CN113522314A - 一种积炭失活加氢催化剂的再生方法 - Google Patents
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Abstract
本发明公开了一种积炭失活加氢催化剂的再生方法，包括如下内容：（1）将积炭失活加氢催化剂进行加氢处理，得到物料M；（2）采用含有有机物X和有机物Y的溶液浸渍处理物料M；其中有机物X为硼酸酯类化合物，有机物Y为含有苯环取代基的有机物；（3）将步骤（2）得到的物料进行水蒸气接触，进行活化处理；（4）将步骤（3）得到的物料进行烧炭处理，烧炭气氛为水蒸气和空气混合气体，得到再生后的加氢催化剂。该方法能够有效恢复再生加氢催化剂的酸性质，再生后的催化剂有着良好的加氢活性。
Description
技术领域
本发明涉及一种积炭失活加氢催化剂的再生方法，特别是具有一定酸量载体的积炭失活加氢脱硫催化剂的再生方法。
背景技术
石油炼制中使用的各种加氢催化剂，如加氢脱硫、加氢脱氮、加氢脱重金属、加氢精制、加氢脱芳烃等，其载体均为具有一定酸性中心的氧化铝或者复合氧化铝。在加氢催化剂的长周期运转过程中，其酸性中心表面会在高温条件下覆盖积炭，导致催化剂活性的下降。当运转了一定的周期后，必须经过再生处理才能够重新恢复酸性。
CN102463153A介绍了一种积炭失活加氢处理催化剂的再生复活方法，积炭失活的催化剂包含VIB族金属组分和VIII族金属组分，在含氧气体作用下，除去失活催化剂的积炭，使催化剂中的碳含量以质量含量计为0.5%～2%；然后与含碱性物质的溶液和有机添加剂的溶液接触，最后经热处理得到活性恢复的催化剂。
CN 106669866 A公开一种失活加氢催化剂的再生方法，包括如下步骤：（1）对失活加氢催化剂进行烧炭处理；（2）采用含有氟硼酸铵和2-氨基-1 ,3丙二醇的溶液浸渍处理步骤（1）烧炭后的失活加氢催化剂；（3）步骤（2）浸渍处理后的催化剂经热处理后失活加氢催化剂得到再生。
CN 106669710 A公开了一种催化柴油加氢裂化催化剂的再生方法，包括如下内容：（1）将催化柴油加氢转化工艺中失活的加氢裂化催化剂在含氧气氛中焙烧至脱炭率为40%~80%，得到脱炭催化剂；（2）将步骤（1）得到的脱炭催化剂在惰性气氛中高温处理，得到再生的加氢裂化催化剂。
CN 109926105 A提供一种加氢催化剂的再生方法，所述再生方法包括如下内容：（1）将待再生加氢催化剂与含氧气体接触进行烧炭处理，得到催化剂A；（2）将催化剂A与有机化合物溶液接触，进行热处理，得到催化剂B；（3）向催化剂B中引入水合肼，然后进行热处理，得到再生的催化剂。
发明内容
针对现有技术的不足，本发明提出了一种积炭失活加氢催化剂的再生方法，本发明方法能够有效恢复再生加氢催化剂的酸性质，再生后的催化剂有着良好的加氢活性。
本发明人在催化剂再生研究过程中有这样的发现：失活催化剂中，不同强弱酸性位的积炭存在油焦质、无定型和石墨化碳等多种形式，焙烧过程中致密的炭层与载体结合很牢固，需要大量氧气，会产生局部氧气量不足，导致积炭在再生过程中由油焦质、无定型形式转变为石墨化碳，原先和新产生的石墨化碳都需要高温焙烧才能脱除，一般要550~750℃焙烧3小时以上，而高温焙烧完全烧除积炭会对催化剂载体造成破坏，酸性质变差，表现为催化剂上中强酸、弱酸的减少，总酸量降低，以及B酸减少L酸增加，
基于上述原因，本发明提供一种积炭失活加氢催化剂的再生方法，包括如下内容：
（1）将积炭失活加氢催化剂进行加氢处理，得到物料M；
（2）采用含有有机物X和有机物Y的溶液浸渍处理物料M；其中有机物X为硼酸酯类化合物，有机物Y为含有苯环取代基的有机物；
（3）将步骤（2）得到的物料进行水蒸气接触，进行活化处理；
（4）将步骤（3）得到的物料进行烧炭处理，烧炭气氛为水蒸气和空气混合气体，得到再生后的加氢催化剂。
本发明方法中，步骤（1）所述的积炭失活加氢催化剂可以为石油炼制中各种加氢脱硫、加氢脱氮、加氢脱重金属、加氢精制、加氢脱芳烃等工艺过程失活的加氢催化剂，以失活的加氢催化剂重量为基准，积炭量一般为4wt%~19wt%；所述催化剂的活性金属组分通常为第VIB族和/或第VIII族金属，第VIB族金属一般为Mo和/或W，第VIII族金属一般为Co和/或Ni。催化剂一般以氧化铝、氧化硅、无定型硅铝、氧化钛、氧化锆、氧化硼或磷酸硅铝等载体中的一种或多种，从而具有一定的酸中心。
本发明方法中，步骤（1）所述的加氢条件为：温度为250~500℃，优选280~450℃，压力大于0.6MPa，优选1.5~6.5MPa，气氛为H2，反应时长1~4小时。
本发明方法中，步骤（2）所述的硼酸酯类化合物为硼酸三甲酯、硼酸三乙酯、硼酸三丙酯或硼酸三丁酯中的一种或多种，优选硼酸三甲酯和/或硼酸三乙酯。所述的含有苯环取代基的有机物为苯甲醇、苯乙醇、苯甲醚、苯乙醚、苯丙醇、苯丁醇、苯甲酸、苯乙酸或苯丙酸中的一种或多种，优选苯甲醇、苯乙醇、苯甲醚、苯乙醚、苯甲酸或苯乙酸中的一种或多种。
本发明方法中，步骤（2）所述的溶液中有机物X与物料M中总活性金属元素的摩尔比为0.05:1～0.15:1；有机物Y与物料M中总活性金属元素的摩尔比为0.08:1～0.2:1，所述活性金属一般为第Ⅷ族和/或ⅥB族金属。
本发明方法中，步骤（2）所述的浸渍处理条件为等体积浸渍。
本发明方法中，步骤（3）所述的活化处理条件为：温度为150~400℃，优选200~350℃；活化压力为小于15MPa，优选1~10MPa，更优选1.2~8MPa；活化时间为1~10小时，优选2~5小时。
本发明方法中，步骤（4）所述的水蒸气与空气的体积比为20:80~50:50。
本发明方法中，步骤（4）所述的烧炭条件为：烧炭温度为250~450℃，优选280~400℃；烧炭压力为小于15MPa，优选1~6MPa；烧炭时间为1~10小时，优选2~6小时。
与现有技术相比，本发明的积炭失活加氢催化剂的再生方法可以恢复催化剂总酸量的91%以上，基本达到新鲜催化剂的酸分布。再生过程中，通过油焦质类、无定型类积炭的加氢处理，终止了油焦质类、无定型类转化为石墨化碳的反应路径，同时配合后续的有机物浸渍步骤、活化步骤、水蒸气和空气烧炭步骤，很好的脱除了积炭，恢复了催化剂表面酸性。
具体实施方式
下面通过实施例进一步说明本发明方案及效果，但并不构成对本发明的限制。
取工业失活的CoMo/Al2O3型加氢催化剂，催化剂中Co元素质量含量以氧化物计为4.8wt%，钼元素质量含量以氧化物计为19.5wt%。以下实施例及比较例均采用该失活催化剂进行再生实验和活性恢复评价。
实施例1
取100g上述失活催化剂置于密闭反应炉中，通入氢气，加氢条件为：温度300℃，压力5MPa，时长3小时。将经过处理后的催化剂采用含有硼酸三甲酯和苯甲酸的乙醇溶液等体积浸渍。浸渍液中硼酸三甲酯与上述新鲜催化剂总金属的摩尔比为0.1，苯甲酸与总金属的摩尔比为0.13。浸渍后的催化剂置于密闭反应炉中，通入水蒸气活化处理，活化处理条件为：温度220℃，压力2.5MPa，时长4小时。最后通入30：70的水蒸气/空气混合气体烧炭处理，烧炭处理条件为：温度350℃，压力5MPa，时长3小时，得到再生催化剂，编号RF-1。
实施例2
取100g上述失活催化剂置于密闭反应炉中，通入氢气，加氢条件为：温度340℃，压力3MPa，时长2.5小时。将经过处理后的催化剂采用含有硼酸三乙酯和苯乙醇的乙醇溶液等体积浸渍。浸渍液中硼酸三乙酯与上述新鲜催化剂总金属的摩尔比为0.08，苯乙醇与总金属的摩尔比为0.16。浸渍后的催化剂置于密闭反应炉中，通入水蒸气活化处理，活化处理条件为：温度330℃，压力6MPa，时长2小时。最后通入45：55的水蒸气/空气混合气体烧炭处理，烧炭处理条件为：温度380℃，压力2MPa，时长5小时，得到再生催化剂，编号RF-2。
实施例3
取100g上述失活催化剂置于密闭反应炉中，通入氢气，加氢条件为：温度420℃，压力1.8MPa，时长2小时。将经过处理后的催化剂采用含有硼酸三甲酯和苯乙醚的乙醇溶液等体积浸渍。浸渍液中硼酸三甲酯与上述新鲜催化剂总金属的摩尔比为0.13，苯乙醚与总金属的摩尔比为0.1。浸渍后的催化剂置于密闭反应炉中，通入水蒸气活化处理，活化处理条件为：温度270℃，压力4MPa，时长3小时。最后通入40：60的水蒸气/空气混合气体烧炭处理，烧炭处理条件为：温度310℃，压力4MPa，时长5小时，得到再生催化剂，编号RF-3。
对比例1
按照实施例1所述方法，但去除加氢步骤，采用直接浸渍硼酸三甲酯和苯甲酸后水蒸气活化烧炭，得到再生催化剂，编号DRF-1。
对比例2
按照实施例1所述方法，但去除浸渍硼酸三甲酯和苯甲酸步骤，得到再生催化剂，编号DRF-2。
对比例3
按照实施例1所述方法，但去除水蒸气活化步骤，得到再生催化剂，编号DRF-3。
对比例4
按照实施例1所述方法，但在烧炭步骤中改为通入纯空气，得到再生催化剂，编号DRF-4。
对比例5
按照常规再生催化剂的方法，取100g上述失活催化剂置于密闭反应炉中，直接通入空气烧炭，温度600℃，时长5小时，得到再生催化剂，编号DRF-5。
新鲜剂、待生剂与实施例、比较例中的再生剂性质列于表1。
表1 新鲜剂、待生剂与实施例、比较例再生催化剂的物化性质
上述实施例及比较例再生催化剂在10mL加氢反应装置中进行活性评价试验，所用原料性质见表2，评价条件及结果见表3，表中的百分含量为质量百分含量。
表2 原料油性质
表3 评价条件及结果
Claims (12)
1.一种积炭失活加氢催化剂的再生方法，其特征在于包括如下内容：（1）将积炭失活加氢催化剂进行加氢处理，得到物料M；（2）采用含有有机物X和有机物Y的溶液浸渍处理物料M；其中有机物X为硼酸酯类化合物，有机物Y为含有苯环取代基的有机物；（3）将步骤（2）得到的物料进行水蒸气接触，进行活化处理；（4）将步骤（3）得到的物料进行烧炭处理，烧炭气氛为水蒸气和空气混合气体，得到再生后的加氢催化剂。
2.根据权利要求1所述的方法，其特征在于：步骤（1）所述的积炭失活加氢催化剂为石油炼制中各种加氢脱硫、加氢脱氮、加氢脱重金属、加氢精制、加氢脱芳烃工艺过程失活的加氢催化剂。
3.根据权利要求1所述的方法，其特征在于：以失活的加氢催化剂重量为基准，积炭量为4wt%~19wt%。
4.根据权利要求1所述的方法，其特征在于：步骤（1）所述的加氢处理条件为：温度为250~500℃，压力1~9MPa，气氛为H2，反应时长1~4小时。
5.根据权利要求1所述的方法，其特征在于：步骤（1）所述的加氢处理条件为：温度为280~450℃，压力为1.5~6.5MPa，气氛为H2，反应时长1~4小时。
6.根据权利要求1所述的方法，其特征在于：步骤（2）所述的硼酸酯类化合物为硼酸三甲酯、硼酸三乙酯、硼酸三丙酯或硼酸三丁酯中的一种或多种。
7.根据权利要求1所述的方法，其特征在于：步骤（2）所述的含有苯环取代基的有机物为苯甲醇、苯乙醇、苯甲醚、苯乙醚、苯丙醇、苯丁醇、苯甲酸、苯乙酸或苯丙酸中的一种或多种。
8.根据权利要求1所述的方法，其特征在于：步骤（2）所述的溶液中有机物X与物料M中总活性金属元素的摩尔比为0.05:1～0.15:1；有机物Y与物料M中总活性金属元素的摩尔比为0.08:1～0.2:1，所述活性金属为第Ⅷ族和/或ⅥB族金属。
9.根据权利要求1所述的方法，其特征在于：步骤（2）所述的浸渍处理条件为等体积浸渍。
10.根据权利要求1所述的方法，其特征在于：步骤（3）所述的活化处理条件为：温度为150~400℃，优选200~350℃；活化压力为小于15MPa，优选1~10MPa，更优选1.2~8MPa；活化时间为1~10小时，优选2~5小时。
11.根据权利要求1所述的方法，其特征在于：步骤（4）所述的水蒸气与空气的体积比为20:80~50:50。
12.根据权利要求1所述的方法，其特征在于：步骤（4）所述的烧炭条件为：烧炭温度为250~450℃，优选280~400℃；烧炭压力为小于15MPa，优选1~6MPa；烧炭时间为1~10小时，优选2~6小时。
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