CN106238074B - 一种Pt-MoS2/LDHS加氢裂化催化剂的制备方法及应用 - Google Patents
一种Pt-MoS2/LDHS加氢裂化催化剂的制备方法及应用 Download PDFInfo
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Abstract
本发明涉及加氢裂化催化领域，尤其涉及一种负载型Pt‑MoS2/LDHS加氢裂化催化剂的制备方法，所得复合材料兼具有铂‑二硫化钼和类水滑石的结构和性能优势，在在合成体系，省去了硫化剂与钼酸盐前体的硫化过程，直接从原料控制，辅以溶剂效应，提高纳米二硫化钼的分散性，催化剂具有良好的耐热性，抗压性、较高的裂化率和热稳定性。
Description
技术领域
本发明涉及加氢裂化领域，尤其涉及一种采用离子液体制备的负载型Pt-MoS2/LDHS加氢裂化催化剂及其应用。
背景技术
重油(如原油的常压渣油、原油的减压渣油、重质原油、油砂、合成重质油品等)中含有大量的重金属(如镍、钒)、硫、氮等杂质，且胶质和沥青质的含量较高，为了满足催化裂化进料的要求，保护下游催化剂，必须将这些杂质尽可能地脱除，而加氢处理是脱除上述杂质的最适宜工艺。重油加氢处理催化剂按使用功能分一般包括保护剂、脱金属催化剂、脱硫催化剂、转化催化剂等。转化催化剂的主要作用就是最大限度地脱除经过脱金属和脱硫剂物料中的硫、氮和残炭等。此外，在重油加氢处理过程中，由于重油粘度高且杂质含量大，因此重油加氢处理过程的空速很小，所以催化剂的用量较比其它炼油过程大大增加，并且重油加氢处理催化剂使用寿命短，可再生性差，因此降低催化剂的成本尤为重要。
二硫化钼作为一种具有类石墨烯结构的层状半导体材料，如今已经得到了人们越来越广泛的关注，并在微电子领域表现出了良好的应用前景。然而，二硫化钼不仅仅具有优异的电学性能，其同样具有良好的催化活性。作为一种传统的加氢脱硫催化剂，二硫化钼在工业上的应用已经有数十年，同时，近些年来的研究表明，二硫化钼对于氢析出反应同样具有优异的催化活性，能够用于环保性的氢能源的获取。这使得其在催化领域和能量转换领域都具有极好的应用潜能。类水滑石（简写LDH）是一类二维纳米阴离子粘土，其组成通式可表示为[M1-x 2+Mx 3+(OH)2]x+(An-)x/n·mH2O，其中M2+指二价金属阳离子，M3+指三价金属阳离子，x为M2+与M3+的摩尔比，A n-为层间可稳定存在的阴离子，具有水滑石层状结构，因其片层元素组成和电荷密度可调、层间客体分子、晶体尺寸可控，以及生物毒性低等优点，已在有机催化、聚合物添加剂、生物医药、环境保护等诸多领域呈现了良好的应用前景。
发明内容
针对现有加氢技术的需求，对于原料越来越恶劣，重油、稠油、渣油或油砂沥青等资源的利用日益扩大，对于特殊油品的加氢脱硫催化剂具有更加严格的需求。
本发明采用离子液体的方法得到类水滑石材料LDHS，进一步负载金属Pt和具有良好加氢作用的MoS2，得到重油加氢裂化催化剂。所述Pt-MoS2/LDHS中，MoS2在类水滑石载体的表面形成密置单层。Pt含量为0.5-3wt%，MoS2占10-15wt% (基于催化剂计算),有效降低Pt的用量，降低成本。
本发明所提供的重油加氢裂化催化剂的制备方法包括：
（1）溶剂法合成纳米二硫化钼：向溶剂乙二醚中加入四硫代钼酸铵，搅拌均匀，然后加入适量的还原剂水合肼，搅拌均匀，配置成初始反应混合物并转移至高压合成釜中。
（2）采用离子液体对LDHS进行功能化：将Zn(NO3)2和Al(NO3)3溶解到水中，配置为总金属粒子浓度为0.5-1mol/L的混合溶液，保持Zn2+：Al3+的摩尔比为2：1，在恒温70～80℃水浴中滴入一定量的碱性溶液，调整PH=11-12，反应2～3h，老化12～24h，在该过程中形成具有层状结构的类水滑石沉淀，沉淀分离，去离子水洗2～3遍,然后在60-80℃干燥5-10小时。然后就将LDHS材料溶于溶剂乙二醇中，加入离子液体，超声搅拌10分钟后在50-60℃回流10-16h，反应结束后洗涤，60-80℃干燥5-10小时。
（3）采用浸渍法负载Pt与二硫化钼MoS2，得到Pt-MoS2/LDHS催化剂：向装有MoS2高压合成釜中加入PdCl2和LDHS，控制80-120℃，静置2-5小时，老化10-12小时，取出，过滤，干燥，400-500℃焙烧2-3h。
优选的，所述溶剂为乙二醚或DMF、离子液体为1-甲基-3-羧乙基咪唑四氟硼酸盐，或1-乙基-3-甲基咪唑四氟硼酸盐，其加入量为类水滑石LDHS的0.5-2wt%。
Pt-MoS2/LDHS中，MoS2在类水滑石载体的表面形成密置单层，且制备的MoS2纳米材料具有3-8nm的粒径尺寸，所述碱性溶液为氢氧化钠或氨水溶液。
所述钼酸盐为四硫代钼酸铵，其摩尔浓度为0.05-2mol/l，优选0.5-1mol/l。
所述还原剂为盐酸羟胺、水合肼或硼氢化钠。所述还原剂为盐酸羟胺、水合肼或硼氢化钠中一种或多种。
本发明主要优点在于：采用功能化离子液体制备类水滑石，本发明所得复合材料兼具有二硫化钼和类水滑石的结构和性能优势，在在合成体系，省去了硫化剂与钼酸盐前体的硫化过程，直接从原料控制，辅以乙二醚、DMF溶剂，利用溶剂效应提高纳米二硫化钼的分散性，优化二硫化钼的颗粒尺寸均匀，其中纳米二硫化钼的尺寸粒径为3-8纳米。并少量加入贵金属Pt组分，进一步增加体系的加氢活性严格降低Pt含量，降低成本。本发明使用了离子液体所制备的Pt-MoS2/LDHS，在极性、非极性的催化反应体系中均具有极好的分散性和催化活性。
现有研究中有人研究了离子液体制备MoS2的加氢催化剂，但是该催化剂仅有活性组分，其耐磨、抗压效果明显不足，不能保持长期运行加氢效果，本申请制备的Pt-MoS2/LDHS不但结合了活性组分Pt与MoS2，通过制备过程调整二者的相互协同作用，使得活性组分相互促进，进一步优化加氢过程，而且活性组分与载体类水滑石在制备过程中，离子液体优化了载体LDHS的制备过程，利于负载活性组分过程，使得催化剂能够具有较佳的加氢效果的同时，还能提高催化剂的使用寿命，直接利用二硫化钼的分散性，催化剂具有良好的耐热性，抗压性和热稳定性。
本发明提供的铂-纳米二硫化钼/类水滑石在重油、超重油、渣油的悬浮床加氢脱硫、加氢脱氮、加氢脱芳烃、加氢脱沥青反应的一种或任意二种以上中表现了极好的催化活性。
而且，由于类水滑石的层状结构，与MoS2负载过程中，可能会有一部分的MoO3出现，但是本发明二硫化钼的制备，利用溶剂效应，不但可以调控复合材料的孔分布，还能控制催化剂的双亲性，扩大应用的领域，优化使用条件；并且使得催化剂中氧化钼含量低于15%。Pt-MoS2/LDHS具有多孔结构，得到纳米粒子的直径20-90nm的纳米材料，且比表面积可以达到480-680m2/g，不但提高二硫化钼的分散性能，还能进一步优化催化剂的加氢效果。
具体实施方式
下面结合具体实施方式对本发明作进一步详细的说明。
实施例1
（1）纳米二硫化钼的制备：向溶剂乙二醚中加入浓度为0.05mol/l四硫代钼酸铵，搅拌均匀，然后加入适量的还原剂水合肼，搅拌均匀，配置成初始反应混合物并转移至高压合成釜中；
（2）将Zn(NO3)2和Al(NO3)3溶解到水中，配置为总金属粒子浓度为0.6mol/L的混合溶液，保持Zn2+：Al3+的摩尔比为2：1，在恒温70～80℃水浴中滴入一定量的碱性溶液，调整PH=11，反应2h，老化12h，在该过程中形成具有层状结构的类水滑石沉淀，沉淀分离，去离子水洗3遍,然后在60℃干燥5小时。然后就将LDHS材料溶于溶剂乙二醇中，加入离子液体1-甲基-3-羧乙基咪唑四氟硼酸盐，超声搅拌10分钟后在60℃回流10h，反应结束后，洗涤，60℃干燥5小时。
（3）向装有MoS2高压合成釜中加入0.1mol/l的PdCl2和LDHS，控制80-120℃，静置2小时，老化10小时，取出，过滤，干燥，500℃焙烧3h。
实施例2
（1）溶剂法合成纳米二硫化钼：向溶剂DMF中加入0.8mol/l四硫代钼酸铵，搅拌均匀，然后加入适量的还原剂水合肼，搅拌均匀，配置成初始反应混合物并转移至高压合成釜中。
（2）将Zn(NO3)2和Al(NO3)3溶解到水中，配置为总金属粒子浓度为0.5-1mol/L的混合溶液，保持Zn2+：Al3+的摩尔比为2：1，在恒温80℃水浴中滴入一定量的碱性溶液，调整PH=11，反应2h，老化12h，在该过程中形成具有层状结构的类水滑石沉淀，沉淀分离，去离子水洗2～3遍,然后在80℃干燥5小时。然后将LDHS材料溶于溶剂乙二醇中，加入离子液体或1-乙基-3-甲基咪唑四氟硼酸盐，超声搅拌10分钟后在50℃回流10h，反应结束后洗涤，60℃干燥5小时。
（3）向装有MoS2高压合成釜中加入0.05mol/l的PdCl2和LDHS，控制80℃，静置2小时，老化12小时，取出，过滤，干燥， 500℃焙烧2h。
实施例3
（1）溶剂法合成纳米二硫化钼：向溶剂乙二醚中加入0.1mol/l四硫代钼酸铵，搅拌均匀，然后加入适量的还原剂水合肼，搅拌均匀，配置成初始反应混合物并转移至高压合成釜中。
（2）采用离子液体对LDHS进行功能化：将Zn(NO3)2和Al(NO3)3溶解到水中，配置为总金属粒子浓度为0.5-1mol/L的混合溶液，保持Zn2+：Al3+的摩尔比为2：1，在恒温70℃水浴中滴入一定量的碱性溶液，调整PH=12，反应2h，老化12h，在该过程中形成具有层状结构的类水滑石沉淀，沉淀分离，去离子水洗2～3遍,然后在60℃干燥8小时。然后就将LDHS材料溶于溶剂乙二醇中，加入离子液体，超声搅拌10分钟后在50-60℃回流10-16h，反应结束后洗涤，60-80℃干燥5-10小时。
（3）采用浸渍法负载Pt与二硫化钼MoS2，得到Pt-MoS2/LDHS催化剂：向装有MoS2的合成釜中加入0.05mol/lPdCl2和LDHS，控制100℃，静置3小时，老化10小时，取出，过滤，干燥，500℃焙烧3h。
对比例1
不加入离子液体，其他参数同实施例1。
应用例
本发明将Pt-MoS2/LDHS用于加拿大油砂沥青加氢反应，测试催化剂活性。催化剂使用量(以二硫化钼计)≤100ppm情况下，脱硫率可以达到98%，沥青质脱除率>98％，轻油产率可以达到66-70%，并可以用于工业放大，实现催化剂长期运行不失活。加拿大油砂沥青的性质更加恶劣，加工难度远远高于普通稠油或重油。
表1 加氢脱硫效果及其他测试指标
| 项目 | 实施例1 | 实施例2 | 实施例3 | 对比例1 |
| 转化率，% | 82.2 | 81.9 | 80.5 | 65.9 |
| 轻油收率，% | 63.1 | 61.9 | 61.5 | 50.2 |
| 馏分油收率，% | 80.2 | 82.1 | 82.1 | 70.4 |
| 液体收率，% | 81.3 | 81.4 | 86.2 | 74.9 |
| 沥青质脱率，% | 99.0 | 98.2 | 98.9 | 82.5 |
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本领域的技术人员在本发明所揭露的技术范围内，可不经过创造性劳动想到的变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应该以权利要求书所限定的保护范围为准。
Claims (6)
1.一种Pt-MoS2/LDHS催化剂的制备方法，其特征在于，包括以下制备步骤：
（1）溶剂法合成纳米二硫化钼：向溶剂中加入四硫代钼酸盐搅拌均匀，然后加入适量的还原剂，搅拌均匀，配置成初始反应混合物并转移至高压合成釜中，所述溶剂为乙二醚或DMF；
（2）对LDHS进行功能化：将Zn(NO3)2和Al(NO3)3溶解到水中，配置为总金属离子浓度为0.5-1mol/L的混合溶液，保持Zn2+：Al3+的摩尔比为2：1，在恒温70～80℃水浴中滴入一定量的碱性溶液，调整pH=11-12，反应2～3h，老化12～24h，在该过程中形成具有层状结构的类水滑石LDHS沉淀，沉淀分离，去离子水洗2～3遍，然后在60-80℃干燥5-10小时，然后就将LDHS材料溶于溶剂乙二醇中，加入离子液体，超声搅拌10分钟后在50-60℃回流10-16h，反应结束后洗涤， 60-80℃干燥5-10小时；所述离子液体为1-甲基-3-羧乙基咪唑四氟硼酸盐或1-乙基-3-甲基咪唑四氟硼酸盐；
（3）采用浸渍法负载Pt与二硫化钼MoS2，得到Pt-MoS2/LDHS催化剂，具体步骤为：向装有MoS2高压合成釜中加入PtCl2和LDHS，控制80-120℃，静置2-5小时，老化10-12小时，取出，过滤，干燥，400-500℃焙烧2-3h得到负载Pt-MoS2/LDHS；MoS2在类水滑石载体的表面形成密置单层，且制备的MoS2纳米材料具有3-8nm的粒径尺寸；Pt-MoS2/LDHS具有多孔结构，得到纳米粒子的直径20-90nm的纳米材料，且比表面积达到480-680m2/g。
2.如权利要求1所述的制备方法，其特征在于，所述还原剂为盐酸羟胺、水合肼或硼氢化钠中一种或多种。
3.如权利要求1所述的制备方法，其特征在于，所述四硫代钼酸盐为四硫代钼酸铵，其摩尔浓度为0.05-2mol/L。
4.如权利要求1所述的制备方法，其特征在于，基于催化剂计算，Pt含量为0.5-3wt%，MoS2占10-15wt%。
5.如权利要求1所述的制备方法，其特征在于，所述离子液体加入量为类水滑石LDHS的0.5-2wt%。
6.如权利要求1-5任一所述制备方法制备得到的催化剂用于重油、超重油、渣油的悬浮床加氢裂化过程中。
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