CN113244932B - 一种合成无定型结构MoS2蛋壳型加氢脱硫催化剂的方法及应用 - Google Patents
一种合成无定型结构MoS2蛋壳型加氢脱硫催化剂的方法及应用 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- 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
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- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
本发明属于催化剂合成领域，提供了一种合成无定型结构MoS2蛋壳型加氢脱硫催化剂的方法及应用，采用溶剂热法合成定型结构MoS2蛋壳型加氢脱硫催化剂，并从宏观结构调控含硫化合物在催化剂表面的吸脱附，使脱硫产物快速从催化剂表面脱附，增加直接脱硫路径选择性，在加氢脱硫反应中能大幅度降低反应的氢耗，节约加氢脱硫工艺成本。
Description
技术领域
本发明属于催化剂合成领域，涉及一种合成无定型结构MoS2蛋壳型加氢脱硫催化剂的方法及应用。
背景技术
含硫化合物是石油中的主要非烃组分之一，其含量随原油产地以及馏分油馏程的不同有很大差别。这些含硫化合物从简单的硫醇、硫醚到多环硫化物(如硫茚、噻吩类等)，在重质油品中，含硫化合物以二苯并噻吩类的硫化物为主。加氢脱硫过程是在一定温度、压力和临氢条件下，石油馏分中的含硫化合物与催化剂的活性中心接触并与氢进行化学反应，使之转化成相应的烃和H2S，从而降低原料中的硫含量。
在石油中特别难脱除的含硫化合物为二苯并噻吩和4,6-二取代二苯并噻吩。二苯并噻吩在金属硫化物催化剂上的加氢脱硫机理有两种反应路径：直接的脱硫路径(DDS)和间接的加氢脱硫(HYD)。在直接脱硫的路径中，通过氢解和消除反应最终生成了联苯(BP)。在间接脱硫的路径中，首先形成了间接的加氢产物，然后脱除间接加氢产物中的硫，形成苯基环己烷(CHB)和联环己烷。该反应的基本化学反应过程包括C-S键的断裂和中间产物的加氢饱和HDS催化剂的典型载体是γ-氧化铝。
针对目前精制过程加氢脱硫所走的反应路径以加氢脱硫路径，加氢精制过程氢耗高的问题。采用溶剂热法合成定型结构MoS2蛋壳型加氢脱硫催化剂，并从宏观结构调控含硫化合物在催化剂表面的吸脱附，使脱硫产物快速从催化剂表面脱附，增加直接脱硫路径选择性，在加氢脱硫反应中能大幅度降低反应的氢耗，具有良好的经济效益及工业应用前景。下述的已知技术，都存在一些不足：
中国专利，公开号：111495393A，公开一种富缺陷1T-2H混合相的二硫化钼催化剂，其为1T相和2H相混合结构，其表面晶格条纹不连续且具有变形和错位，晶体边缘和基面存在缺陷。本发明还公开该催化剂制备方法和用途。本发明基于水热合成法，采用水和乙醇的混合溶剂，采用有机酸作为调控剂，合成了具有富缺陷1T-2H混合相的二硫化钼催化剂。该催化剂用于催化加氢脱硫反应中具有高催化活性、高稳定性和高间接脱硫选择性，间接脱硫选择性高脱硫过程所走路径为加氢脱硫路径。
中国专利，公开号：108568309A介绍了一种油品深度加氢脱硫催化剂及其制备方法，采用设计特定的多重乳液体系，制备空心球形SBA-15载体材料，并通过铝修饰改善SBA-15水热稳定性并提高其酸性位数量，然后采用等体积分布浸渍法将金属活性组分负载到载体上，所制备NiMo/SBA-15-SP催化剂，不仅具有适宜的MoS2分散度和B、L酸性位数量，还具有优异的DBT反应分子扩散性能，能够提高其总体反应速率，对二苯并噻吩(DBT)加氢脱硫反应活性进行评价，显示出优异的DBT脱硫转化频率TOF和速率常数。但加氢脱硫反应所走的路径还是以加氢脱硫路径为主。
现有技术中存在反应温度及压力高，反应温度难于控制，加氢脱硫路径以加氢脱硫路径为主，氢耗大、生产成本高。
发明内容
本发明提供了一种合成无定型结构MoS2蛋壳型加氢脱硫催化剂的方法及应用。
本发明的技术方案：
一种合成无定型结构MoS2蛋壳型加氢脱硫催化剂的方法，将Ni盐、Mo 盐和S源置于对二甲苯溶液中，剧烈搅拌使其混合均匀，确保S/Mo+Ni的摩尔比大于2。将混合后的反应液移入到装有成型载体Al2O3的高压反应釜中，在 220-240℃反应4-24h，反应结束后自然冷却降至室温，得到黑色蛋壳型 NiMoS2@载体的催化剂，NiMoS2壳层厚度由前体浓度和载体质量比确定，用丙酮和水清洗去除溶剂催化剂表面杂质，真空干燥后制备出MoS2蛋壳型催化剂。将所制备催化剂用于二苯并噻吩的加氢脱硫反应，反应条件：反应温度 320-380℃，反应压力3-5MPa，液体体积空速为1-4h-1，二苯并噻吩浓度为 200ppm-10000ppm，氢油体积比为200-400，催化剂的脱硫率大于95％。
所述的镍盐为硝酸镍、氯化镍、乙酰丙酮镍中的一种或两种以上混合。
所述的Mo盐为MoCl5或钼酸铵。
所述的硫前体为S粉、苄硫醇、二甲基二硫醚中的一种或两种以上混合。
所述的成型载体Al2O3为2-6mm的球型Al2O3。
本发明的有益效果：本发明的一种合成无定型结构MoS2蛋壳型加氢脱硫催化剂的方法，采用溶剂热法合成无定型结构MoS2蛋壳型加氢脱硫催化剂，并从宏观结构调控含硫化合物在催化剂表面的吸脱附，使脱硫产物快速从催化剂表面脱附，增加直接脱硫路径选择性，在加氢脱硫反应中能大幅度降低反应的氢耗，节约加氢脱硫工艺成本。
具体实施方式
以下结合技术方案，进一步说明本发明的具体实施方式。
实施例1：溶剂热法制备无定型结构体相MoS2，取MoCl5 6.21g，S粉1.4g，置于对二甲苯溶液中，剧烈搅拌30min使其混合均匀。将混合后的反应液移入到100ml聚四氟乙烯内衬的高压反应釜中，在220℃反应24h。反应结束后自然冷却降至室温。通过离心分离出黑色沉淀物，并用丙酮和水各清洗三次，最后将产品置于真空干燥箱内，80℃真空干燥12h。扫描电镜可以看到样品的外观形貌为无定型结构，每个无定型状MoS2颗粒直径约为50-100nm无规则团聚在一起。
实施例2：溶剂热法制备无定型结构体相NiMoS2，取NiCl50.99g，MoCl54.14g， S粉1.4g，置于对二甲苯溶液中，剧烈搅拌30min使其混合均匀。将混合后的反应液移入到100ml聚四氟乙烯内衬的高压反应釜中，在220℃反应24h。反应结束后自然冷却降至室温。通过离心分离出黑色沉淀物，并用丙酮和水各清洗三次，最后将产品置于真空干燥箱内，80℃真空干燥12h。
实施例3：溶剂热法制备无定型结构NiMoS2@Al2O3，取NiCl50.99g， MoCl54.14 g，S粉1.4g，置于对二甲苯溶液中，剧烈搅拌30min使其混合均匀。将混合后的反应液移入到100ml聚四氟乙烯内衬的高压反应釜中，加入直径为 2mm球型载体3.6g(理论担载量为25％)，通过控制载体的质量控制催化剂的担载量。在220℃反应24h。反应结束后自然冷却降至室温。得黑色小球，并用丙酮和水各清洗三次，最后将产品置于真空干燥箱内，80℃真空干燥12h。
实施例4：单源前体热解法可控制备类石墨烯结构MoS2，合成有机单源前体(Mo(Et2NCS2)4)，在惰性气氛下通过简单调变热解温度达到层数可控制备类石墨烯结构的MoS2。与传统的剥离制备方法相比有三个优点：(i)可以控制类石墨烯结构MoS2的层数。(ii)整个制备过程简单并且重复性好。(iii)制备的MoS2纳米片分散良好。
实施例5：类石墨烯结构MoS2，无定型结构体相MoS2，体相NiMoS2和 NiMoS2@Al2O3，加氢脱硫性能对比。二苯并噻吩的加氢脱硫是在连续的固定床反应器中进行的。首先，把0.5g体相催化剂压片后的不同形貌MoS2催化剂稀释在石英砂10mL当中，达到等温平推流的条件。在613K的温度下，催化剂在H2气氛中吹扫30分钟去除样品表面的钝化层。活化完成后，压力保持在3.0MPa，反应温度保持在340℃，氢气流量为144mL/min，质量空速为21.1h-1。液体通过液体进料泵打到固定床反应，进料是0.3wt％DBT的十氢萘。对于NiMoS2@Al2O3取2g稀释在石英砂8mL当中，催化剂前处理条件一样。
下表1见各催化剂加氢脱硫性能：
类石墨烯结构MoS2和无定型结构体相MoS2在二苯并噻吩加氢脱硫反应中活性都很低，基本维持在50％左右。不同方法制备的催化剂影响加氢脱硫的反应路径：类石墨烯结构的MoS2的催化剂主要沿着加氢脱硫路径反应，而无定形的 MoS2则主要沿着直接脱硫路径反应。为了提高无定形MoS2加氢脱硫活性，添加Ni，反应结果表明催化剂中引入元素镍后对二苯并噻吩的转化率和联苯的选择性有显著的影响。二苯并噻吩的转化率有了显著的提高,从40％升高到了98％，脱硫率达到了98％。HYD/DDS的比值可以通过式子[CHB]/[BP]估计出来。从表中可以看出，添加Ni后HYD/DDS的比值从0.4变化到0.1呈现显著的降低。二苯并噻吩加氢脱硫的选择性向直接脱硫路径发生偏移。从以前的报道得知，过渡金属硫化物催化剂加入助剂镍以后有助于C-S键的直接断裂，而此催化剂对直接加氢路径的高选择性也恰恰说明元素镍存在于Ni-Mo活性相当中。体相Ni0.5-MoS2比表面积偏小，进一步增加活性蛋壳型的NiMoS2@Al2O3的活性，因为增加活性表面及增加了催化剂的酸性。
实施例6：NiMoS2@Al2O3催化剂加氢脱硫反应条件优化，反应条件：反应温度320-380℃，反应压力3-5MPa，液体体积空速为1-4h-1，二苯并噻吩浓度为 3000ppm，氢油体积比为200-400，下表2见反应结果的影响。
由表可知：增加反应温度，脱硫转化率明显增加，直接脱硫的选择性也明显增加；增加反应压力，加氢脱硫活性增加，有利于加氢脱硫路径的提高；增加空速有利于直接脱硫反应的发生。
Claims (9)
1.一种合成无定型结构NiMoS2蛋壳型加氢脱硫催化剂的方法，其特征在于，Ni盐、Mo盐和S源置于对二甲苯溶液中，搅拌使其混合均匀，确保S/Mo+Ni的摩尔比大于2；将混合后的反应液移入到装有成型载体Al2O3的高压反应釜中，在220-240oC反应4-24 h，反应结束后自然冷却降至室温，得到黑色蛋壳型NiMoS2@载体的催化剂，NiMoS2壳层厚度由前体浓度和载体质量比确定，用丙酮和水清洗，去除催化剂表面杂质，真空干燥后制备出无定型结构NiMoS2蛋壳型加氢脱硫催化剂。
2.根据权利要求1所述的方法，其特征在于，所述的Ni盐为硝酸镍、醋酸镍、乙酰丙酮镍中的一种或两种以上混合。
3.根据权利要求1或2所述的方法，其特征在于，所述的Mo盐为MoCl5或钼酸铵。
4.根据权利要求1或2所述的方法，其特征在于，所述的S源为S粉、苄硫醇、二甲基二硫醚中的一种或两种以上混合。
5.根据权利要求3所述的方法，其特征在于，所述的S源为S粉、苄硫醇、二甲基二硫醚中的一种或两种以上混合。
6.根据权利要求1、2或5所述的方法，其特征在于，所述的成型载体Al2O3为2-6mm的球型Al2O3。
7.根据权利要求3所述的方法，其特征在于，所述的成型载体Al2O3为2-6mm的球型Al2O3。
8.根据权利要求4所述的方法，其特征在于，所述的成型载体Al2O3为2-6mm的球型Al2O3。
9.根据权利要求1-8任一所述方法制备得到的无定型结构NiMoS2蛋壳型加氢脱硫催化剂用于二苯并噻吩的加氢脱硫反应的应用，其特征在于，反应条件：反应温度320-380oC，反应压力3-5MPa，液体体积空速为1-4h-1，二苯并噻吩浓度为200ppm-10000ppm，氢油体积比为200-400，催化剂的脱硫率大于95%。
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