CN116159569B - 一种废润滑油临氢脱硅剂 - Google Patents
一种废润滑油临氢脱硅剂 Download PDFInfo
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Abstract
本发明公开了一种废润滑油临氢脱硅剂，该临氢脱硅剂包括载体和活性组分，载体为Al2O3‑SiO2‑活性炭的复合氧化物载体，活性组分是将Fe、Mo负载于复合载体的表面。该临氢脱硅剂以复合氧化物为载体，具有丰富有序的孔道结构，大孔径，大孔容，在一定的条件下能有效地脱除废润滑油中的硅元素，保护后续的加氢催化剂，保证了后续加氢装置长周期运行。
Description
技术领域
本发明涉及一种废润滑油临氢脱硅剂，属于危险废物回收、环境保护、石油化工、油品净化领域。
背景技术
大多数情况下，回收的废润滑油中的硅来源于添加剂，润滑油中通常都含有消泡剂，而甲基硅油是用途较为广泛的一款消泡剂；除此之外还有来自于外界的污染，机械设备的许多密封胶都是硅基密封胶，如果这些密封胶进入润滑油中，也会引起硅含量增高；许多发动机冷却液含有含硅抑制剂，冷却剂泄漏也会导致硅含量增高；部分清洗剂也含有有机硅表面活性剂，这些也会引起回收的废润滑油硅含量增高。
废润滑油加氢再生基础油工艺常使用加氢精制和加氢补充精制催化剂，加氢精制组合工艺与常规的废润滑油再生工艺相比，不产生污染环境的酸渣、废水，具有绿色环保、回收率高、产品质量好等优点，有广阔的应用前景。由于有机硅类的物质具有较好的热稳定性、化学稳定性，常规的酸-碱精制、溶剂精制、热处理、蒸馏都不能将有机硅类完全破坏掉。而这些有机硅是废润滑油加氢再生过程中的毒物，它沉积在加氢催化剂表面和孔道内上，导致加氢催化剂的孔道堵塞和活性组分被覆盖，造成加氢催化剂不可逆的失活。因此废润滑油加氢再生基础油装置需要先进行脱硅处理，以避免后续的加氢再生装置因催化剂中毒失活而导致频繁停车。
CN108452807公开了一种焦化石脑油脱硅催化剂，以Ni、Mo为主活性金属，Al2O3-TiO2-La2O3-石墨烯复合氧化物为载体,具备特定孔径、较大孔容，能高效脱除焦化石脑油中有机硅，保护主加氢精制催化剂。CN112705251B公开了一种含分子筛的脱硅剂，稀土元素以氧化物计为0.5%-3%， NiO计为3%-10%，第VIB族元素以氧化物计为1%-4%，分子筛为5%-35%，氧化铝为48%-90%，该脱硅剂具有适宜的酸性质、活性金属配比和大孔径分布，脱硅和抗积炭性能好。CN112705213B公开了一种加氢脱硅催化剂，ZrO2为5%-15%，稀土金属氧化物为1%-3%，NiO为2%-7%，第ⅥB族金属氧化物为0.5%-2.5%；Ni/第ⅥB族金属摩尔比5-30，该催化剂具有适宜的酸性质、金属配比和大孔径分布，脱硅和抗积炭性能好，在焦化石脑油脱硅处理中有着良好的应用前景。
上述专利中，脱硅催化剂基本上都是应用于焦化石脑油、焦化柴油脱硅装置中，在废润滑油加氢再生基础油领域还未见报道。本发明的临氢脱硅剂能够在较温和的条件下，有效地脱除废润滑油中的有机硅，使其沉积在脱硅催化剂的表面和孔道中，有利于延长后续的加氢催化剂的使用周期，保证加氢催化剂的精制效果。
发明内容
本发明的目的在于开发出一种临氢脱硅剂，主要适用于废润滑油加氢再生基础油装置，该临氢脱硅剂具有较大的孔容和孔径，同时具有适宜的加氢活性，在一定的条件下，可以将废润滑油中的有机硅转变为无机硅沉积在临氢脱硅剂的表面和孔道内，达到保护后续加氢催化剂、延长加氢装置运行周期的目的。
本发明的临氢脱硅剂是以Al2O3、SiO2和活性炭合成的复合氧化物为载体，以Fe、Mo为活性组分；该剂的活性组分含量以临氢脱硅剂总质量计，其活性组分中Fe2O3含量为1.5-4.5%，MoO3含量为6.4-10.4%。
所述的临氢脱硅剂的载体是由Al2O3、SiO2和活性炭合成的复合氧化物载体，按载体的重量百分比计Al2O3含量为30%-50%，SiO2含量为5-15%，其余为活性炭。
所述的临氢脱硅剂具有较大的比表面、孔容和孔径，比表面积为230-450m2/g，孔容为0.47-1.09ml/g，孔径为10-19nm。
所述的临氢脱硅剂的制备方法如下：将一定量的铝源、硅源、炭源、粘接剂、助挤剂和水混合均匀，经过碾压混合均匀，然后挤条成型，经干燥后在550-650℃的条件下焙烧2-4小时，得到Al2O3、SiO2和活性炭合成的复合氧化物载体。然后将活性组分Fe、Mo负载在载体上，经干燥、焙烧后即为废润滑油临氢脱硅剂。
上述的铝源、硅源和炭源分别为为大孔拟薄水铝石、气相白炭黑和椰壳活性炭。
上述粘接剂为硅溶胶、铝溶胶、硝酸和柠檬酸的混合物，按载体的重量百分比计，其添加量为2-5%，优选为3-4%。
上述助挤剂为田菁粉和羧甲基纤维素的混合物，按载体的重量百分比计，其添加量为3-6%，优选为3-5%。
所述的临氢脱硅剂中的Fe、Mo活性组分的前驱物为柠檬酸盐、硝酸盐或铵盐中的一种。
本发明的优点：
⑴开发出一种适用于废润滑油加氢再生基础油的临氢脱硅剂，能应用于现有的加氢精制装置的前端，起到保护后续加氢催化剂的作用。
⑵大孔拟薄水铝石、气相白炭黑和椰壳活性炭具有较大的孔容、孔径，增加了临氢脱硅剂的容垢能力，提高了临氢脱硅剂的活性和选择性。
⑶Fe、Mo活性组分具有适宜的加氢活性，在较高的温度下，防止废润滑油在临氢脱硅剂的作用下发生裂解反应，导致再生基础油的收率下降。
具体实施方式
以下对本发明的具体实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和过程，但本发明的保护范围不限于下述的实施例，下列实施例中未注明具体条件的实验方法，通常按照常规条件进行。
本发明所使用的大孔拟薄水铝石、气相白炭黑和椰壳活性炭均为市售。
本发明的临氢脱硅剂可以在废润滑油主加氢精制剂前使用，起到保护主精制剂和补充精制剂的作用。
实施例1：取85g拟薄水铝石（重量以Al2O3计）、20g 白炭黑(重量以SiO2计)、椰壳活性炭120g混合均匀，加入5g田菁粉和5g羧甲基纤维素的混合物，混合均匀，然后滴加含有2g硅溶胶(重量以SiO2计)、2g铝溶胶（重量以Al2O3计）、1g硝酸和1g柠檬酸混合物的水溶液，碾压混捏均匀，挤条成3mm的三叶草形，低温干燥，然后550℃焙烧4h，制成载体。再用27.56g柠檬酸铁、15.7g仲钼酸铵配制的浸渍液等体积浸渍，干燥焙烧后制得催化剂A。
实施例2：取114g拟薄水铝石（重量以Al2O3计）、30g 白炭黑(重量以SiO2计)、椰壳活性炭90g混合均匀，加入4g田菁粉和4g羧甲基纤维素的混合物，混合均匀，然后滴加含有2g硅溶胶(重量以SiO2计)、2g铝溶胶（重量以Al2O3计）、2g硝酸和2g柠檬酸混合物的水溶液，碾压混捏均匀，挤条成3mm的三叶草形，低温干燥，然后650℃焙烧3h，制成载体。再用18.40g柠檬酸铁、20.61g仲钼酸铵配制的浸渍液等体积浸渍，干燥焙烧后制得催化剂B。
实施例3：取143g拟薄水铝石（重量以Al2O3计）、10g 白炭黑(重量以SiO2计)、椰壳活性炭90g混合均匀，加入3g田菁粉和3g羧甲基纤维素的混合物，混合均匀，然后滴加含有2g硅溶胶(重量以SiO2计)、2g铝溶胶（重量以Al2O3计）、2g硝酸和2g柠檬酸混合物的水溶液，碾压混捏均匀，挤条成3mm的三叶草形，低温干燥，然后600℃焙烧3h，制成载体。再用15.15g硝酸铁、25.51g仲钼酸铵配制的浸渍液等体积浸渍，干燥焙烧后制得催化剂C。
实施例4：取143g拟薄水铝石（重量以Al2O3计）、20g 白炭黑(重量以SiO2计)、椰壳活性炭80g混合均匀，加入3.5g田菁粉和3.5g羧甲基纤维素的混合物，混合均匀，然后滴加含有2g硅溶胶(重量以SiO2计)、2g铝溶胶（重量以Al2O3计）、2g硝酸和1g柠檬酸混合物的水溶液，碾压混捏均匀，挤条成3mm的三叶草形，低温干燥，然后580℃焙烧3.5h，制成载体。再用20.2g硝酸铁、22.08g仲钼酸铵配制的浸渍液等体积浸渍，干燥焙烧后制得催化剂D。
对实施例中临氢脱硅剂进行物化性质分析，分析结果如表1。
表1 不同临氢脱硅剂的物化性质
| 项目 | 催化剂A | 催化剂B | 催化剂C | 催化剂D |
| Fe2O3，wt% | 4.5 | 3.0 | 1.5 | 2.0 |
| MoO3，wt% | 6.4 | 8.4 | 10.4 | 9.0 |
| 比表面，m2/g | 230 | 300 | 450 | 370 |
| 孔容，mL/g | 1.09 | 0.95 | 0.47 | 0.71 |
| 平均孔径，nm | 19 | 16 | 10 | 14 |
实施例5：本实施例介绍上述实施例制备的临氢脱硅剂的小试评价结果。
小试评价试验以废润滑油减压蒸馏后的毛油为评价原料，硅含量为30ppm，进行脱硅性能的对比试验。反应条件如下：氢分压为3.5MPa、反应温度为370℃、体积空速为1.0h-1、氢油比为500:1。将各实施例制备的临氢脱硅剂粉碎过筛后，分别取60mL装入Φ20×650的反应器中，催化剂床层高度为60mm，催化剂的小试评价结果见表2。
表2为小试试验评价结果
| 催化剂 | 毛油中硅含量（连续运行240h后），ppm | 脱除率，% |
| A | 0.15 | 99.50 |
| B | 0.11 | 99.63 |
| C | 0.09 | 99.70 |
| D | 0.13 | 99.57 |
| E（市售脱硅剂） | 0.81 | 97.3 |
从表2的数据可以看出，临氢脱硅剂A、B、C、D比市售脱硅剂E有较好的脱除效果，能够改善目前废润滑油加氢装置运行周期短，加氢催化剂更换频繁的不利局面，可以满足工业化使用要求，具有良好的应用前景。
Claims (6)
1.一种废润滑油临氢脱硅剂，其特征在于：该临氢脱硅剂是以Al2O3、SiO2和活性炭合成的复合氧化物为载体，以Fe、Mo为活性组分；所述的活性组分含量以临氢脱硅剂总质量计，其活性组分中Fe2O3含量为1.5-4.5%，MoO3含量为6.4-10.4%；
所述的Al2O3、SiO2和活性炭合成的复合氧化物载体，按重量百分比计Al2O3含量为30%-50%，SiO2含量为5-15%，其余为活性炭；
该临氢脱硅剂的比表面积为230-450m2/g，孔容为0.47-1.09ml/g，孔径为10-19nm。
2.根据权利要求1任一项所述的临氢脱硅剂，其特征在于，所述临氢脱硅剂的制备方法为：将一定量的铝源、硅源、炭源、粘接剂、助挤剂和水混合均匀，然后挤条成型，经干燥后在550-650℃的条件下焙烧2-4小时，得到Al2O3、SiO2和活性炭合成的复合氧化物载体,然后将活性组分Fe、Mo负载在载体上，经干燥、焙烧后即为废润滑油临氢脱硅剂。
3.根据权利要求2所述的临氢脱硅剂，其特征在于,所述的制备方法中的铝源、硅源和炭源分别为大孔拟薄水铝石、气相白炭黑和椰壳活性炭。
4.根据权利要求2所述的临氢脱硅剂，其特征在于,所述的制备方法中的粘接剂为硅溶胶、铝溶胶、硝酸和柠檬酸的混合物。
5.根据权利要求2所述的临氢脱硅剂，其特征在于,所述的制备方法中的助挤剂为田菁粉和羧甲基纤维素的混合物。
6.根据权利要求2所述的临氢脱硅剂，其特征在于,所述的制备方法中的活性组分Fe、Mo的前驱物为柠檬酸盐、硝酸盐或铵盐中的一种。
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