CN110201691A - 一种渣油加氢脱金属脱硫催化剂及其制备方法 - Google Patents
一种渣油加氢脱金属脱硫催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种渣油加氢脱金属脱硫催化剂及其制备方法，其是以不同晶体尺寸的两种拟薄水铝石为前驱体制成氧化铝载体，并以至少一种的VIB族金属组分和至少一种的VIII族金属组分构成加氢活性金属组分，以制得所述渣油加氢脱金属脱硫催化剂，该催化剂的孔容为0.4~0.8 mL/g，比表面积为100~200 m2/g，平均介孔孔径为12~20 nm，可用于渣油等重质油的加氢脱金属和脱硫。
Description
技术领域
本发明属于催化剂制备领域，具体涉及一种渣油加氢脱金属脱硫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、金属（主要是镍和钒）等。渣油加氢通过催化剂作用，在高温高压条件下将金属、硫、氮等杂质脱除，为下游催化裂化提供优质原料。渣油分子结构复杂、尺寸大，扩散困难，同时脱除的金属Ni和V会沉积在催化剂上，导致催化剂的孔道逐渐堵塞。因此为了兼顾渣油加氢脱金属和脱硫的性能，要求催化剂不仅有好的反应活性，同时还需要具备较好的扩散性能，从而有效促进杂质向催化剂的内部孔道快速扩散，并为反应提供反应场所。
为了实现催化剂同时具有较好的加氢脱金属和脱硫活性，现有公开的专利技术如下：
US5089463公开了一种适用于加氢脱金属和加氢脱硫的催化剂。该催化剂含有5-11 %的大孔，比表面积大于75 m2/g，平均介孔直径大于16 nm。该催化剂载体在制备过程中采用硝酸胶溶、氨水中和，经900 ℃高温焙烧而得。制备过程中不仅产生大量NOx，易对环境造成污染，同时能耗大，催化剂生产成本高。
CN1205314C公开了一种重油加氢脱金属、脱硫催化剂的制备方法。该方法将一部分氢氧化铝干胶粉高温焙烧后，与氢氧化铝干胶粉混合，经成型、活化制得催化剂载体，并添加碱金属和/或碱土金属为助剂。该方法需对氢氧化铝干胶粉高温预焙烧，流程长，能耗高。
发明内容
本发明针对现有渣油加氢脱金属脱硫催化剂制备中存在的缺点，提供一种同时具有较高脱金属和脱硫活性的催化剂及其制备方法。与现有方法相比，本发明制备方法简单，易于操作，所得催化剂可用于渣油等重质油的加氢脱金属和脱硫。
为实现上述目的，本发明采用如下技术方案：
一种渣油加氢脱金属脱硫催化剂，其孔容为0.4~0.8 mL/g（压汞法），比表面积为100~200 m2/g，平均介孔孔径为12~20 nm。
所述催化剂中含有氧化铝载体和加氢活性金属组分；所述氧化铝载体来源于晶体尺寸d（120）分别为1~10nm及10~30nm的两种拟薄水铝石（d（120）表示拟薄水铝石XRD谱图中代表晶面120衍射峰的晶体尺寸，所述晶面120衍射峰是指XRD谱图中2θ为23-33°的峰，d=kλ/(βcosθ)，k为Scherrer常数，λ为X射线波长，β为衍射峰的半峰宽，θ为布拉格衍射角）；所述加氢活性金属组分由至少一种的VIB族金属组分和至少一种的VIII族金属组分构成；以金属氧化物计算，所述VIB族金属组分的含量为催化剂重量的0.5-20 %，所述VIII族金属组分的含量为催化剂重量的0.5-5 %。
所述催化剂中还含有助剂磷，以其氧化物计算，助剂磷的含量为催化剂重量的0-5%。
所述渣油加氢脱金属脱硫催化剂的制备方法包括如下步骤：
（1）将一定比例的两种拟薄水铝石与助挤剂、胶溶剂混合，进行混捏、成型、干燥并焙烧，制得氧化铝载体；
（2）配制含有加氢活性金属组分和助剂磷的氧化物溶液，并用该溶液浸渍氧化铝载体，然后进行干燥和焙烧。
步骤（1）中两种拟薄水铝石的质量比为5:95-95:5。
步骤（1）所述助挤剂为田菁粉、甲基纤维素、淀粉、聚乙烯醇、聚丙烯酰胺中的一种或者几种，其加入量为氧化铝干基质量的1-5 %。
步骤（1）所述胶溶剂可以是有机酸如甲酸、乙酸、酒石酸或柠檬酸中的一种或者几种，其加入量为氧化铝干基质量的0-3 %。
步骤（1）所述成型方法为压片、滚球或挤条等。载体的形状可根据不同要求制成球型、类球型、圆柱型、三叶草型或四叶草型等。
步骤（1）所述干燥的温度为60-200 ℃，时间为1-24 h；所述焙烧的温度为400-800℃，时间为1-8 h。
步骤（2）所述浸渍采用等体积浸渍或者过量体积浸渍，其浸渍温度为10-60 ℃，浸渍时间为1-24 h；所述干燥的温度为80-200 ℃，时间为1-24 h；所述焙烧的温度为300-600℃，时间为1-12 h。
本发明的显著优点在于：
本发明提供了一种新的制备渣油加氢脱金属脱硫催化剂的方法，其通过两种不同晶体尺寸的拟薄水铝石的结合，可实现催化剂孔道结构的调整，进而制备出加氢脱金属和脱硫活性较高的催化剂，且其方法简单，易于操作。本发明方法制备的催化剂可用于渣油等重质油的加氢脱金属和脱硫。
附图说明
图1为所用拟薄水铝石PB1的XRD谱图。
图2为所用拟薄水铝石PB2的XRD谱图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
所用拟薄水铝石PB1、PB2的XRD谱图分别见图1、2。
实施例1
称取240 g商业拟薄水铝石PB1（干基72 %，d(120) = 4 nm）、60 g商业拟薄水铝石PB2（干基81%，d(120) = 20 nm），加入6 g田菁粉，混合均匀，然后加入280 mL乙酸溶液（含4 g乙酸），混捏成可塑体，然后在挤条机上挤成直径为1.3 mm的四叶草型条状物。将湿条在120℃干燥4 h，于焙烧炉中550℃恒温处理2 h，得到氧化铝载体A1。
取100 g载体A1，加入75 mL含3 g NiO，12 g MoO3，4 g P2O5的溶液浸渍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。
实施例2
称取210 g商业拟薄水铝石PB1（干基72 %，d(120) = 4 nm）、90 g商业拟薄水铝石PB2（干基81%，d(120) = 20 nm），加入6 g田菁粉，混合均匀，然后加入270 mL乙酸溶液（含4 g乙酸），混捏成可塑体，然后在挤条机上挤成直径为1.3 mm的四叶草型条状物。将湿条在120℃干燥4 h，于焙烧炉中550 ℃恒温处理2 h，得到氧化铝载体A2。
取100 g载体A2，加入70 mL含3 g NiO，12 g MoO3，4 g P2O5的溶液浸渍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。
实施例3
称取180 g商业拟薄水铝石PB1（干基72 %，d(120) = 4 nm）、120 g商业拟薄水铝石PB2（干基81%，d(120) = 20 nm），加入6 g田菁粉，混合均匀，然后加入260 mL乙酸溶液（含4 g乙酸），混捏成可塑体，然后在挤条机上挤成直径为1.3 mm的四叶草型条状物。将湿条在120℃干燥4 h，于焙烧炉中550 ℃恒温处理2 h，得到氧化铝载体A2。
取100 g载体A2，加入70 mL含3 g NiO，12 g MoO3，4 g P2O5的溶液浸渍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。
对比例1
称取180 g商业拟薄水铝石PB1-1（干基72%，d(120) = 4 nm）和120g商业拟薄水铝石PB1-2（干基72%，d(120) = 3 nm），加入6 g田菁粉，混合均匀，然后加入290 mL乙酸溶液（含4 g乙酸），混捏成可塑体，然后在挤条机上挤成直径为1.3 mm的四叶草型条状物。将湿条在120 ℃干燥4 h，于焙烧炉中550 ℃恒温处理2 h，得到氧化铝载体B1。
取100 g载体B1，加入86 mL含3 g NiO，12 g MoO3，4 g P2O5的溶液浸渍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。
对比例2
称取180 g商业拟薄水铝石PB2-1（干基81%，d(120) = 20 nm）和120 g商业拟薄水铝石PB2-2（干基80%，d(120) = 20 nm），加入6 g田菁粉，混合均匀，然后加入260 mL乙酸溶液（含3 g乙酸），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550 ℃恒温处理2 h，得到氧化铝载体B2。
取100 g载体B2，加入65 mL含3 g NiO，12 g MoO3，4 g P2O5的溶液浸渍2 h，于120℃烘干2 h，400 ℃焙烧0.5 h，500 ℃焙烧2 h，得到催化剂D2。
表1
应用实施例
以镍含量为25 ppm、钒含量为83 ppm、硫质量含量为4.46 %、残炭质量含量为12.1 %、氮含量为2940 ppm的渣油为原料，在100 mL小型固定床反应器上评价催化剂性能。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300 h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）。能量色散X射线荧光光谱法测定加氢处理前后油中硫的含量（具体方法参见GB/T 17040-2008）。按照下列公式计算金属脱除率和硫脱除率：
；
。
评价结果列于表2。
表2
表2为评价反应进行300小时后的结果。由表中可以看出，与对比例催化剂相比，本发明提供的催化剂同时具有较高的加氢脱金属和加氢脱硫活性。
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 (9)
1. 一种渣油加氢脱金属脱硫催化剂，其特征在于：所述催化剂的孔容为0.4~0.8 mL/g，比表面积为100~200 m2/g，平均介孔孔径为12~20 nm。
2.根据权利要求1所述的渣油加氢脱金属脱硫催化剂，其特征在于：所述催化剂中含有氧化铝载体和加氢活性金属组分；
所述氧化铝载体来源于晶体尺寸d（120）分别为1~10nm及10~30nm的两种拟薄水铝石；
所述加氢活性金属组分由至少一种的VIB族金属组分和至少一种的VIII族金属组分构成；以金属氧化物计算，所述VIB族金属组分的含量为催化剂重量的0.5-20 %，所述VIII族金属组分的含量为催化剂重量的0.5-5 %；
所述催化剂中还含有助剂磷，以其氧化物计算，助剂磷的含量为催化剂重量的0-5 %。
3.一种如权利要求1或2所述的渣油加氢脱金属脱硫催化剂的制备方法，其特征在于：包括如下步骤：
（1）将一定比例的两种拟薄水铝石与助挤剂、胶溶剂混合，进行混捏、成型、干燥并焙烧，制得氧化铝载体；
（2）配制含有加氢活性金属组分和助剂磷的氧化物溶液，并用该溶液浸渍氧化铝载体，然后进行干燥和焙烧。
4.根据权利要求3所述的渣油加氢脱金属脱硫催化剂的制备方法，其特征在于：步骤（1）中两种拟薄水铝石的质量比为5:95-95:5。
5. 根据权利要求3所述的渣油加氢脱金属脱硫催化剂的制备方法，其特征在于：步骤（1）所述助挤剂为田菁粉、甲基纤维素、淀粉、聚乙烯醇、聚丙烯酰胺中的一种或者几种，其加入量为氧化铝干基质量的1-5 %。
6. 根据权利要求3所述的渣油加氢脱金属脱硫催化剂的制备方法，其特征在于：步骤（1）所述胶溶剂为甲酸、乙酸、酒石酸或柠檬酸中的一种或者几种，其加入量为氧化铝干基质量的0-3 %。
7.根据权利要求3所述的渣油加氢脱金属脱硫催化剂的制备方法，其特征在于：步骤（1）所述成型方法为压片、滚球或挤条。
8. 根据权利要求3所述的渣油加氢脱金属脱硫催化剂的制备方法，其特征在于：步骤（1）所述干燥的温度为60-200 ℃，时间为1-24 h；所述焙烧的温度为400-800 ℃，时间为1-8 h。
9. 根据权利要求3所述的渣油加氢脱金属脱硫催化剂的制备方法，其特征在于：步骤（2）所述浸渍采用等体积浸渍或者过量体积浸渍，其浸渍温度为10-60 ℃，浸渍时间为1-24h；所述干燥的温度为80-200 ℃，时间为1-24 h；所述焙烧的温度为300-600 ℃，时间为1-12 h。
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