液定容至135mL。取140g载体ZT-1放置浸渍双锥中,滚动浸渍2.0h,将浸渍后的载体养生4h,再于120℃干燥箱中脱水4h,最后放置活化炉中升温至200℃活化2h,即得到催化剂DTC-1。
实施例-5
催化剂设计:NiO:4.0wt%,WO3:24.0wt%,F:2.0wt%,载体ZT-2,载体含量70wt%。
在100mL去离子水中依次溶解6.0g柠檬酸、4.0g乙二醇、31.4g六水硝酸镍、55.0g偏钨酸铵、7.9g氟化铵,溶解澄清后将浸渍液定容至130mL。取140g载体ZT-2放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理2.0h后喷入浸渍液,真空状态下滚动浸渍3.0h,将浸渍后的载体养生8h,再于60℃微波干燥箱中脱水60min,最后放置微波活化炉中升温至150℃活化120min,即得到催化剂TC-5。
实施例-6
催化剂设计:NiO:4.0wt%,MoO3:24.0wt%,P2O5:4.0wt%,载体ZT-2,载体含量68wt%。
在100mL去离子水中依次加入4.0g乙二胺四乙酸、4.0g氨基三乙酸、3.0g乙二醇、14.8g碱式碳酸镍、48.5g三氧化钼、13.0g磷酸(浓度为85wt%),加热至溶解澄清后将浸渍液定容至130mL。取140g载体ZT-2放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理2.0h后喷入浸渍液,真空状态下滚动浸渍4.0h,将浸渍后的载体养生6h,再于90℃微波干燥箱中脱水30min,最后放置微波活化炉中升温至200℃活化90min,即得到催化剂TC-6。
实施例-7
催化剂设计:NiO:4.0wt%,MoO3:24.0wt%,P2O5:2.0wt%,B2O3:4.0wt%,载体ZT-2,载体含量68wt%。
在100mL去离子水中依次加入4.0g乙二胺四乙酸、4.0g氨基三乙酸、3.0g乙二醇、14.8g碱式碳酸镍、48.5g三氧化钼、6.5g磷酸(浓度为85wt%)、14.2g硼酸,加热至溶解澄清后将浸渍液定容至130mL。取140g载体ZT-2放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理2.0h后喷入浸渍液,真空状态下滚动浸渍4.0h,将浸渍后的载体养生6h,再于90℃微波干燥箱中脱水30min,最后放置微波活化炉中升温至200℃活化90min,即得到催化剂TC-7。
实施例-8
催化剂设计:NiO:4.0wt%,MoO3:12.0wt%,WO3:12.0wt%,P2O5:2.0wt%,F:2.0wt%,载体ZT-4,载体含量68wt%。
在100mL去离子水中依次加入4.0g三乙醇胺、4.0g氨基三乙酸、3.0g柠檬酸、14.8g碱式碳酸镍、24.2g三氧化钼、27.3g偏钨酸铵、6.5g磷酸(浓度为85wt%)、7.9g氟化铵,加热至溶解澄清后将浸渍液定容至135mL。取140g载体ZT-4放置浸渍双锥中,将浸渍双锥中的真空压力抽至小于5kPa,对载体进行处理2.0h后喷入浸渍液,真空状态下滚动浸渍4.0h,将浸渍后的载体养生6h,再于90℃微波干燥箱中脱水30min,最后放置微波活化炉中升温至200℃活化90min,即得到催化剂TC-8。
表1为本发明实施例制备的载体物化性质
表2为本发明实施例与对比例制备的催化剂物化性质
实施例-9
本实施例介绍由本发明所制备的部分加氢裂化预处理催化剂及对比催化剂的活性评价。在100mL固定床加氢反应装置上进行评价,催化剂评价条件为:反应温度为385℃,氢分压力8.5MPa,氢油体积比800:1,体积空速1.0h-1。评价原料为舟山石化焦化重馏分油,其原料性质及加氢评价结果如表-3所示。
表-3本发明制备的催化剂与对比催化剂的加氢性能
*相对脱氮活性=ln(Ntol/NC)/ln(Ntol/NDC)*100,其中Ntol为原料油中的总氮,NDC为对比催化剂加氢产物中的氮含量,NC为其他催化剂加氢产物中的氮含量。
Claims (5)
1.一种高活性加氢裂化预处理催化剂,其特征在于:
所述的加氢裂化预处理催化剂由活性组分、载体与助剂组成;所述的活性组分为Ni、Mo、W中的一种或几种,所述的载体由大孔氧化铝、改性氧化铝、改性分子筛组成,所述的助剂为B、F、P中的一种或者几种;
所述的加氢预处理催化剂组分质量百分含量为:改性氧化铝20~40%,改性分子筛10~20%,活性组分总量18~30%,助剂2~8%,其余组分为大孔氧化铝;
所述的加氢预处理催化剂载体比表面积为300~480m2/g,孔容为0.68~0.90cm3/g,中强B酸含量为0.20~0.50mmol/g;催化剂比表面积为160~300m2/g,孔容为0.38~0.60cm3/g;
所述的大孔氧化铝为一步水热法制备所得,BET比表面积为280~400m2/g,孔容为0.90~1.4cm3/g,最可几孔径12.0~18.0nm;
所述的改性氧化铝为溶胶凝胶法制备所得,改性元素为Si、Ti、Zr、P中的一种或几种元素,改性元素氧化物总含量占改性氧化铝粉体的2~12wt%;BET比表面积为320~450m2/g,孔容为0.80~1.2cm3/g,最可几孔径8.0~12.0nm;
所述的改性分子筛为十二元环的USY分子筛、H-Beta分子筛与H-SAPO-5分子筛中的一种或几种;
所述的加氢裂化预处理催化剂是将所述的载体放置于浸渍双锥中进行抽真空处理0.5-12.0h后,在真空下采用等体积浸渍法负载所述的活性组分,再经养生后置于微波干燥箱中进行脱水,脱水温度60~90℃,脱水时间10~60min,最后在微波加热至150~250℃下活化10~120min后制得。
2.根据权利要求1所述的高活性加氢裂化预处理催化剂,其特征在于,所述的USY分子筛的骨架SiO2/Al2O3摩尔比25.0~40.0,氧化钠含量<0.08wt%,晶粒大小为100~400nm,吡啶-红外酸量0.50~1.0mmol/g,中强B酸含量占总酸量的30~50%,比表面积为500~800m2/g,孔容为0.30~0.70mL/g;
所述的H-Beta分子筛的整体SiO2/Al2O3摩尔比25.0~100.0,氧化钠含量<0.05wt%,晶粒大小为50~200nm,吡啶-红外酸量0.40~0.85mmol/g,中强B酸含量占总酸量的30~60%,比表面积为400~750m2/g,孔容为0.30~0.70mL/g;所述的H-SAPO-5分子筛SiO2/Al2O3摩尔比0.10~0.40,氧化钠含量<0.05wt%,颗粒大小为2.0~8.0μm,吡啶-红外酸量0.20~0.60mmol/g,中强B酸含量占总酸量的40~60%,比表面积为360~600m2/g,孔容为0.28~0.50mL/g。
3.一种根据权利要求1所述的高活性加氢裂化预处理催化剂的制备方法,其特征在于,包括以下步骤:
1)加氢裂化预处理催化剂载体的制备:将大孔氧化铝、改性氧化铝、改性分子筛、助挤助剂混合均匀,加入酸性溶液混捏、挤压成型,干燥、焙烧后得到载体;
2)络和浸渍液的配制:在浸渍槽中加入去离子水,再依次加入络合剂、活性组分前驱物种和助剂,均匀搅拌至溶解,定容后得到稳定的浸渍液;
3)催化剂的真空浸渍:将所制备的载体放入浸渍双锥中,进行载体的抽真空处理,在真空条件下对载体进行处理0.5~12.0h后喷入浸渍液,然后进行真空状态下浸渍0.5~4.0h,浸渍结束后养生2~12h;
4)将养生后的催化剂放置于微波干燥箱中进行脱水,脱水温度60~90℃,脱水时间10~60min,然后再放置于微波活化炉中进行活化,控制活化温度150~250℃,活化时间10~120min,活化结束后得到加氢裂化预处理催化剂;
步骤1)中所述的粘结剂为田菁粉、甲基纤维素与可溶性淀粉中的一种或几种,所述的酸性溶液为醋酸与柠檬酸的混合溶液;
步骤2)中所述的络合剂为柠檬酸、乙二醇、聚乙二醇、乙醇胺、二乙醇胺、三乙醇胺、氨基三乙酸、乙二胺、乙二胺四乙酸中的一种或者几种,所述的活性组分前驱物种为硝酸镍、碱式碳酸镍、乙酸镍一种或几种,或为偏钨酸铵,或为七钼酸铵、三氧化钼中的一种或二种。
4.根据权利要求3所述的制备方法,其特征在于,步骤4)中所述的真空压力小于5kPa,真空处理时间为0.5-4h。
5.根据权利要求1所述的高活性加氢裂化预处理催化剂经硫化后在加氢裂化工艺中的应用。
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CN116139895A (zh) * | 2022-12-31 | 2023-05-23 | 中国海洋石油集团有限公司 | 一种硫化型加氢脱金属催化剂的制备方法 |
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