CN113976143B - 一种含铁沉积失活加氢催化剂的再生方法 - Google Patents
一种含铁沉积失活加氢催化剂的再生方法 Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种含铁沉积失活加氢催化剂的再生方法，本发明提供一种含铁沉积失活加氢催化剂的再生方法，包括如下内容：（1）将含铁沉积失活加氢催化剂进行加氢处理，得到物料M；（2）将步骤（1）得到的物料M进行水蒸气接触，进行活化处理，得到物料N；（3）采用含有有机羧酸的溶液浸泡处理物料N，过滤洗涤后，再浸渍一定量的α‑羟酸水溶液，然后干燥；（4）将步骤（3）得到的干燥物料进行脱碳处理，得到再生催化剂。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。
Description
技术领域
本发明涉及一种含铁沉积失活加氢催化剂的再生方法。
背景技术
加氢催化剂在长周期的运转过程中，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。同时，由于原料油中有时含有游离铁离子，或是脂肪酸、氯等腐蚀设备产生铁离子，铁离子吸附于催化剂表面，堵塞催化剂孔道。积炭和铁元素沉积造成催化剂失活，需要再生恢复其酸性和活性。
CN 106669865 A介绍了一种铁中毒失活加氢脱硫催化剂再生液及再生方法。以再生液总重量为基准，包括如下组分：油酸3wt%~20wt%；水50wt%~70wt%；萃取液10wt%~47wt%；其中所述萃取液为***和/或苯。再生方法包括如下内容：（1）将铁中毒失活的加氢脱硫催化剂依次进行烧油、烧硫和烧炭处理；（2）步骤（1）处理后的催化剂加入到上述的再生液中进行浸泡处理，然后静置分层，水相中的催化剂经过滤、洗涤、干燥和焙烧，得到再生催化剂。
如何高效的恢复含铁沉积失活催化剂的酸性和活性，是催化剂再生工业中需要解决的问题。
发明内容
针对现有技术的不足，本发明提出了一种含铁沉积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。
发明人在催化剂再生研究过程中有这样的发现：含铁沉积失活催化剂中，部分铁属于表面沉积，易于去除；而部分铁与催化剂载体/活性金属有较强的结合，需要将此部分铁去除或良好分散，不影响催化剂的酸性及活性位的暴露。此外，对于催化剂上积炭，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，本发明提供一种含铁沉积失活加氢催化剂的再生方法，包括如下内容：
（1）将含铁沉积失活加氢催化剂进行加氢处理，得到物料M；
（2）将步骤（1）得到的物料在水蒸气气氛下活化处理，得到物料N；
（3）采用有机羧酸水溶液浸泡处理物料N，过滤洗涤后，再用α-羟酸水溶液浸渍处理，然后干燥；
（4）将步骤（3）得到的干燥物料在水蒸气和氧气混合气氛下进行脱炭处理，得到再生后的加氢催化剂。
本发明方法中，步骤（1）所述的含铁沉积加氢催化剂可以为化工生产和石油炼制中沉积少量铁元素的各种加氢脱硫、加氢脱氮、加氢精制、加氢脱芳烃等工艺过程使用的催化剂。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。载体一般为硅、钛、锆、硼或磷等改性氧化铝中的一种或多种，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250~500℃，优选280~450℃。压力一般不小于0.6MPa，优选为0.6~10MPa，更优选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）所述的活化处理条件为：温度为200~500℃，优选250~450℃；活化压力小于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（3）所述的有机羧酸为酸度系数pKa大于4的酸，如苯甲酸、苯乙酸、苯丙酸、乙酸、丙酸、丁酸、丙烯酸、丁烯酸等中的一种或多种。
本发明方法中，步骤（3）所述的有机羧酸溶液pH值为3~6，优选3.5~5.5。
本发明方法中，步骤（3）所述的有机羧酸溶液与失活催化剂的体积比为10：1~50：1。本发明方法中，步骤（3）所述的α-羟酸选自苹果酸、柠檬酸、水杨酸、乙醇酸、酒石酸或乳酸中的一种或多种。
本发明方法中，步骤（3）所述的α-羟酸与催化剂上总金属元素摩尔比为0.005:1～0.08:1。
本发明方法中，步骤（3）所述的浸渍为本领域熟知的方法，一般为等体积浸渍法，通过催化剂α-羟酸与催化剂上总金属比值和催化剂的吸液率计算确定α-羟酸水溶液浓度。
本发明方法中，步骤（4）所述的水蒸气与氧气的体积比为20:80~50:50。脱炭温度为230~450℃，优选250~430℃。脱炭压力为小于15MPa，优选1~6MPa，脱炭时间为1~10h，优选2~6h。
本发明方法中，再生后催化剂总酸量恢复至新鲜催化剂总酸量的85%以上，更优选91%以上。
与现有技术相比，本发明方法，经过加氢、活化处理后，先洗去表面易于去除的铁元素，再通过α-羟酸络合作用将催化剂上残余铁良好分散，不影响酸性位和金属活性位的暴露，铁元素作为第VIII族金属，良好分散后硫化具有有益的加氢效果。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、水蒸气和空气脱炭步骤，很好的脱除了积炭，恢复催化剂的总酸量，基本达到新鲜催化剂的酸分布。
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型加氢脱硫催化剂，催化剂中Co元素质量含量为2.8wt%，钼元素质量含量为17.5wt%。催化剂上铁元素沉积量以Fe2O3计为4wt%。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330℃，压力4MPa，时长3小时。再通入水蒸气活化处理，活化处理条件为：温度280℃，压力2MPa，时长4小时。将经过处理后的催化剂用2500mLpH值为4.5的乙酸水溶液浸泡处理，过滤洗涤后，再浸渍负载柠檬酸，柠檬酸含量与催化剂上总金属元素摩尔比为0.05:1。浸渍后的催化剂置于密闭反应炉中，通入体积比为35：65的水蒸气/空气混合气体脱炭处理，脱炭处理条件为：温度300℃，压力4MPa，时长4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370℃，压力3MPa，时长2.5小时。再通入水蒸气活化处理，活化处理条件为：温度330℃，压力4MPa，时长2小时。将经过处理后的催化剂用3500mLpH值为5的苯甲酸水溶液浸泡处理，过滤洗涤后，再浸渍负载水杨酸，水杨酸含量与催化剂上总金属元素摩尔比为0.02:1。浸渍后的催化剂置于密闭反应炉中，通入体积比为45：55的水蒸气/空气混合气体脱炭处理，脱炭处理条件为：温度350℃，压力3MPa，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410℃，压力2MPa，时长3小时。再通入水蒸气活化处理，活化处理条件为：温度370℃，压力3MPa，时长3小时。将经过处理后的催化剂用1500mLpH值为4的丙烯酸水溶液浸泡处理，过滤洗涤后，再浸渍负载苹果酸，苹果酸含量与催化剂上总金属元素摩尔比为0.04:1。浸渍后的催化剂置于密闭反应炉中，通入体积比为40：60的水蒸气/空气混合气体脱炭处理，脱炭处理条件为：温度380℃，压力2MPa，时长5小时，得到再生催化剂，编号RF-3。
对比例1
按照实施例1所述方法，但去除加氢步骤，水蒸气活化后直接采用乙酸水溶液浸泡处理，过滤洗涤后，再浸渍柠檬酸，然后脱炭后得到再生催化剂，编号DRF-1。
对比例2
按照实施例1所述方法，但去除水蒸气活化步骤，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，但去除乙酸溶液浸泡处理步骤，水蒸气活化后直接浸渍柠檬酸步骤，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，但去除柠檬酸浸渍步骤，乙酸溶液浸泡处理后直接脱炭，得到再生催化剂，编号DRF-4。
对比例5
按照实施例1所述方法，但在脱炭步骤中改为通入纯空气，得到再生催化剂，编号DRF-5。
对比例6
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，直接通入空气脱炭，温度600℃，时长5小时，得到再生催化剂，编号DRF-6。
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
| C，wt% | Fe，wt% | 比表面积，m2/g | 孔容, mL/g | 总酸量，mmol/g | <350℃酸量，mmol/g | B酸量/L酸量 | |
| 新鲜剂 | - | - | 248 | 0.25 | 0.592 | 0.357 | 0.42 |
| 待生剂 | 13 | 4.5 | 110 | 0.09 | 0.193 | 0.179 | 0.62 |
| RF-1 | 1.2 | 0.8 | 231 | 0.24 | 0.556 | 0.363 | 0.42 |
| RF-2 | 1.5 | 1.0 | 226 | 0.24 | 0.571 | 0.355 | 0.41 |
| RF-3 | 0.9 | 0.7 | 221 | 0.23 | 0.567 | 0.360 | 0.40 |
| DRF-1 | 2.6 | 0.7 | 204 | 0.20 | 0.401 | 0.263 | 0.35 |
| DRF-2 | 2.4 | 1.4 | 181 | 0.17 | 0.362 | 0.233 | 0.35 |
| DRF-3 | 2.1 | 4.3 | 148 | 0.12 | 0.358 | 0.227 | 0.36 |
| DRF-4 | 1.6 | 0.9 | 217 | 0.22 | 0.502 | 0.318 | 0.39 |
| DRF-5 | 1.9 | 0.8 | 205 | 0.22 | 0.457 | 0.306 | 0.36 |
| DRF-6 | 0.1 | 4.4 | 197 | 0.21 | 0.308 | 0.105 | 0.19 |
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，反应压力6.0MPa，反应温度 370℃，空速1.5 h-1，氢油体积比500：1，原料性质见表2，评价结果见表3。
表2 原料油性质
| 原料油 | 某炼厂常三线柴油 |
| 硫含量,wt% | 1.4 |
| 氮含量, ng/μL | 280 |
| 多环芳烃, wt% | 10.5 |
表3 评价结果
| 新鲜剂 | RF-1 | RF-2 | RF-3 | DRF-1 | DRF-2 | DRF-3 | DRF-4 | DRF-5 | DRF-6 | |
| S, ng/μL | 20.5 | 28.6 | 26.9 | 30.5 | 66.7 | 70.5 | 86.7 | 72.4 | 69.4 | 89.1 |
| N, ng/μL | 1.0 | 1.2 | 1.2 | 1.4 | 3.6 | 3.9 | 4.7 | 3.8 | 4.5 | 6.9 |
| 多环芳烃,wt% | 2.9 | 3.5 | 3.4 | 3.6 | 4.9 | 5.3 | 5.6 | 4.8 | 5.5 | 5.8 |
Claims (12)
1.一种含铁沉积失活加氢催化剂的再生方法，其特征在于包括如下内容：（1）将含铁沉积失活加氢催化剂进行加氢处理，得到物料M；（2）将步骤（1）得到的物料在水蒸气气氛下活化处理，得到物料N；（3）采用有机羧酸水溶液浸泡处理物料N，过滤洗涤后，再用α-羟酸水溶液浸渍处理，然后干燥；（4）将步骤（3）得到的干燥物料在水蒸气和氧气混合气氛下进行脱碳处理，得到再生加氢催化剂；步骤（1）所述的加氢条件为：温度250~500℃，压力0.6~10MPa，气氛为H2，反应时长1~4小时；步骤（2）所述的活化处理条件为：温度为200~500℃；活化压力为小于15MPa；活化时间为1~10小时；步骤（3）所述的有机羧酸的酸度系数pKa大于4。
2.根据权利要求1所述的方法，其特征在于：步骤（1）所述的加氢条件为：温度250~500℃，压力1.5~6.5MPa，气氛为H2，反应时长1~4小时。
3.根据权利要求1所述的方法，其特征在于：步骤（2）所述的活化处理条件为：温度为250~450℃；活化压力为1~10MPa；活化时间为2~5小时。
4.根据权利要求1所述的方法，其特征在于：步骤（3）所述的有机羧酸为苯甲酸、苯乙酸、苯丙酸、乙酸、丙酸、丁酸、丙烯酸或丁烯酸中的一种或多种。
5.根据权利要求1所述的方法，其特征在于：步骤（3）所述的有机羧酸水溶液pH值为3~6。
6.根据权利要求1所述的方法，其特征在于：步骤（3）所述的有机羧酸水溶液与失活催化剂的体积比为10：1~50：1。
7.根据权利要求1所述的方法，其特征在于：步骤（3）所述的α-羟酸选自苹果酸、柠檬酸、水杨酸、乙醇酸、酒石酸或乳酸中的一种或多种。
8.根据权利要求1所述的方法，其特征在于：步骤（3）所述的α-羟酸与催化剂上总金属元素摩尔比为0.005:1～0.08:1。
9.根据权利要求1所述的方法，其特征在于：步骤（4）所述的水蒸气与氧气的体积比为20:80~50:50。
10.根据权利要求1所述的方法，其特征在于：步骤（4）所述的脱炭处理条件为：温度为230~450℃，压力小于15MPa，时间为1~10小时。
11.根据权利要求1所述的方法，其特征在于：步骤（4）所述的脱炭处理条件为：温度为250~430℃，压力1~6MPa，时间为2~6小时。
12.根据权利要求1所述的方法，其特征在于：再生后的加氢催化剂总酸量恢复为原来新鲜催化剂的85%以上。
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