CN106238073B - 一种MoS2/LDHS加氢脱硫催化剂的制备方法及应用 - Google Patents
一种MoS2/LDHS加氢脱硫催化剂的制备方法及应用 Download PDFInfo
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- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
本发明涉及加氢脱硫催化领域，尤其涉及一种用离子液体分步制备的负载型MoS2/LDHS加氢脱硫催化剂，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，辅以离子液体，提高纳米二硫化钼的分散性，催化剂具有良好的耐热性，抗压性和热稳定性。
Description
技术领域
本发明涉及加氢脱硫领域，尤其涉及一种采用离子液体分步加入制备的负载型MoS2/LDHS加氢脱硫催化剂的制备方法及其应用。
背景技术
近年来，随着汽车保有量的快速增加，对燃油的需求量也在逐年增加，但是燃油中的含硫化合物在燃烧过程中所形成的硫氧化物对大气造成了严重的污染，可以引起PM2.5污染进而引发雾霾天气。我国目前的燃油标准与发达国家还有一定距离，据环保部介绍，经测试即使现有汽车不做改造，仅是使用国五标准燃油，汽车尾气有关污染物的排放至少减少10%。因此，燃油中实现低成本高效深度脱硫成为燃油精制领域的热点之一。
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，其同样在吸附剂领域具有良好的催化活性。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
针对现有加氢脱硫技术的需求，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。
本发明采用两种离子液体分布制备的方法得到MoS2与类水滑石材料LDHS，并且将二者进行浸渍负载，得到能够用于超重油加氢脱硫过程的催化剂。所述MoS2/LDHS中，MoS2在类水滑石载体的表面形成密置单层。MoS2/LDHS的质量比为1-5：10-15。
本发明所提供的重油加氢催化剂的制备方法包括：
（1）离子液体制备纳米二硫化钼：向溶剂中加入四硫代钼酸盐、离子液体A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；
（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B，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)装有MoS2高压合成釜中加入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，即得到MoS2/LDHS加氢脱硫催化剂。优选的，所述溶剂为乙二醇、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，离子液体与Mo的摩尔比为0. 2-10：1。
所述离子液体A为1-甲基-3-羧乙基咪唑四氟硼酸盐，离子液体B为1-乙基-3-甲基咪唑四氟硼酸盐，离子液体A与Mo的摩尔比为0. 2-10：1，离子液体B加入量为类水滑石LDHS的0.5-2wt%。
MoS2/LDHS中，MoS2在类水滑石载体的表面形成密置单层。 MoS2/LDHS的质量比为1-5：10-15。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。
本发明与现有技术相比，本发明主要优点在于：采用功能化离子液体分步制备二硫化钼与载体类水滑石，在制备二硫化钼的过程中，离子液体的加入可以起到优化粒径分布，提高活性组分含量的作用；在制备水滑石载体过程中，采用离子液体一方面可以利用官能团起到功能化载体的作用，另一反面可以提供亲水、亲油的、亲两性的体系，有利于二硫化钼的负载，提高催化剂的加氢效果。
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，辅以溶剂和离子液体效应，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。本发明使用了离子液体所制备的纳米二硫化钼/类水滑石材料，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MoS2/LDHS不但结合了MoS2与类水滑石，而且在制备过程中，离子液体同时在制备MoS2与载体过程，优化了负载过程，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，但是本发明通过离子液体既参与了二硫化钼的制备，而且还有部分参与到负载过程，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10%。 MoS2/LDHS具有多孔结构，得到纳米粒子的直径20-70nm的纳米材料，且比表面积可以达到480-600m2/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脱硫效果。为了更进一步优化加氢脱硫的效果，本发明还进一步负载了一定的镍，发现不但起到的加氢脱硫的效果，还可以优化催化剂加氢脱氮的效果。
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）离子液体制备纳米二硫化钼：向溶剂乙醇中加入浓度为0.05mol/l四硫代钼酸铵、1-甲基-3-羧乙基咪唑四氟硼酸盐搅拌均匀，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；其中离子液体与Mo的摩尔比为1：1；
(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0.5mol/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3遍,然后在80℃干燥10小时。然后就将LDHS材料溶于溶剂乙二醇中，加入1wt%的离子液体1-乙基-3-甲基咪唑四氟硼酸盐，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)装有MoS2高压合成釜中加入LDHS，控制80℃，静置2小时，老化12小时，取出，过滤，干燥， 500℃焙烧3h，即得到MoS2/LDHS加氢脱硫催化剂。
实施例2
（1）离子液体制备纳米二硫化钼：向溶剂乙醇中加入0.1mol/l四硫代钼酸铵、1-甲基-3-羧乙基咪唑四氟硼酸盐搅拌均匀，然后加入适量的硼氢化钠，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=12，反应3h，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10小时。然后就将LDHS材料溶于溶剂乙二醇中，加入0.8wt%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)装有MoS2高压合成釜中加入LDHS，控制120℃，静置5小时，老化12小时，取出，过滤，干燥，500℃焙烧3h，即得到MoS2/LDHS加氢脱硫催化剂。
实施例3
（1）离子液体制备纳米二硫化钼：向乙二醇中加入四硫代钼酸铵、1-甲基-3-羧乙基咪唑四氟硼酸盐搅拌均匀，然后加入适量的硼氢化钠，搅拌均匀，配置成初始反应混合物并转移至高压合成釜中；四硫代钼酸铵的摩尔浓度为0.8mol/l;
（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3h，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10小时。然后就将LDHS材料溶于溶剂乙二醇中，加入1wt%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)装有MoS2高压合成釜中加入LDHS，控制100℃，静置5小时，老化12小时，取出，过滤，干燥，500℃焙烧3h，即得到MoS2/LDHS加氢脱硫催化剂。
对比例1
仅采用离子液体制备二硫化钼，不采用LDHS，其他参数同实施例1。
对比例2
不加入离子液体，制备MoS2/LDHS, 其他参数同实施例1。
应用例
本发明将MoS2/LDHS用于委内瑞拉超稠油用于悬浮床加氢反应统一测试催化剂活性。催化剂使用量(以二硫化钼计)≤80ppm情况下，脱硫率可以达到99%，沥青质脱除率>99％。明显好于单纯采用MoS2的加氢效果。
将400g委内瑞拉超稠油、催化剂5g以及1.0g硫化钠加入高温高压搅拌釜中，搅拌均匀，密封、氢气初压9.0MPa，在350℃，反应15min；继续升温至430℃，反应30min。反应完毕在180℃左右卸压，同时计量气体量并采样分析气体组成。
表1 委内瑞拉超稠油性质参数
| 项目 | 委内瑞拉超稠油 |
| 密度（20℃，g/cm<sup>3</sup>） | 1.27 |
| 100℃运动粘度，mm<sup>2</sup>/s | 3301 |
| 饱和分，wt% | 21.4 |
| 芳烃，wt% | 31.8 |
| 胶质,wt% | 27.8 |
| 沥青质,wt% | 19.0 |
| 残炭，wt% | 20.8 |
| 元素S分析，wt% | 6.5 |
| 元素N分析，wt% | 1.3 |
轻质油收率=小于350℃馏分段质量/原料油质量×100%
馏分油收率=小于550℃馏分段质量/原料油质量×100%
液体收率=液体产品质量/原料油质量×100%
转化率=小于550℃组分质量（含气）/原料油质量×100%
表2 加氢测试效果
| 项目 | 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 |
| 转化率% | 86.1 | 87.9 | 80.5 | 72.1 | 73.1 |
| 轻油收率% | 70.1 | 68.9 | 68.5 | 45.2 | 49.4 |
| 馏分油收率% | 80.6 | 89.1 | 80.1 | 71.4 | 75.6 |
| 液体收率% | 86.3 | 86.4 | 86.2 | 74.9 | 76.5 |
| 脱硫率% | 98.7 | 98.9 | 99.1 | 80.1 | 81.4 |
| 沥青质脱率% | 99.0 | 99.1 | 98.9 | 82.4 | 83.4 |
本发明将MoS2/LDHS用于委内瑞拉超稠油用于悬浮床加氢反应统一测试催化剂活性。催化剂使用量(以二硫化钼计)≤100ppm情况下，脱硫率可以达到99%，沥青质脱除率>99％。明显好于单纯采用MoS2，及不采用两步法离子液体制备MoS2/LDHS催化剂的加氢效果。
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 (7)
1.一种MoS2/LDHS加氢脱硫催化剂的制备方法，其特征在于，包括以下制备步骤：
（1）离子液体制备纳米二硫化钼：向溶剂中加入四硫代钼酸盐、离子液体A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;
（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，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B，超声搅拌10分钟后在50-60℃回流10-16h，反应结束后洗涤，在60-80℃干燥5-10小时；
(3)装有MoS2高压合成釜中加入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，即得到MoS2/LDHS加氢脱硫催化剂；所述离子液体A为1-甲基-3-羧乙基咪唑四氟硼酸盐，离子液体B为1-乙基-3-甲基咪唑四氟硼酸盐；
其中，MoS2/LDHS中，MoS2在类水滑石载体的表面形成密置单层；其中纳米二硫化钼的尺寸粒径为3-8纳米；MoS2/LDHS具有多孔结构，得到纳米粒子的直径20-70nm的纳米材料，且比表面积为480-600m2/g。
2. 如权利要求1所述的制备方法，其特征在于，离子液体A与Mo的摩尔比为0. 2-10：1，离子液体B加入量为类水滑石LDHS的0.5-2wt%。
3.如权利要求1所述的制备方法，其特征在于，所述溶剂为乙醇，还原剂为盐酸羟胺、水合肼或硼氢化钠的一种或多种。
4.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。
5.如权利要求1所述的制备方法，其特征在于，所述碱性溶液为氢氧化钠或氨水溶液。
6.如权利要求1所述的制备方法，其特征在于，MoS2/LDHS的质量比为1-5：10-15。
7.如权利要求1-6任一所述的制备方法制备的MoS2/LDHS加氢脱硫催化剂用于重油、超重油或渣油的悬浮床加氢脱硫反应。
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| Ionic liquid assisted hydrothermal synthesis of uniform MoS2 microspheres using (NH4)2MoS4 as precursors;X.X.Zhao,et al;《Materials Research Innovations》;20131206;第18卷(第5期);文章第369页Conclusions |
| 离子液体耦合固体催化剂在油品脱硫中的应用;王红岩等;《中国化工学会2013年学术年会论文集》;20151127;第405页摘要 |
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| CN109821557A (zh) | 2019-05-31 |
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