CN108654700B - 一种三峰孔分布加氢脱金属催化剂及其制备方法 - Google Patents
一种三峰孔分布加氢脱金属催化剂及其制备方法 Download PDFInfo
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- CN108654700B CN108654700B CN201810518525.2A CN201810518525A CN108654700B CN 108654700 B CN108654700 B CN 108654700B CN 201810518525 A CN201810518525 A CN 201810518525A CN 108654700 B CN108654700 B CN 108654700B
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Abstract
本发明公开了一种加氢脱金属催化剂及其制备方法。该催化剂具有三峰孔分布结构,其孔容为0.5‑1.3 mL/g,比表面积为50‑200 m2/g,孔直径小于50 nm的孔体积占总孔容的30‑50%,孔直径为50‑100 nm的孔体积占总孔容的10‑30%,孔直径大于100 nm的孔体积占总孔容的30‑50%。与现有技术相比,本发明采用全新的三峰孔分布的加氢脱金属催化剂的制备方法,对双峰孔分布的氧化铝载体进行水热处理,在介孔和大孔之间制造出过渡孔,可以弥补介孔和大孔之间的孔缺失。本发明方法制备的三峰孔分布的加氢脱金属催化剂更适用于渣油等重油加氢脱金属、脱沥青质催化剂。
Description
技术领域
本发明涉及一种三峰孔分布加氢脱金属催化剂及其制备方法。
背景技术
近年来,随着原油资源的重质化,对燃料油消费需求的增长和环保法规的日益严格,采用加氢技术将包括渣油在内的重质油转化为优质的轻质燃料油和化工产品,有助于提高原油加工深度、减少环境污染、提高轻质油收率和改善产品质量等。
渣油富集原油中大部分的硫、氮、稠环芳烃、金属(主要是Fe、Ni和V等)。与脱硫和脱氮不同,Fe、Ni和V等金属经加氢脱除后,将在催化剂孔道内逐渐沉积,覆盖在催化活性位上,并堵塞催化剂孔道导致催化剂最终完全失活,因此必须先进行加氢脱除,以免毒化下游的加氢脱硫、加氢脱氮和催化裂化催化剂等。渣油等重质油中的金属主要存在于胶质和沥青质等大分子化合物中。这部分化合物结构复杂、分子尺寸大,扩散困难,金属常在孔口附近沉积而使催化剂过早失活,降低催化剂的利用率。因此为了达到最大化渣油加氢脱金属的性能,要求催化剂不仅有好的反应活性,同时还需要具备合理的孔道分布,能够有效的改善大分子反应物的传质扩散、反应和金属沉积。解决的办法是制备存在不同孔径分布的氧化铝载体,既存在大孔(孔径在50 nm以上)又存在介孔(孔径在50 nm以下),大孔可为含金属的沥青质等大分子的扩散提供通道,促进含杂质大分子向催化剂的内部孔道快速扩散和沉积,提高催化剂的利用率,而介孔能为反应提供尽可能大的比表面,促进杂质的脱除和沉积。研究报道[J. Ancheyta et al. /Catalysis Today 109 (2005) 3–15],含有大量大孔的双峰催化剂与单峰催化剂相比,金属在催化剂径向分布较为均匀。在确定了活性和催化剂多孔性的最优组合条件下,多峰孔连续分布的催化剂金属在径向上的沉积分布更为均匀。因此,孔道连续分布的三峰及其它多峰催化剂载体,将使金属在催化剂孔道内更均匀的沉积,提高催化剂活性和容杂质能力,有助于延长催化剂的运转周期。
现有技术中,用于渣油等重质油加氢的双峰孔分布的加氢脱金属催化剂的制备和应用的报道较多,三峰及其它多峰加氢脱金属催化剂及其制备方法的报道极少。现有制备的具有双峰孔分布的加氢脱金属催化剂中,其双峰一般包括介孔和大孔,介孔直径处在2-50 nm,大孔直径在100 nm以上。双峰孔分布催化剂的大孔和介孔之间缺乏过渡孔,比如缺少50-100 nm的孔。渣油中一些大分子尺寸的化合物,可以利用大孔进行扩散,却不能很好的扩散进入介孔进行反应和沉积金属,导致金属在催化剂的孔道内分布不够均匀。因此,开发三峰及其它多峰孔分布催化剂可提高重油加氢处理尤其是加氢脱金属、脱沥青质的性能。
US5266300公开了一种具有三峰孔分布的重油加氢催化剂及其制备与应用。所述载体的制备方法包括将含有双峰孔分布的拟薄水铝石及其氧化铝混合、成型、干燥并焙烧。该载体具有三峰孔分布,其三峰孔分别分布在孔直径为3-100 nm,孔直径为100-1000 nm和孔直径为1000-10000 nm。该三峰孔催化剂比商业催化剂具有更高的加氢脱沥青质和脱金属活性。但该三峰孔催化剂有两种孔直径在100 nm以上,介孔和大孔之间仍缺乏过渡孔,无法实现介孔和大孔孔道分布的连续性。
US7790130公开了一种三峰孔分布氧化铝的制备方法。该方法包括将水合氧化铝与碳酸盐混合、成型并焙烧。所制得的氧化铝载体具有三峰孔分布,主要是小于15 nm的小孔、15-50 nm介孔和50 nm以上的大孔。该方法制得的三峰孔分布的氧化铝孔容较低,同时还有大量的碱金属钠,不适合作为重油加氢处理催化剂。
发明内容
本发明目的是针对现有的双峰和三峰孔分布的加氢脱金属催化剂在渣油加氢脱沥青质、脱金属中存在的缺点,提供一种新的三峰孔分布的加氢脱金属催化剂,并提供一种新的制备具有三峰孔分布的加氢脱金属催化剂的方法。与现有专利的双峰和三峰孔分布的催化剂的制备方法相比,本发明采用全新的三峰孔分布的加氢脱金属催化剂的制备方法,对双峰孔分布的氧化铝载体进行水热处理,在介孔和大孔之间制造出过渡孔,可以弥补介孔和大孔之间的孔缺失。本发明方法制备的三峰孔分布的加氢脱金属催化剂更适用于渣油等重油加氢脱金属、脱沥青质催化剂。
为实现上述目的,本发明采用如下技术方案:
本发明提供的一种加氢脱金属催化剂。该催化剂含有一种三峰孔分布的氧化铝载体和负载在该载体上的活性金属组分。采用压汞法测定,该催化剂具有典型的三峰孔分布结构,其孔容为0.5-1.3 mL/g,比表面积为50-200 m2/g,孔直径小于50 nm的孔体积占总孔容的30-50 %,孔直径为50-100 nm的孔体积占总孔容的10-30 %,孔直径大于100 nm的孔体积占总孔容的30-50 %。催化剂所含的活性金属组分为至少一种的VIB族的金属组分和至少一种的VIII族的金属组分,以氧化物计算并以催化剂为基准,所述VIB族的金属组分氧化物的含量为0.1-15 wt%,所述VIII族的金属组分氧化物的含量为0.1-5 wt%。催化剂还含有助剂磷,以氧化物计算并以催化剂为基准,助剂磷的氧化物的含量为0-5 wt%。
本发明还提供了一种三峰孔分布加氢脱金属催化剂的制备方法,该方法包括双峰氧化铝载体的制备、双峰氧化铝载体经水热处理制备三峰氧化铝载体和在三峰氧化铝载体上负载加氢活性金属组分。
(1)所述的双峰氧化铝载体的制备:将含拟薄水铝石的氧化铝前驱体与助挤剂、胶溶剂混捏,成型并焙烧。所述氧化铝前驱体可以选自三水铝石、拟薄水铝石、薄水铝石和无定形氢氧化铝中的一种或几种的混合物,可以是市售商品或者现有技术中任意一种方法制备的产品。优选为拟薄水铝石。所述助挤剂可以是田菁粉、甲基纤维素、淀粉、聚乙烯醇中的一种或者几种,加入量为氧化铝(由氧化铝前驱体折算氧化铝的量)的1-5 wt%。所述胶溶剂可以为无机酸或有机酸的水溶液,酸溶液的浓度为0.05-5 wt %;无机酸水溶液为盐酸、硫酸溶液或硝酸溶液;有机酸水溶液为甲酸溶液、乙酸溶液或柠檬酸溶液。所述成型方法可以采用压片、滚球或挤条等。载体的形状可根据不同要求制成片状、球型、圆柱型、三叶草型或四叶草型等。焙烧温度为500-1000 ℃,焙烧时间为1-8 h。所制得的氧化铝载体具有双峰孔分布结构。采用压汞法测定,双峰氧化铝载体的孔容为0.6-1.4 mL/g,比表面积为50-300m2/g,孔直径小于50 nm的孔体积占总孔容的50-70 %,孔直径为50-100 nm的孔体积占总孔容的0-5 %,孔直径大于100 nm的孔体积占总孔容的30-50 %。
(2)所述的双峰氧化铝载体经水热处理制备三峰氧化铝载体:将所制备的双峰孔分布氧化铝载体在密闭条件下进行水热处理,干燥并焙烧得到三峰氧化铝载体。所述水热处理是将双峰氧化铝载体和水分隔并放进反应釜等密闭容器中,在密闭条件下,加热至一定温度,然后在该水热温度下水热处理一段时间。所述水热处理的温度为150-300 ℃,时间为1-24 h。所述水热处理中水的用量为双峰氧化铝载体质量的5-200 %。干燥温度为80-200℃,干燥时间为1-24 h。焙烧温度为400-800 ℃,焙烧时间为1-8 h。制得的氧化铝载体具有三峰孔分布结构,采用压汞法测定,三峰氧化铝载体的孔容为0.6-1.4 mL/g,比表面积为50-200 m2/g,孔直径小于50 nm的孔体积占总孔容的30-50 %,孔直径为50-100 nm的孔体积占总孔容的10-30 %,孔直径大于100 nm的孔体积占总孔容的30-50 %。
(3)所述在三峰氧化铝载体上负载活性金属组分:负载方法为浸渍法,包括配制含有活性金属组分的化合物的溶液并用该溶液浸渍载体,然后进行干燥、焙烧或者不焙烧得到催化剂。催化剂所含的加氢活性金属组分选自至少一种VIB族的金属组分和至少一种VIII族的金属组分,以氧化物计算并以催化剂为基准,所述VIB族的金属组分氧化物的含量为0.1-15 wt%,所述VIII族的金属组分氧化物的含量为0.1-5 wt%。催化剂还含有助剂磷,以氧化物计算并以催化剂为基准,助剂磷的氧化物的含量为0-5 wt%。所述的浸渍温度为10-60 ℃,浸渍时间为1-24 h。所述的干燥温度为80-200 ℃,干燥时间为1-24 h。所述的焙烧温度为300-600 ℃,焙烧时间为1-10 h。
本发明的有益效果:本发明提供一种三峰孔分布的加氢脱金属催化剂以及制备方法。采用水热处理,从双峰孔分布氧化铝载体的介孔和大孔之间制造出过渡孔,实现加氢脱金属催化剂孔分布的连续化,从而提高加氢脱金属催化剂的活性。
本发明可以控制水热条件,如水的加入量和加入方式,调变过渡孔的孔径和比例。该过渡孔可以弥补大孔和介孔之间的孔缺失,实现不同孔径的孔连续分布。本发明方法简单,易于操作。
本发明提供的加氢脱金属催化剂具有三峰孔分布,可作为渣油等重质油加氢脱金属、加氢脱沥青质等催化剂。
本发明提供的催化剂可以单独使用,也可以与其它催化剂组合使用。本发明提供的催化剂和其它加氢催化剂组合使用,对重油特别是劣质渣油进行加氢处理,为后续工艺(如催化裂化)提供合格的原料油。
附图说明
图1为双峰孔分布载体A1的压汞法孔径分布图;
图2为三峰孔分布载体B2的压汞法孔径分布图。
具体实施方式
本发明用下列实施例来进一步说明本发明,但本发明的保护范围并不限于下列实施例。
实施例1-3说明本发明提供的具有三峰孔径分布的氧化铝载体及其制备方法。
实施例1
分别称取144 g市售的拟薄水铝石P1和71 g市售的拟薄水铝石P2,加入4.5 g田菁粉,混合均匀。加入250 g稀硝酸溶液(含3.0 g硝酸),混捏成可塑体,然后在挤条机上挤成直径为1.3 mm的四叶草型的条状物。将湿条在120 ℃干燥4 h,于焙烧炉中900 ℃恒温2 h,得到氧化铝载体A1。
称取80 g氧化铝载体A1,置于水热釜中。称取8 g去离子水于玻璃杯中。玻璃杯放入水热釜中。将水热釜密闭后放入烘箱中,升至220 ℃,恒温水热处理6 h。水热处理后的样品在120 ℃干燥4 h,于焙烧炉中500 ℃恒温2 h,得到水热处理的氧化铝载体B1。其孔体积和孔径分布见表1。
实施例2
称取80 g氧化铝载体A1,置于水热釜中。称取20 g去离子水于玻璃杯中。玻璃杯放入水热釜中。将水热釜密闭后放入烘箱中,升至220 ℃,恒温水热处理6h。水热处理后的样品在120 ℃干燥4 h,于焙烧炉中500 ℃恒温2 h,得到水热处理的氧化铝载体B2。其孔体积和孔径分布见表1。
实施例3
称取80 g氧化铝载体A1,置于水热釜中。称取40 g去离子水于玻璃杯中。玻璃杯放入水热釜中。将水热釜密闭后放入烘箱中,升至220 ℃,恒温水热处理6 h。水热处理后的样品在120 ℃干燥4 h,于焙烧炉中500 ℃恒温2 h,得到水热处理的氧化铝载体B3。其孔体积和孔径分布见表1。
对比例1
将实施例1中制备得到的氧化铝载体A1不进行水热处理。其孔体积和孔径分布见表1。
表1
表1和图1-2的结果表明,与对比例1相比较,本发明方法制备的氧化铝载体具有明显的三峰孔分布结构。水热处理后,介孔和大孔之间的过渡孔的比例和孔径显著增大,孔分布实现连续化。
实施例4-6说明本发明提供的催化剂及其制备方法
实施例4
取80 g载体B1,加入100 mL含12.7 g/L NiO,62.2 g/L MoO3,8.9 g/L P2O5的Ni-Mo-P溶液浸渍2 h,于120℃烘干2 h,400℃焙烧0.5 h,500℃焙烧2 h,得到催化剂C1。催化剂C1中的氧化镍和氧化钼的含量列于表2。
实施例5
取80 g载体B2,加入95 mL含13.4 g/L NiO,65.5 g/L MoO3,9.3 g/L P2O5的Ni-Mo-P溶液浸渍2 h,于120℃烘干2 h,400℃焙烧0.5 h,500℃焙烧2 h,得到催化剂C2。催化剂C2中的氧化镍和氧化钼的含量列于表2。
实施例6
取80 g载体B3,加入97 mL含13.1 g/L NiO,64.1 g/L MoO3,9.2 g/L P2O5的Ni-Mo-P溶液浸渍2 h,于120℃烘干2 h,400℃焙烧0.5 h,500℃焙烧2 h,得到催化剂C3。催化剂C3中的氧化镍和氧化钼的含量列于表2。
对比例2
取80 g载体A1,加入100 mL含12.7 g/L NiO,62.2 g/L MoO3,8.9 g/L P2O5的Ni-Mo-P溶液浸渍2 h,于120℃烘干2 h,400℃焙烧0.5 h,500℃焙烧2 h,得到催化剂D1。催化剂D1中的氧化镍和氧化钼的含量列于表2。
表2
实施例7提供本发明的渣油加氢处理方法的具体实施方式,并说明催化剂的渣油加氢脱金属性能。
实施例7
以镍含量为15 ppm、钒含量为50 ppm、硫含量为4.23 wt%、残炭为10.1wt %、氮含量为2607 ppm的渣油为原料,在100毫升小型固定床反应器上评价催化剂,结果见表3。
催化剂装填体积为100 mL。评价各例催化剂采用的工艺条件均相同。反应条件为:反应温度380 ℃,氢分压15 MPa,液时空速为1.0 h-1,氢油体积比为760,反应200小时后取样。采用电感耦合等离子体发射光谱仪(ICP-AES)测定加氢处理前后油中镍和钒的含量(具体方法参见RIPP124-90)。采用石油沥青组分测定法分析加氢处理前后油中沥青质质量分数(具体方法参见NB/SH/T 0509-2010)。按照下列公式计算金属和沥青质脱除率:
评价结果列于表3。
对比例3
按照实施例7的方法评价催化剂D1的脱沥青质率和脱金属率。结果见表3。
表3
表3给出的结果为评价反应进行200小时后的结果。比较可以看出,本发明提供的加氢脱金属催化剂的加氢脱金属活性以及加氢脱沥青质的活性高于参比催化剂。
以上所述仅为本发明的较佳实施案例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (8)
1.一种三峰孔分布加氢脱金属催化剂,其特征在于:该催化剂具有三峰孔分布结构,其孔容为0.5-1.3 mL/g,比表面积为50-200 m2/g,孔直径小于50 nm的孔体积占总孔容的30-50 %,孔直径为50-100 nm的孔体积占总孔容的10-30 %,孔直径大于100 nm的孔体积占总孔容的30-50 %;
该催化剂含有一种三峰孔分布的氧化铝载体和负载在该载体上的活性金属组分,催化剂所含的活性金属组分为至少一种的VIB族的金属组分和至少一种的VIII族的金属组分,以氧化物计算并以催化剂为基准,所述VIB族的金属组分氧化物的含量为0.1-15 wt%,所述VIII族的金属组分氧化物的含量为0.1-5 wt%;
该催化剂还含有助剂磷,以氧化物计算并以催化剂为基准,助剂磷的氧化物的含量为0-5 wt%。
2.一种制备如权利要求1所述的三峰孔分布加氢脱金属催化剂的方法,其特征在于:包括如下步骤:
(1)双峰氧化铝载体的制备:将含拟薄水铝石的氧化铝前驱体与助挤剂、胶溶剂混捏,成型、干燥并焙烧;
(2)双峰氧化铝载体经水热处理制备三峰氧化铝载体:将所制备的双峰氧化铝载体在密闭条件下进行水热处理,干燥并焙烧得到三峰氧化铝载体;所述水热处理是将双峰氧化铝载体和水分隔并放进反应釜密闭容器中,在密闭条件下,加热至一定温度,然后在该温度下水热处理一段时间;
(3)在三峰氧化铝载体上负载活性金属组分:负载方法为浸渍法,包括配制含有活性金属组分的化合物的溶液并用该溶液浸渍载体,然后进行干燥、焙烧或者不焙烧得到催化剂。
3.根据权利要求2所述的方法,其特征在于:步骤(1)中的所述助挤剂为田菁粉、甲基纤维素、淀粉、聚乙烯醇中的一种或者几种,加入量为氧化铝的1-5 wt%;所述胶溶剂为无机酸水溶液或有机酸水溶液,酸溶液的浓度为0.05-5 wt %。
4.根据权利要求2所述的方法,其特征在于:步骤(1)中的成型采用压片、滚球或挤条;载体的形状为球型、圆柱型、三叶草型或四叶草型;所述焙烧的温度为500-1000 ℃,焙烧时间为1-8 h。
5.根据权利要求2所述的方法,其特征在于:步骤(1)中所述的氧化铝载体具有双峰孔分布结构,采用压汞法测定,双峰氧化铝载体的孔容为0.6-1.4 mL/g,比表面积为50-300m2/g,孔直径小于50 nm的孔体积占总孔容的50-70 %,孔直径为50-100 nm的孔体积占总孔容的0-5 %,孔直径大于100 nm的孔体积占总孔容的30-50 %。
6.根据权利要求2所述的方法,其特征在于:步骤(2)中所述水热处理的温度为150-300℃,时间为1-24 h;所述水热处理中水的用量为双峰氧化铝载体质量的5-200 %;干燥温度为80-200 ℃,干燥时间为1-24 h;焙烧温度为400-800 ℃,焙烧时间为1-8 h。
7.根据权利要求2所述的方法,其特征在于:步骤(2)中制得的氧化铝载体具有三峰孔分布结构,采用压汞法测定,三峰氧化铝载体的孔容为0.6-1.4 mL/g,比表面积为50-200m2/g,孔直径小于50 nm的孔体积占总孔容的30-50 %,孔直径为50-100 nm的孔体积占总孔容的10-30 %,孔直径大于100 nm的孔体积占总孔容的30-50 %。
8.根据权利要求2所述的方法,其特征在于:步骤(3)中所述浸渍的温度为10-60 ℃,浸渍时间为1-24 h;所述干燥的温度为80-200 ℃,干燥时间为1-24 h;所述焙烧的温度为300-600 ℃,焙烧时间为1-10 h。
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