CN108325548B - Molybdenum sulfide-based catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof - Google Patents

Abstract

Translated fromChinese

本发明涉及一种合成气制低碳醇硫化钼基催化剂的制备方法，包括如下步骤:（1）将四水合七钼酸铵和硫脲按照摩尔比Mo:S=1:2‑4加入水中，溶解后制成溶液A；（2）将溶液A加入水热反应釜中，220℃反应，产物经洗涤、干燥，得到沉淀物A，即花瓣状MoS₂；（3）将沉淀物A与碳酸钾按照摩尔比Mo:K=1:0.5‑1机械研磨即得合成气制低碳醇催化剂。该催化剂具有制备方法简单，抗硫性能好，产物总醇、C₂₊醇选择性高等优点，具有良好的工业应用前景。The invention relates to a preparation method of a low-carbon alcohol molybdenum sulfide-based catalyst for synthesis gas, comprising the following steps: (1) adding ammonium heptamolybdate tetrahydrate and thiourea into water according to the molar ratio Mo:S=1:2‑4 , and dissolved to make solution A; (2) Add solution A to the hydrothermal reaction kettle and react at 220°C. The product is washed and dried to obtain precipitate A, which is petal-shaped MoS₂ ; (3) The precipitate A is mixed with Potassium carbonate is mechanically ground according to the molar ratio Mo:K=1:0.5‑1 to obtain a low-carbon alcohol catalyst for synthesis gas. The catalyst has the advantages of simple preparation method, good sulfur resistance, high selectivity of product total alcohol and C2₊ alcohol, etc., and has good industrial application prospect.

Description

Translated fromChinese

一种用于合成气制低碳醇的硫化钼基催化剂及其制备方法A kind of molybdenum sulfide-based catalyst for producing low-carbon alcohol from syngas and preparation method thereof

技术领域technical field

本发明涉及化工催化剂技术领域,具体涉及一种用于合成气制低碳醇的硫化钼基催化剂制备方法和反应条件,尤其是涉及一种以水热合成法制备硫化钼基催化剂。The invention relates to the technical field of chemical catalysts, in particular to a preparation method and reaction conditions for a molybdenum sulfide-based catalyst used for producing low-carbon alcohols from synthesis gas, and in particular to a molybdenum sulfide-based catalyst prepared by a hydrothermal synthesis method.

背景技术Background technique

能源短缺和环境恶化是当前人类面临的重大问题。随着石油资源的日益消耗，开发高效清洁的“绿色能源”不但具有广阔的应用前景，而且具有十分重大的战略意义。其中，经由煤炭或生物质产生合成气制备清洁液体燃料及其他高附加值化学品是能源资源清洁高效利用的重要途径。Energy shortage and environmental degradation are major problems facing mankind at present. With the increasing consumption of petroleum resources, the development of efficient and clean "green energy" not only has broad application prospects, but also has very important strategic significance. Among them, the preparation of clean liquid fuels and other high value-added chemicals through coal or biomass to produce syngas is an important way to cleanly and efficiently utilize energy resources.

目前，中国销售的车用乙醇汽油(E10)，即为加入10%（体积分数）变性燃料乙醇调合而成的汽油。受原料供应和生产成本制约，以粮食为原料生产的乙醇无法满足不断增长的工业乙醇和燃料乙醇消费需求。新型非粮乙醇技术，包括醋酸（醋酸酯）加氢制乙醇、纤维素制乙醇、合成气制乙醇等将冲击传统粮食乙醇技术，为乙醇行业带来变革。根据统计，2016年中国汽油的产量为12932万吨。按照国家规定10%添加，燃料乙醇需求为1293.2万吨，考虑生物法乙醇的生产量（年产量200多万吨），合成气制燃料乙醇有约1000万吨的市场空间。中国对燃料乙醇巨大的潜在消费需求，与燃料乙醇有限的供应能力，为合成气制乙醇带来了较大的市场机遇。Currently, ethanol gasoline (E10) for vehicles sold in China is gasoline blended with 10% (volume fraction) denatured fuel ethanol. Constrained by the supply of raw materials and production costs, ethanol produced from grains cannot meet the growing demand for industrial ethanol and fuel ethanol. New non-grain ethanol technologies, including hydrogenation of acetic acid (acetate) to ethanol, cellulose to ethanol, and synthesis gas to ethanol, will impact traditional grain ethanol technologies and bring changes to the ethanol industry. According to statistics, China's gasoline production in 2016 was 129.32 million tons. According to the national regulation of 10% addition, the demand for fuel ethanol is 12.932 million tons. Considering the production volume of biological ethanol (annual output of more than 2 million tons), there is about 10 million tons of market space for fuel ethanol produced from syngas. China's huge potential consumption demand for fuel ethanol and the limited supply capacity of fuel ethanol have brought great market opportunities for syngas-based ethanol.

从合成气直接合成乙醇是国内外科研部门的热门课题，有不少成果，但均未工业化。关键问题是目前还没有一个高选择性、高活性、高稳定性且价廉易得的催化剂适用于大规模工业化运行。目前，合成气制低碳醇催化剂的研究主要集中在贵金属铑基催化剂、改性费托催化剂、改性甲醇催化剂以及改性钼基催化剂。虽然铑基催化剂的醇类选择性较高，但由于铑是贵金属，价格昂贵，不适合工业化生产。改性费托催化剂和改性甲醇催化剂虽然具有反应条件温和等优点，但由煤炭气化生产的合成气中常含有S元素，对催化剂有毒化作用，而对合成气脱硫又会进一步增加生产成本。改性钼基催化剂，特别是碱改性的硫化钼催化剂具有良好的抗硫性能，且醇类选择性较高，具有潜在的研发价值。美国的Dow Chemical公司于1987年在其申请的专利中首次报道了硫化钼基催化剂在合成气制低碳醇中的应用，该催化体系具有良好的抗硫性能，低碳醇产品含水量少，C₂₊醇选择性较高。国内关于合成气制低碳醇硫化钼基催化剂的专利较少，但值得一提的是，中国科学院山西煤炭化学研究所孙予罕课题组通过向硫化钼催化剂中加入Ni、Fe、Mn、K等助剂，获得了性能优良的合成气制低碳醇催化剂，总醇选择性可达60%以上。美中不足的是，该催化体系主要产物是甲醇。传统的热解法制备的硫化钼基催化剂由于经过高温焙烧，导致催化活性位较少，活性较低。经由水热合成制备的硫化钼结晶性较低，片层较薄，有利于暴露更多的催化活性位，所以可能对合成气制低碳醇具有更高的催化活性。The direct synthesis of ethanol from synthesis gas is a hot topic in scientific research departments at home and abroad, and there are many achievements, but none of them have been industrialized. The key problem is that there is still no catalyst with high selectivity, high activity, high stability and low price which is suitable for large-scale industrial operation. At present, the research on low-carbon alcohol catalysts from syngas mainly focuses on noble metal rhodium-based catalysts, modified Fischer-Tropsch catalysts, modified methanol catalysts and modified molybdenum-based catalysts. Although the alcohol selectivity of rhodium-based catalysts is high, because rhodium is a noble metal, it is expensive and unsuitable for industrial production. Although modified Fischer-Tropsch catalysts and modified methanol catalysts have the advantages of mild reaction conditions, the synthesis gas produced by coal gasification often contains S element, which is poisonous to the catalyst, and the desulfurization of the synthesis gas will further increase the production cost. Modified molybdenum-based catalysts, especially alkali-modified molybdenum sulfide catalysts, have good sulfur resistance and high alcohol selectivity, and have potential research and development value. The Dow Chemical Company of the United States first reported the application of molybdenum sulfide-based catalysts in the production of low-carbon alcohols from syngas in its patent application in 1987. The catalytic system has good sulfur resistance, and the low-carbon alcohol products have less water content. C₂₊ alcohols are more selective. There are few domestic patents on molybdenum sulfide-based catalysts for the production of low-carbon alcohols from syngas, but it is worth mentioning that Sun Yuhan’s research group at the Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences added Ni, Fe, Mn, K to molybdenum sulfide catalysts. and other additives, obtained a low-carbon alcohol catalyst for syngas production with excellent performance, and the total alcohol selectivity can reach more than 60%. The fly in the ointment is that the main product of this catalytic system is methanol. The molybdenum sulfide-based catalyst prepared by the traditional pyrolysis method has fewer catalytic active sites and lower activity due to high-temperature calcination. Molybdenum sulfide prepared by hydrothermal synthesis has lower crystallinity and thinner sheets, which is conducive to exposing more catalytic active sites, so it may have higher catalytic activity for the synthesis of low-carbon alcohols from syngas.

发明内容Contents of the invention

本发明目的在于提供一种合成气制低碳醇高效硫化钼基催化剂的新型制备方法,即采用水热合成法制备硫化钼催化剂。该催化剂具有优异的合成气制低碳醇总醇选择性和C₂₊醇选择性,成本低廉，工艺简单,具有很好的实际应用价值。The purpose of the present invention is to provide a novel preparation method of a molybdenum sulfide-based catalyst with high efficiency for producing low-carbon alcohols from synthesis gas, that is, a molybdenum sulfide catalyst is prepared by a hydrothermal synthesis method. The catalyst has excellent total alcohol selectivity and C₂₊ alcohol selectivity of low-carbon alcohols produced from synthesis gas, low cost, simple process and good practical application value.

发明主要包括活性组分硫化钼的制备、助剂的添加和催化剂反应评价等步骤。以下为本发明的操作步骤及原理性说明:The invention mainly includes the steps of preparation of active component molybdenum sulfide, addition of additives and evaluation of catalyst reaction. The following are operation steps and principle explanations of the present invention:

（1）将四水合七钼酸铵和硫脲在水中溶解，将溶液转移至带聚四氟乙烯衬底的不锈钢高压反应釜中，在220℃恒温干燥箱中反应24h，反应结束后，所得沉淀物经反复离心、水洗、乙醇洗后，在60℃干燥，得到花瓣状MoS₂固体粉末。(1) Dissolve ammonium heptamolybdate tetrahydrate and thiourea in water, transfer the solution to a stainless steel autoclave with a polytetrafluoroethylene substrate, and react in a constant temperature drying oven at 220°C for 24 hours. After the reaction, the obtained The precipitate was repeatedly centrifuged, washed with water, and washed with ethanol, and then dried at 60 °C to obtain a petal-shaped_MoS2 solid powder.

（2）将花瓣状MoS₂固体粉末与碳酸钾机械研磨1h，所得固体粉末经12MPa压片造粒，过筛，收集40-60目的颗粒，即为改性硫化钼催化剂。(2) Mechanically grind the petal-shaped MoS₂ solid powder with potassium carbonate for 1 hour, and the resulting solid powder is tabletted and granulated at 12 MPa, and sieved to collect 40-60 mesh particles, which is the modified molybdenum sulfide catalyst.

本发明还提供了所述催化剂在加氢合成醇反应中的反应条件。The invention also provides the reaction conditions of the catalyst in the hydrogenation alcohol synthesis reaction.

本发明的优点:Advantage of the present invention:

（1）催化剂制备工艺简单，条件温和，适合工业生产；(1) The catalyst preparation process is simple, the conditions are mild, and it is suitable for industrial production;

（2）合成的催化剂具有总醇选择性高、C₂₊醇选择性高、抗硫性能好等优点。(2) The synthesized catalyst has the advantages of high selectivity to total alcohols, high selectivity to C2₊ alcohols, and good sulfur resistance.

附图说明Description of drawings

图1是水热法合成硫化钼的XRD谱图Figure 1 is the XRD spectrum of molybdenum sulfide synthesized by hydrothermal method

图2是水热法合成硫化钼的SEM照片Figure 2 is a SEM photo of molybdenum sulfide synthesized by hydrothermal method

图3是水热法合成硫化钼的HRTEM照片Figure 3 is the HRTEM photo of molybdenum sulfide synthesized by hydrothermal method

具体实施方式Detailed ways

实施例1Example 1

称取1.2359g四水合七钼酸铵和1.0657g硫脲（Mo:S为1:2）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度300℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g ammonium heptamolybdate tetrahydrate and 1.0657g thiourea (Mo:S ratio 1:2) and dissolve in 75ml water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 300℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例2Example 2

称取1.2359g四水合七钼酸铵和1.0657g硫脲（Mo:S为1:2）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度330℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g ammonium heptamolybdate tetrahydrate and 1.0657g thiourea (Mo:S ratio 1:2) and dissolve in 75ml water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 330℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例3Example 3

称取1.2359g四水合七钼酸铵和1.0657g硫脲（Mo:S为1:2）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度350℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g ammonium heptamolybdate tetrahydrate and 1.0657g thiourea (Mo:S ratio 1:2) and dissolve in 75ml water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 350℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例4Example 4

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度300℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 300℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例5Example 5

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度330℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 330℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例6Example 6

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度350℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 350℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例7Example 7

称取1.2359g四水合七钼酸铵和2.1314g硫脲（Mo:S为1:4）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度300℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g ammonium heptamolybdate tetrahydrate and 2.1314g thiourea (Mo:S ratio 1:4) and dissolve in 75ml water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 300℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例8Example 8

称取1.2359g 四水合七钼酸铵和2.1314g硫脲（Mo:S为1:4）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度330℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g ammonium heptamolybdate tetrahydrate and 2.1314g thiourea (Mo:S ratio 1:4) and dissolve in 75ml water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 330℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例9Example 9

称取1.2359g 四水合七钼酸铵和2.1314g硫脲（Mo:S为1:4）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.3g碳酸钾混合（Mo:K=1:1），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度350℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g ammonium heptamolybdate tetrahydrate and 2.1314g thiourea (Mo:S ratio 1:4) and dissolve in 75ml water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.3g of potassium carbonate (Mo:K=1:1), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 350℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例10Example 10

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.15g碳酸钾混合（Mo:K=1:0.5），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度300℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.15g of potassium carbonate (Mo:K=1:0.5), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 300℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例11Example 11

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.15g碳酸钾混合（Mo:K=1:0.5），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度330℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.15g of potassium carbonate (Mo:K=1:0.5), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 330℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例12Example 12

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.15g碳酸钾混合（Mo:K=1:0.5），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度350℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产生产物使用装有的毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.15g of potassium carbonate (Mo:K=1:0.5), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 350℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction produces products that are analyzed using gas chromatography equipped with a capillary column. The test results are listed in Table 1.

实施例13Example 13

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.21g碳酸钾混合（Mo:K=1:0.7），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度300℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.21g of potassium carbonate (Mo:K=1:0.7), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 300℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例14Example 14

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.21g碳酸钾混合（Mo:K=1:0.7），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度330℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.21g of potassium carbonate (Mo:K=1:0.7), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 330℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

实施例15Example 15

称取1.2359g四水合七钼酸铵和1.5986g硫脲（Mo:S为1:3）溶解在75ml水中，溶液装入100ml聚四氟乙烯反应釜中，并密封在不锈钢外壳中。反应釜在烘箱中220℃反应24h，待冷却至室温后，固体产物水洗3次，乙醇洗1次，60℃干燥12h。将0.7g产品与0.21g碳酸钾混合（Mo:K=1:0.7），机械研磨1h ,压片过筛，收集40-60目的催化剂。将上述方法制备的K-MoS₂催化剂在不锈钢固定床反应器中进行催化性能评价。反应器内径8mm,催化剂装填量0.4g,混合40-60目石英砂填装于恒温段,上部预热段和下部保温段均填装石英砂。反应条件:温度350℃,压力10MPa,空速3000h^-1,合成气H₂/CO=1:1。反应产物使用装有毛细管柱的气相色谱分析。测试结果列于表1。Weigh 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo:S ratio 1:3) and dissolve them in 75ml of water, put the solution into a 100ml polytetrafluoroethylene reactor and seal it in a stainless steel shell. The reaction kettle was reacted in an oven at 220°C for 24h. After cooling to room temperature, the solid product was washed three times with water and once with ethanol, and dried at 60°C for 12h. Mix 0.7g of the product with 0.21g of potassium carbonate (Mo:K=1:0.7), mechanically grind for 1h, press into tablets and sieve to collect the 40-60 mesh catalyst. The K-_MoS2 catalyst prepared by the above method was evaluated for catalytic performance in a stainless steel fixed-bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, the mixed 40-60 mesh quartz sand is filled in the constant temperature section, and the upper preheating section and the lower insulation section are filled with quartz sand. Reaction conditions: temperature 350℃, pressure 10MPa, space velocity 3000h^-1 , synthesis gas H₂ /CO=1:1. The reaction products were analyzed using a gas chromatograph equipped with a capillary column. The test results are listed in Table 1.

表

. 催化剂对合成气制低碳醇催化性能评价结果surface

. Catalytic Performance Evaluation Results for Syngas to Low Carbon Alcohols

由表1可知，制备硫化钼催化剂时Mo:S的摩尔比为1:3，Mo:K的摩尔比为1:0.7，反应温度为350℃时CO转化率可达23.4%，总醇选择性达到75.6%，C₂₊醇选择性高达79.4%，表明该催化剂显示出良好的总醇选择性和C₂₊醇选择性,是优良的合成气制低碳醇催化剂。而当制备硫化钼催化剂时Mo:S的摩尔比为1:3，Mo:K的摩尔比为1:0.5时，反应温度为300℃时，CO转化率可达14.4%，总醇选择性达到80.9%，C₂₊醇选择性达51.6%，总醇中乙醇占37.1%，表明该催化剂显示出良好的总醇选择性、C₂₊醇选择性和乙醇选择性,也是优良的合成气制乙醇催化剂。It can be seen from Table 1 that when the molybdenum sulfide catalyst is prepared, the molar ratio of Mo:S is 1:3, and the molar ratio of Mo:K is 1:0.7. When the reaction temperature is 350°C, the conversion rate of CO can reach 23.4%. It reached 75.6%, and the C₂₊ alcohol selectivity was as high as 79.4%, indicating that the catalyst showed good total alcohol selectivity and C₂₊ alcohol selectivity, and was an excellent low-carbon alcohol catalyst for syngas production. When preparing the molybdenum sulfide catalyst, when the molar ratio of Mo:S is 1:3, and the molar ratio of Mo:K is 1:0.5, when the reaction temperature is 300°C, the conversion rate of CO can reach 14.4%, and the selectivity of total alcohol can reach 80.9%, C₂₊ alcohol selectivity reached 51.6%, and ethanol accounted for 37.1% of the total alcohol, indicating that the catalyst showed good total alcohol selectivity, C₂₊ alcohol selectivity and ethanol selectivity, and was also an excellent syngas production ethanol catalyst.

Claims (1)

1. The application of molybdenum sulfide-based catalyst in preparing low carbon alcohol with synthetic gas is characterized by that,

putting a molybdenum sulfide-based catalyst into a stainless steel fixed bed reactor, wherein the inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, mixing quartz sand with 40-60 meshes, filling the quartz sand into a constant temperature section, and filling the quartz sand into an upper preheating section and a lower heat preservation section; reaction conditions are as follows: the temperature is 350 ℃, the pressure is 10MPa, and the space velocity is 3000h^-1 Synthesis gas H₂ /CO =1: 1; CO conversion rate up to 23.4%, total alcohol selectivity up to 75.6%, C₂₊ The alcohol selectivity reaches 79.4 percent, and the good total alcohol selectivity and C are shown₂₊ Alcohol selectivity;

the preparation method of the molybdenum sulfide-based catalyst comprises the following steps:

weighing 1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea, dissolving in 75ml of water, putting the solution into a 100ml polytetrafluoroethylene reaction kettle, sealing the reaction kettle in a stainless steel shell, reacting the reaction kettle in an oven at 220 ℃ for 24h, cooling to room temperature, washing a solid product with water for 3 times, washing with ethanol for 1 time, and drying at 60 ℃ for 12h to obtain petal-shaped MoS₂ A solid powder; 0.7g of petaloid MoS₂ Mixing the solid powder with 0.21g of potassium carbonate, mechanically grinding for 1 hour, tabletting and sieving, and collecting the catalyst with 40-60 meshes.

Images