CN109420513A - 劣质重整原料预处理催化剂及其制备方法、劣质重整原料预处理方法 - Google Patents
劣质重整原料预处理催化剂及其制备方法、劣质重整原料预处理方法 Download PDFInfo
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- CN109420513A CN109420513A CN201710719253.8A CN201710719253A CN109420513A CN 109420513 A CN109420513 A CN 109420513A CN 201710719253 A CN201710719253 A CN 201710719253A CN 109420513 A CN109420513 A CN 109420513A
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明公开了一种劣质重整原料预处理催化剂及其制备方法。该催化剂由活性组分、助剂和载体组成,所述活性组分由第VIB族元素和第VIII族元素组成,所述助剂为磷;所述催化剂中,以氧化物计,含有10~30wt%第VIB族元素,2~10wt%第VIII族元素;第VIB族元素与P的重量之比为0.05~0.20,第VIII族元素与P的重量之比为0.8~2.0。本发明还公开了一种劣质重整原料预处理方法。该催化剂在劣质重整原料预处理方法中可将劣质重整原料中的硫氮脱至0.5μg/g以下,实现劣质重整原料的超深度加氢脱硫脱氮,加氢后生成油满足重整装置进料要求。
Description
技术领域
本发明涉及一种劣质重整原料预处理加氢催化剂的制备方法和应用,尤其涉及一种三叶草形用于劣质重整原料加氢预处理的催化剂及其应用。本发明的加氢催化剂具有超深度脱硫、脱氮、烯烃饱和及脱砷功能,能够对劣质重整原料进行加氢处理,加氢处理后的生成油能够满足重整进料要求;与其它催化剂相比,加氢反应过程中催化剂活性高,催化剂性能稳定,抗结焦能力强,具有处理原料广泛的特点。
背景技术
催化重整是主要的原油二次加工工艺之一,是低硫、低烯烃、高辛烷值汽油的主要来源,同时副产大量廉价氢气。为了提高我国汽油质量,尽早与国际接轨,解决我国汽油构成不合理问题,提高催化重整汽油所占比重显得十分必要。预计未来5-6年内,我国连续重整将新增产能2500万吨以上。催化重整过程使用的催化剂主要为铂铼或铂锡催化剂。重整原料石脑油中所含的微量杂质如硫、氮、砷、硅、铜、铅、锌、汞、钠、钾、钙、镁等,都是重整催化剂的毒物。因此,为了保证重整催化剂的催化性能和工业装置的长周期稳定运转,必须对重整原料石脑油进行加氢预精制,脱除石脑油中的有害杂质,使原料油质量达到重整装置进料质量指标要求。
原料来源不足成为我国催化重整装置总体加工能力占原油一次加工能力比例较低的重要原因。我国焦化石脑油产量较大,多是在较苛刻的工艺条件下进行单独加氢或是与柴油等进行混合原料加氢,然后分离出的加氢石脑油再作为重整预加氢单元进料,因此存在装置套数多、占地而积大、建设投资高、综合能耗大、操作费用高等问题,不符合未来“低碳”炼油的发展要求。因此,未来催化重整装置的原料愈来愈劣质化是未来炼化企业石脑油加工的一个重要的发展方向。
专利96106586.9公开了一种烃类加氢处理催化剂,它是由γ-Al2O3负载Ni、W、Co活性组分,还可以加入选自Mg、Zn、Fe、Ca中的任一元素作为助催化剂成分。活性组分含量:WO310~30%、NiO 1.0~7.0%、CoO0.01~1.0%,助催化剂成分的含量:MgO 0.1~5.0%、ZnO 0.1~2.0%、Fe2O30.1~3.0%、CaO 2~10%。该催化剂用于重整原料、汽油榴分和中间情分油加氢处理,同时具有高的加氢脱疏和加氢脱缸活性。
专利200410048348.4公开了一种焦化汽油的重整方法,包括如下步骤(1)将焦化馆分油进行加氢精制,切割榴程为70~175℃的馆分进行重整预精制脱除杂质,并脱水至原料水含量不超过5ppm,(2)将脱水后原料,在470~540℃、0.2~2.OMPa、氢气存在下与重整催化剂接触反应,同时将未反应的氢气进行循环,并控制循环氢气中水含量为5~20ppm。该法可有效提高焦化汽油的辛烷值,延长重整催化剂的使用寿命。
专利201110191663.2公开了一种加氢处理催化剂及其制备方法,其特征在于催化剂以含硅氧化铝为载体,钼、钴为活性组分,硼及碱金属和/或碱土金属为助剂,以催化剂总重量计,氧化钼10~20wt%,氧化钴1~8wt%,硼氧化物0~5wt%,碱金属和/或碱土金属氧化物0~5wt%,氧化硅3.25~35.6wt%。催化剂比表面积220~300m2/g,孔容0.55~0.75ml/g。含硅氧化铝载体前驱体为含无定形硅铝的拟薄水铝石,其是通过首先制备出无定形硅铝浆液和拟薄水铝石浆液,然后将这两种浆液混合、老化、过滤及干燥等后处理过程得到。该催化剂加氢脱硫、脱氮活性高,稳定性好,适用于重整原料的预加氢处理。
专利201210452002.5公开了一种重整预加氢催化剂浸渍液的配制方法,其特征在于:该溶液含有Mo、Ni、Co、W、Mg、P和助剂,含有MoO310-16g/100ml,NiO 5-9g/l,CoO33-5g/100ml,WO320-28g/100ml,MgO 0.5-2g/100ml,P/MoO3摩尔比0.3-0.5,助剂5-15g/100ml;其配制过程为:将磷酸水溶液加热至70-80℃,加入三氧化钼加热沸腾搅拌至溶解,将溶液冷却至70-80℃,缓慢加入碱式碳酸镍加热沸腾搅拌溶解,浓缩至所需体积,浓缩液降温冷却至室温,加入硝酸钴搅拌溶解,加入偏钨酸铵搅拌溶解,加入镁化合物搅拌溶解,加入助剂搅拌溶解,定容,得到浸渍液。
因而,适用于劣质重整原料预处理加氢催化剂的开发成为重整技术发展的一个重要部分,新型重整预加氢催化剂必须具备能够加氢处理劣质重整预加氢原料,在比较缓和的工艺条件下,表现出优异的加氢脱硫、加氢脱氮活性及活性稳定性,确保在工业装置连续运转3年以上。
发明内容
本发明要解决的技术问题在于克服现有技术缺陷,提供一种劣质重整原料预处理加氢催化剂及其制备方法,本发明提供的加氢催化剂,其具有比表面积大,机械强度高,孔容大,表面酸量适中,用于劣质重整原料加氢处理时,具有床层压降小、反应温度低、加氢脱硫脱氮活性高、烯烃饱和能力强等特点,同时针对重整预加氢装置特点,该催化剂具备冗杂能力大,抗结焦能力强的特点。
本发明提供一种劣质重整原料预处理催化剂,由活性组分、助剂和载体组成,所述活性组分由第VIB族元素和第VIII族元素组成,所述助剂为磷;所述催化剂中,以氧化物计,含有10~30wt%第VIB族元素,2~10wt%第VIII族元素;第VIB族元素与P的重量之比为0.05~0.20,第VIII族元素与P的重量之比为0.8~2.0;所述载体包括不同孔容和/或不同晶型的氧化铝,不同孔容氧化铝包括0.6~1.0ml/g的大孔容氧化铝和0.2~0.4ml/g的小孔容氧化铝,不同晶型的氧化铝包括γ-Al2O3和θ-Al2O3。
本发明所述的劣质重整原料预处理催化剂,其中,所述第VIII族元素优选选自Ni和Co中至少一种,所述VIB族元素优选选自Mo和W中至少一种。
本发明所述的劣质重整原料预处理催化剂,所述载体中,大孔容氧化铝/小孔容氧化铝的重量比优选为0.2~1.0,γ-Al2O3/θ-Al2O3的重量比优选为0.8~1.0。
本发明所述的劣质重整原料预处理催化剂,其中,优选的是,所述催化剂的比表面积为200~350m2/g,孔容为0.45-0.6ml/g,平均孔径为堆密度为0.8-0.9kg/L,机械强度为190-210N/cm。
本发明所述的劣质重整原料预处理催化剂,其中,所述载体优选是三叶草形的。
本发明还提供一种劣质重整原料预处理催化剂的制备方法,其是上述的劣质重整原料预处理催化剂的制备方法,包括以下步骤:
S1制备载体
将具有不同晶型和/或不同孔容的拟薄水铝石粉末、钛化合物、胶溶剂、扩孔剂、成型助剂,混合均匀后加入去离子水和酸,混捏成可塑体软块,将可塑体软块挤条、切粒,然后室温下养生,经干燥焙烧得到载体;
S2配制浸渍液
将磷酸加入到去离子水中,搅拌均匀后,加入含活性组分的化合物,充分搅拌,使含活性组分的化合物全部溶解,得浸渍液;所述含活性组分的化合物由含第VIB族元素的化合物和含第VIII族元素的盐组成;
S3制备催化剂
将载体置于浸渍槽中,加入浸渍液,得到催化剂湿条,经养生干燥焙烧制得催化剂。
本发明所述的劣质重整原料预处理催化剂的制备方法,步骤S1中,所述钛化合物优选选自氧化钛和偏钛酸中至少一种。
本发明所述的劣质重整原料预处理催化剂的制备方法,步骤S1中,所述酸优选为有机酸和无机酸中至少一种。
本发明所述的劣质重整原料预处理催化剂的制备方法,步骤S1中,所述无机酸优选为硝酸。
本发明所述的劣质重整原料预处理催化剂的制备方法,步骤S1中,所述养生的时间优选为2~4h,干燥条件优选为100~150℃、2~6h,焙烧条件优选为400~600℃、4~8h。
本发明所述的劣质重整原料预处理催化剂的制备方法,步骤S2中,所述浸渍液中,所述含第VIB族元素的盐的浓度优选为0.07~0.2mol/L,所述含第VIII族元素的盐的浓度优选为0.014~0.08mol/L。
本发明所述的劣质重整原料预处理催化剂的制备方法,步骤S2中,优选的是,所述含第VIB族元素的化合物为金属氧化物或含酸根的盐,所述含第VIII族元素的盐为硝酸盐、碱式碳酸盐中的一种或两种。
本发明所述的劣质重整原料预处理催化剂的制备方法,步骤S3中,养生、干燥和焙烧条件优选为:室温下养生2~10h,100~150℃下干燥2~6h,400~600℃焙烧2~10h。
本发明还提供一种劣质重整原料预处理方法,该预处理方法为加氢预处理,所使用催化剂为上述的劣质重整原料预处理催化剂,或为上述的方法制得的催化剂,包括以下步骤:将馏程为40~230℃的重整原料进行加氢处理,采用单段单剂的工艺流程,催化剂硫化后在氢气存在的条件下,反应温度为220~320℃,氢分压为0.5~5.0MPa,氢油体积比为50~200:1,液时体积空速为1.0~10.0h-1。
所述的活性组分中,钴化物为氧化钴、硝酸钴或碱式碳酸钴,镍化物为氧化镍、硝酸镍、碱式碳酸镍或碳酸镍,钼化物为氧化钼、硝酸钼或钼酸铵,钨化物为三氧化钨、钨酸铵、偏钨酸铵或仲钨酸铵。
所述劣质重整原料预处理加氢催化剂的制备方法,具体包括以下制备步骤:
(1)催化剂载体的制备:将不同孔容或不同晶型的一种或多种拟薄水铝石粉末、氧化钛或偏钛酸或二者混合物、胶溶剂、扩孔剂、成型助剂,混合均匀后加入去离子水和硝酸,于混捏机中混捏成可塑体软块,将可塑体软块放入挤条机料槽中,通过三叶草形孔板挤条、切粒,然后室温下养生2~4h,100~150℃下干燥2~6h,400~600℃焙烧4~8h;得到三叶草形载体;
(2)浸渍液的配制:将磷酸加入到去离子水中,搅拌均匀后将活性组分盐中的一种或两种加入到磷酸水溶液中,充分搅拌,使得活性组分金属盐全部溶解,继续加入去离子水至配制溶液体积,其中所述第Ⅷ族金属的盐溶液的浓度为0.014~0.08mol/L,所述第ⅣB族金属的盐溶液浓度为0.07~0.2mol/L,得到活性组分的共浸渍液;
(3)催化剂制备:将步骤(1)制得的三叶草形氧化铝载体置于浸渍槽中,加入步骤(2)制得的浸渍液,得到催化剂湿条,养生干燥焙烧条件为:室温下养生2~10h,100~150℃下干燥2~6h,400~600℃焙烧2~10h,制得三叶草形具有处理劣质重整原料的预处理加氢催化剂。
所述的含第VIII族金属化合物为硝酸类、碱式碳酸类中的一种或两种;所述的含ⅥB族金属化合物为金属氧化物或含该金属酸根的盐类化合物,可以是一种或几种盐类的组合。
所述的具有处理劣质重整原料的预处理加氢催化剂,适用于馏程为40~230℃的重整原料进行加氢处理,尤其适用于劣质重整原料的加氢预处理,采用单段单剂的工艺流程,催化剂硫化后在氢气存在的条件下,反应温度为220~320℃,氢分压为0.5~5.0MPa,氢油体积比为50~200:1,液时体积空速为1.0~10.0h-1。
本发明达到的效果:其催化剂具有比表面积大,机械强度高,孔容大,表面酸量适中,用于劣质重整原料加氢处理时,具有床层压降小、反应温度低、加氢脱硫脱氮活性高、烯烃饱和能力强等特点,该催化剂具备冗杂能力大,抗结焦能力强的特点,加氢生成油能够满足重整进料要求。该催化剂在劣质重整原料预处理方法中可将劣质重整原料中的硫氮脱至0.5μg/g以下,实现劣质重整原料的超深度加氢脱硫脱氮,加氢后生成油满足重整装置进料要求。
附图说明
图1为实施例中不同晶型氧化铝的XRD图;
图2为实施例中不同晶型氧化铝的N2吸附-脱附等温线及孔径分布图。
具体实施方式
以下通过具体实施例具体说明本发明的技术方案,本发明包括但不限于以下实施例。
实施例1
(1)将孔容为0.6ml/g的大孔容氧化铝/孔容为0.2ml/g小孔容氧化铝比值为1.0的商品拟薄水铝石1000g,田箐粉30g,硅胶100g,机械混合30min;柠檬酸30g溶于80g去离子水中,再加入20g浓度60%的硝酸,加入到混合均匀的粉末中,湿混35min,制得可塑体软块。
(2)将步骤(1)中制得的可塑体软块加入到挤条机的料槽中,用三叶草形孔板挤出,再经切粒得三叶草形载体。然后室温下养生3h,在空气气氛下120℃干燥4h,放入马弗炉中450~550℃,空气气氛下焙烧4h,制得含SiO2的三叶草形氧化铝载体1。
(3)将40g磷酸加入到300g去离子水中,搅拌均匀后将90g工业级三氧化钼,170g工业级偏钨酸铵,100g工业级硝酸镍加入到磷酸溶液中不停的搅拌,40分钟后升温至90~100℃,将60g工业级硝酸钴加入,搅拌20分钟后,降至室温,将溶液定容为500ml,得到浸渍液1。
(4)将含SiO2的三叶草形载体100g置于浸渍槽中,加入80mL浸渍液1,采用等体积浸渍,浸渍时间40min,然后进行养生2h,120℃干燥4h,放入马弗炉中500℃,空气气氛下焙烧4h,制得M1。
实施例2
(1)将孔容为1.0ml/g大孔容氧化铝/孔容为0.3ml/g小孔容氧化铝比值为0.2的商品拟薄水铝石1000g,田箐粉30g,硅胶100g,机械混合30min;柠檬酸30g溶于80g去离子水中,再加入20g浓度60%的硝酸,加入到混合均匀的粉末中,湿混35min,制得可塑体软块。
(2)将步骤(1)中制得的可塑体软块加入到挤条机的料槽中,用三叶草形孔板挤出,再经切粒得三叶草形载体。然后室温下养生3h,在空气气氛下120℃干燥4h,放入马弗炉中450~550℃,空气气氛下焙烧4h,制得含SiO2的三叶草形氧化铝载体2。
(3)将70g磷酸加入到300g去离子水中,搅拌均匀后将60g工业级三氧化钼,30g工业级偏钨酸铵,20g工业级碱式碳酸镍加入到磷酸溶液中不停的搅拌,40分钟后升温至90~100℃,将120g柠檬酸与35g工业级硝酸钴加入,搅拌20分钟后,降至室温,将溶液定容为500ml,得到浸渍液2。
(2)将100g三叶草形氧化铝载体2置于浸渍槽中,加入80mL浸渍液2,采用等体积浸渍,浸渍时间40min,然后进行养生2h,120℃干燥4h,放入马弗炉中500℃,空气气氛下焙烧4h,制得M2。
实施例3
(1)γ-Al2O3/θ-Al2O3的比值为0.8的商品拟薄水铝石1000g(其中孔容为0.8ml/g氧化铝与孔容为0.4ml/g氧化铝的质量比为3.5),田箐粉60g,机械混合30min;柠檬酸40g溶于80g去离子水中,再加入25g浓度68%的硝酸,加入到混合均匀的粉末中,湿混35min,制得可塑体软块。其他同实施例1,制得三叶草形氧化铝载体3。
(2)将40g磷酸加入到300g去离子水中,搅拌均匀后将120g工业级三氧化钼,100g工业级偏钨酸铵,100g工业级碱式碳酸镍加入到磷酸溶液中不停的搅拌,40分钟后升温至90~100℃,将50g工业级硝酸钴与80g柠檬酸加入,搅拌20分钟后,降至室温,将溶液定容为500ml,得到浸渍液3。
其他同实施例2,制得M3。
实施例4
(1)γ-Al2O3/θ-Al2O3的比值为1.0的商品拟薄水铝石1000g(其中孔容为0.9ml/g氧化铝与孔容为0.3ml/g氧化铝的质量比为5.2),田箐粉60g,机械混合30min;柠檬酸40g溶于80g去离子水中,再加入25g浓度68%的硝酸,加入到混合均匀的粉末中,湿混35min,制得可塑体软块。其他同实施例1,制得三叶草形氧化铝载体4。
(2)将75g磷酸加入到300g去离子水中,搅拌均匀后将120g工业级三氧化钼,150g工业级偏钨酸铵与100g工业级碱式碳酸镍加入到磷酸溶液中不停的搅拌,40分钟后升温至90~100℃,将60g工业级硝酸镍与80g工业级硝酸钴加入,搅拌20分钟后,降至室温,将溶液定容为500ml,得到浸渍液4。
其他同实施例3,制得M4。
将实施例1~4制得的M1-M4与对照品的物理性质进行比较,详见表1。对照品为国内重整预加氢催化剂(DZF-10)。
表1催化剂的物理化学性质
对照品 | M1 | M2 | M3 | M4 | |
MoO<sub>3</sub>,ω% | 13.1 | 10.9 | 8.3 | 14.2 | 15.2 |
CoO,ω% | 1.5 | 1.9 | 1.2 | 1.4 | 2.5 |
NiO,ω% | 1.2 | 3.0 | 1.5 | 6.3 | 8.4 |
WO<sub>3</sub>,ω% | 2.3 | 18.6 | 3.8 | 10.8 | 17.1 |
P<sub>2</sub>O<sub>5</sub>,ω% | -- | 4.1 | 8.4 | 4.0 | 8.1 |
SiO<sub>2</sub>,ω% | -- | 5.8 | 4.9 | -- | -- |
比表面积,m<sup>2</sup>/g | 180 | 312 | 348 | 246 | 265 |
孔容,mL/g | 0.310 | 0.595 | 0.468 | 0.504 | 0.523 |
平均孔径,nm | 3.8 | 10.8 | 12.5 | 6.9 | 7.5 |
堆密度,kg/L | 0.66 | 0.87 | 0.85 | 0.85 | 0.84 |
机械强度,N/cm | 140 | 198 | 202 | 196 | 199 |
形状 | 三叶草 | 三叶草 | 三叶草 | 三叶草 | 三叶草 |
由以上数据可以看出,实施例1~4提供的催化剂M1~M4的比表面积、孔容、孔体积、堆密度、机械强度均优于对照品。
实施例5
本实施例对实施例1~4提供的催化剂M1~M4和对照品进行评价,采用的装置为200mL小型加氢评价装置。
反应器中装入催化剂200mL,在氢气气氛下逐渐升温,升温至300℃,用含2%CS2的煤油对催化剂进行预硫化,硫化时间36h。
原料油为劣质重整原料,反应条件为:压力3.0MPa,温度:280℃,空速:4.0h-1,氢油比:150:1。M1~M4生成油和对照品生成油的对比评价结果见表2。
表2劣质重整原料对比评价结果
由表2的对比评价结果可以看出,本发明提供的劣质重整原料预处理加氢催化剂,即M1~M4加氢后产品,M1~M4生成油的主要指标如硫、氮、溴价等均优于对照品生成油。
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 (14)
1.一种劣质重整原料预处理催化剂,其特征在于,由活性组分、助剂和载体组成,所述活性组分由第VIB族元素和第VIII族元素组成,所述助剂为磷;所述催化剂中,以氧化物计,含有10~30wt%第VIB族元素,2~10wt%第VIII族元素;第VIB族元素与P的重量之比为0.05~0.20,第VIII族元素与P的重量之比为0.8~2.0;所述载体包括不同孔容和/或不同晶型的氧化铝,不同孔容氧化铝包括0.6~1.0ml/g的大孔容氧化铝和0.2~0.4ml/g的小孔容氧化铝,不同晶型的氧化铝包括γ-Al2O3和θ-Al2O3。
2.根据权利要求1所述的劣质重整原料预处理催化剂,其特征在于,所述第VIII族元素选自Ni和Co中至少一种,所述VIB族元素选自Mo和W中至少一种。
3.根据权利要求1所述的劣质重整原料预处理催化剂,其特征在于,所述载体中,大孔容氧化铝/小孔容氧化铝的重量比为0.2~1.0,γ-Al2O3/θ-Al2O3的重量比为0.8~1.0。
4.根据权利要求1所述的劣质重整原料预处理催化剂,其特征在于,所述催化剂的比表面积为200~350m2/g,孔容为0.45-0.6ml/g,平均孔径为堆密度为0.8-0.9kg/L,机械强度为190-210N/cm。
5.根据权利要求1所述的劣质重整原料预处理催化剂,其特征在于,所述载体是三叶草形的。
6.一种劣质重整原料预处理催化剂的制备方法,其是权1-5任一项所述的劣质重整原料预处理催化剂的制备方法,其特征在于,包括以下步骤:
S1制备载体
将具有不同晶型和/或不同孔容的拟薄水铝石粉末、钛化合物、胶溶剂、扩孔剂、成型助剂,混合均匀后加入去离子水和酸,混捏成可塑体软块,将可塑体软块挤条、切粒,然后室温下养生,经干燥焙烧得到载体;
S2配制浸渍液
将磷酸加入到去离子水中,搅拌均匀后,加入含活性组分的化合物,充分搅拌,使含活性组分的化合物全部溶解,得浸渍液;所述含活性组分的化合物由含第VIB族元素的化合物和含第VIII族元素的盐组成;
S3制备催化剂
将载体置于浸渍槽中,加入浸渍液,得到催化剂湿条,经养生干燥焙烧制得催化剂。
7.根据权利要求6所述的劣质重整原料预处理催化剂的制备方法,其特征在于,步骤S1中,所述钛化合物选自氧化钛和偏钛酸中至少一种。
8.根据权利要求6所述的劣质重整原料预处理催化剂的制备方法,其特征在于,步骤S1中,所述酸为有机酸和无机酸中至少一种。
9.根据权利要求6所述的劣质重整原料预处理催化剂的制备方法,其特征在于,步骤S1中,所述无机酸为硝酸。
10.根据权利要求6所述的劣质重整原料预处理催化剂的制备方法,其特征在于,步骤S1中,所述养生的时间为2~4h,干燥条件为100~150℃、2~6h,焙烧条件为400~600℃、4~8h。
11.根据权利要求6所述的劣质重整原料预处理催化剂的制备方法,其特征在于,步骤S2中,所述浸渍液中,所述含第VIB族元素的盐的浓度为0.07~0.2mol/L,所述含第VIII族元素的盐的浓度为0.014~0.08mol/L。
12.根据权利要求6所述的劣质重整原料预处理催化剂的制备方法,其特征在于,步骤S2中,所述含第VIB族元素的化合物为金属氧化物或含酸根的盐,所述含第VIII族元素的盐为硝酸盐、碱式碳酸盐中的一种或两种。
13.根据权利要求6所述的劣质重整原料预处理催化剂的制备方法,其特征在于,步骤S3中,养生、干燥和焙烧条件为:室温下养生2~10h,100~150℃下干燥2~6h,400~600℃焙烧2~10h。
14.一种劣质重整原料预处理方法,其特征在于,该预处理方法为加氢预处理,所使用催化剂为权利要求1-5任一项所述的劣质重整原料预处理催化剂,或为权利要求6-13任一项所述的方法制得的催化剂,包括以下步骤:将馏程为40~230℃的重整原料进行加氢处理,采用单段单剂的工艺流程,催化剂硫化后在氢气存在的条件下,反应温度为220~320℃,氢分压为0.5~5.0MPa,氢油体积比为50~200:1,液时体积空速为1.0~10.0h-1。
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