CN112547034A - 一种渣油加氢处理催化剂及其制备方法 - Google Patents
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Abstract
本发明属于催化剂材料技术领域,具体涉及一种渣油加氢处理催化剂及其制备方法。该催化剂含有氧化铝载体和负载在该载体上的活性金属组分。氧化铝载体物相为δ相或θ相,或δ相和θ相的混合相。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,本发明所提供催化剂具有适宜的孔道结构和独特的通道结构。催化剂具有良好的扩散和反应通道,降低渣油分子的扩散阻力,同时也具有较高的活性,适用于上流式渣油加氢处理过程,尤其是用于渣油加氢脱金属反应,能够消除渣油大分子扩散对反应的影响,提高催化剂利用率。
Description
技术领域
本发明属于催化剂材料技术领域,具体涉及一种渣油加氢处理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燃料油和化工产品,有助于提高原油利用率、减少环境污染、提高轻质油收率和改善产品质量等。
渣油加氢处理工艺一般包括固定床、沸腾床和浆态床渣油加氢工艺等。相对于其它渣油加氢技术,固定床渣油加氢是比较成熟的,投资和操作费用低,运行安全简单,是目前渣油加氢首选技术。在固定床渣油加氢处理技术中,为了延长装置运转周期,可在前部设置上流动反应器(UFR)。在上流式反应器中,原料油和气体混合物从反应器底部向上流动通过催化剂床层,使整个催化剂床层呈现轻微膨胀的状态,压力降较小,同时能够有效降低进入后续反应器进料的金属含量,保护下游固定床反应器,较好发挥整体催化剂的性能。通常认为比较适宜的颗粒形状为粒度较小的球形。
渣油等劣质重油中含有大量的金属(Fe、Ni和V等)、硫、氮等杂质,残碳含量高。这些杂质主要存在于胶质和沥青质等大分子化合物中。这部分物质结构复杂、分子尺寸大,扩散困难,而且金属脱除后将在催化剂表面及孔道内沉积。因此为了达到最大化渣油加氢脱沥青质、脱金属的性能,要求催化剂不仅有好的反应活性,同时还需要具备优良的扩散性能,使沥青质等大分子易接近催化剂内表面。
CN1665907A公开了一种上流式加氢催化剂,其载体由氧化铝组成,孔体积为0.6~1.1 mL/g,比表面积为110~190 m2/g,直径大于1000埃的孔小于35%以及氮脱附法峰值孔径为80~140埃,催化剂的形状为球形或椭圆形,粒度约为0.1英寸(约2 .5 mm)。该催化剂的平均孔径较小,与US5472928方法制备的催化剂相比,具有较高的加氢脱硫活性和较低的加氢脱金属活性。在重质油加氢过程中,重质原料先与根据US5472928方法制备的催化剂在加氢脱金属条件下接触,然后产物再与该催化剂接触进行加氢脱硫。该催化剂适宜作为加氢脱硫催化剂,需要之前级配加氢脱金属催化剂,才能延长该催化剂的使用寿命,因此,不适合在上流式反应器中单独使用。
发明内容
本发明目的是针对现有技术中的不足之处,提供一种渣油加氢处理催化剂及制备方法。与现有技术相比,本发明提供的催化剂,特别适用于上流式渣油加氢处理过程,具有加氢脱金属活性好、催化剂利用率高等特点。本发明所提供的制备方法具有制备过程简单、成本低等优点,易在工业上应用。
为实现上述目的,本发明采用如下技术方案:
一种渣油加氢处理催化剂,该催化剂含有氧化铝载体和负载在该载体上的活性金属组分。氧化铝载体物相为δ相或θ相,或δ相和θ相的混合相。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,以金属氧化物计算并以催化剂为基准,所述VIB族的金属组分的氧化物含量为1~10 wt%,所述VIII族的金属组分氧化物含量为0~3 wt%。所述加氢处理催化剂为球形,球形直径为3~5 mm,表面具有蜂窝孔,孔径为200~1000 μm。所述加氢处理催化剂的孔容为0.5~0.9 mL/g,最可几孔径为20~30 nm,比表面积为60~180 m2/g。
本发明还提供了一种渣油加氢处理催化剂的制备方法,该方法包括:
(1)将氧化铝前驱体、助挤剂和模板剂按一定比例混合后,加入一定量的胶溶剂,混捏、挤条,造粒机转动成球,经干燥、焙烧得到球形氧化铝载体;
(2)用含VI B族和VIII B族的活性金属组分的有机醇溶液浸渍步骤(1)得到的所述氧化铝载体,经干燥后得到催化剂。
步骤(1)所述氧化铝前驱体选自三水铝石、拟薄水铝石、薄水铝石和无定形氢氧化铝中的一种或多种的混合物,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。
步骤(1)所述助挤剂是田菁粉、甲基纤维素、羟甲基纤维素、聚乙烯醇、聚丙烯酰胺中的一种或者几种,加入量为氧化铝前驱体的1.0~5.0 wt%。
步骤(1)所述模板剂为聚苯乙烯、聚乙烯、聚丙烯、聚氨酯中的任意一种或至少两种的组合。所述模板剂的粒径为200~1000 μm。所述模板剂的加入量为氧化铝前驱体体积的20~100 %。
步骤(1)所述胶溶剂为无机酸或有机酸,所用胶溶剂的加入量为氧化铝前驱体重量的0.5~5.0%。
步骤(1)所述造粒机转速为300~800 rpm,转动时间为10~60分钟。
步骤(1)所述干燥温度为80~200 ℃,干燥时间为1~24 h。所述的焙烧温度为800~1050 ℃,焙烧时间为1~8 h。
步骤(1)所述氧化铝载体的物相为δ相或θ相,或δ相和θ相的混合相。
步骤(2)所述活性金属为至少一种的VIB族的金属组分和至少一种的VIII族的金属组分。所述有机醇为乙二醇、二乙二醇、三乙二醇、丙二醇、丙三醇、甘露醇中的一种或者多种,其加入量为VIB族的金属氧化物重量的10~100 %。
步骤(2)所述干燥温度为80~200 ℃,干燥时间为1~24 h。
本发明的显著优点在于:
(1)本发明提供开发出表面具有蜂窝孔的高性能渣油加氢处理球形催化剂,制备工艺流程简单。
(2)本发明所提供催化剂具有适宜的孔道结构和独特的通道结构。催化剂具有良好的扩散和反应通道,降低渣油分子的扩散阻力,同时也具有较高的活性,适用于上流式渣油加氢处理过程,尤其是用于渣油加氢脱金属反应,能够消除渣油大分子扩散对反应的影响,提高催化剂利用率。
附图说明
图1为本发明渣油加氢处理催化剂的外观照片。
图2为本发明渣油加氢处理催化剂C2的XRD谱图。
图3为对比例渣油加氢处理催化剂D1的XRD谱图。
具体实施方式
为进一步公开而不是限制本发明,以下结合实例对本发明作进一步的详细说明。
实施例1
称取300 g商业拟薄水铝石(干基为68 %质量),6 g田菁粉,加入6 g聚苯乙烯颗粒(200~1000 μm),搅拌混合均匀。加入300 mL含10 g柠檬酸的水溶液,混捏成可塑体,在挤条机上挤成直径为3.0 mm的圆柱形条状物。将条状物置于造粒机中,以500 rpm的转速转动30min,得到圆球。圆球在120 ℃干燥12 h,之后以2 ℃/min的升温速度升温至900 oC恒温2h,得到球形氧化铝载体A1。
称取3.3 g碱式碳酸镍,8.0 g三氧化钼,1.8 g磷酸,2.0 g乙二醇,加入110 mL去离子水,加热搅拌溶解,制得溶液B1。
取150 g载体A1,用溶液B1浸渍2 h,于120 ℃干燥12 h,得到催化剂C1。催化剂C1的物化性质列于表1。
实施例2
称取300 g商业拟薄水铝石(干基为68 %质量),6 g田菁粉,加入8 g聚苯乙烯颗粒(200~1000 μm),搅拌混合均匀。加入300 mL含6 g硝酸的水溶液,混捏成可塑体,在挤条机上挤成直径为3.0 mm的圆柱形条状物。将条状物置于造粒机中,以600rpm的转速转动30min,得到圆球。圆球在120 ℃干燥12 h,之后以2℃/min的升温速度升温至950 oC恒温2h,得到球形氧化铝载体A2。
称取2.5 g碱式碳酸镍,6.0 g三氧化钼,1.4 g磷酸,2.0 g二乙二醇,加入115 mL去离子水,加热搅拌溶解,制得溶液B2。
取150 g载体A2,用溶液B2浸渍2 h,于120 ℃干燥12 h,得到催化剂C2。催化剂C2的物化性质列于表1。
实施例3
称取300 g商业拟薄水铝石(干基为68 %质量),6 g田菁粉,加入6 g聚苯乙烯颗粒(200~1000 μm),搅拌混合均匀。加入300 mL含10 g柠檬酸的水溶液,混捏成可塑体,在挤条机上挤成直径为3.0 mm的圆柱形条状物。将条状物置于造粒机中,以500 rpm的转速转动30min,得到圆球。圆球在120 ℃干燥12 h,之后以2℃/min的升温速度升温至1000 oC恒温2h,得到球形氧化铝载体A3。
称取3.3 g碱式碳酸镍,8.0 g三氧化钼,1.8 g磷酸,2.0 g丙二醇,加入110 mL去离子水,加热搅拌溶解,制得溶液B3。
取150 g载体A3,用溶液B3浸渍2 h,于120 ℃干燥12 h,得到催化剂C3。催化剂C3的物化性质列于表1。
对比例1
称取300 g商业拟薄水铝石(干基为68 %质量),6 g田菁粉,加入6 g聚苯乙烯颗粒(200~1000 μm),搅拌混合均匀。加入300 mL含10 g柠檬酸的水溶液,混捏成可塑体,在挤条机上挤成直径为3.0 mm的圆柱形条状物。将条状物置于造粒机中,以500 rpm的转速转动30min,得到圆球。圆球在120 ℃干燥12 h,之后以2 ℃/min的升温速度升温至600 oC恒温2h,得到球形氧化铝载体A4。
取150 g载体A4,用实施例1的溶液B1浸渍2 h,于120 ℃干燥12 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1。
对比例2
称取300 g商业拟薄水铝石(干基为68 %质量),6 g田菁粉,搅拌混合均匀。加入300 mL含10 g柠檬酸的水溶液,混捏成可塑体,在挤条机上挤成直径为3.0 mm的圆柱形条状物。将条状物置于造粒机中,以500rpm的转速转动30min,得到圆球。圆球在120 ℃干燥12h,之后以2℃/min的升温速度升温至900 oC恒温2 h,得到球形氧化铝载体A5。
取150 g载体A5,用实施例1中的溶液B1浸渍2 h,于120 ℃干燥12 h,得到催化剂D2。催化剂D2中的氧化镍和氧化钼的含量列于表1。
表1
实施例4-6
实施例4-6提供本发明的渣油加氢处理方法的具体实施方式,并说明以上各实施例催化剂的渣油加氢脱金属性能。
以镍含量为31 ppm、钒含量为82 ppm、硫含量为4.31wt%的渣油为原料。催化剂装填体积为100 mL。评价前采用湿法预硫化对催化剂进行硫化处理。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300,反应3000小时后取样分析。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GB/T 37160)。按照下列公式计算金属脱除率:
催化剂利用率是指渣油原料中的金属Ni和V在球形催化剂中沉积的体积占整体球形体积的比例。
评价结果列于表2。
对比例2-3
按照实施例4-6的方法评价对比例催化剂D1和D2的渣油加氢脱金属性能。
评价结果列于表2。
表2
表2给出的结果为评价反应进行3000小时后的结果,比较可以看出,本发明提供的催化剂加氢脱金属活性优于参比催化剂,同时催化剂利用率明显高于参比催化剂。这主要是由于本发明所提供催化剂具有超大孔,提供渣油大分子扩散的孔道,同时具有适宜的反应通道,提供反应场所,从而有利于加氢脱金属活性和催化剂利用率的提高。
以上所述仅为本发明的较佳实施例,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 (10)
1.一种渣油加氢处理催化剂,其特征在于:该催化剂含有氧化铝载体和负载在该载体上的活性金属组分;氧化铝载体物相为δ相或θ相,或δ相和θ相的混合相;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。
2.根据权利要求1所述的一种渣油加氢处理催化剂,其特征在于:以金属氧化物计算并以催化剂为基准,所述VIB族的金属组分的氧化物含量为1~10 wt%,所述VIII族的金属组分氧化物含量为0.1~3 wt%。
3.根据权利要求1所述的一种渣油加氢处理催化剂,其特征在于:所述催化剂为球形,球形直径为3~5 mm,表面具有蜂窝孔,孔径为200~1000 μm。
4.一种如权利要求1-3任一项所述渣油加氢处理催化剂的制备方法,其特征在于:该方法包括以下步骤:
(1)将氧化铝前驱体、助挤剂和模板剂按一定比例混合后,加入一定量的胶溶剂,混捏、挤条,造粒机转动成球,经干燥、焙烧得到球形氧化铝载体;
(2)用含VI B族和VIII B族的活性金属组分的有机醇溶液浸渍步骤(1)得到的所述氧化铝载体,经干燥后得到催化剂。
5.根据权利要求4所述的制备方法,其特征在于:步骤(1)所述氧化铝前驱体选自三水铝石、拟薄水铝石、薄水铝石和无定形氢氧化铝中的一种或多种的混合物。
6.根据权利要求4所述的制备方法,其特征在于:步骤(1)所述助挤剂是田菁粉、甲基纤维素、羟甲基纤维素、聚乙烯醇、聚丙烯酰胺中的一种或者几种,加入量为氧化铝前驱体的1.0~5.0 wt%。
7.根据权利要求4所述的制备方法,其特征在于:步骤(1)所述模板剂为聚苯乙烯、聚乙烯、聚丙烯、聚氨酯中的任意一种或至少两种的组合;所述模板剂的粒径为200~1000 μm;所述模板剂的加入量为氧化铝前驱体体积的20~100 %。
8.根据权利要求4所述的制备方法,其特征在于:步骤(1)所述胶溶剂为无机酸或有机酸,所用胶溶剂的加入量为氧化铝前驱体重量的0.5~5.0%。
9.根据权利要求4所述的制备方法,其特征在于:步骤(1)所述造粒机转速为300~800rpm,转动时间为10~60分钟;步骤(1)所述干燥温度为80~200 ℃,干燥时间为1~24 h;所述的焙烧温度为800~1050 ℃,焙烧时间为1~8 h。
10.根据权利要求4所述的制备方法,其特征在于:步骤(2)所述有机醇为乙二醇、二乙二醇、三乙二醇、丙二醇、丙三醇、甘露醇中的一种或者多种,其加入量为VIB族的金属氧化物重量的10~100 %;步骤(2)所述干燥温度为80~200 ℃,干燥时间为1~24 h。
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