CN108325548B - Molybdenum sulfide-based catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof - Google Patents
Molybdenum sulfide-based catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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Abstract
The invention relates to a preparation method of a molybdenum sulfide-based catalyst for preparing low carbon alcohol from synthesis gas, which comprises the following steps of (1) adding ammonium heptamolybdate tetrahydrate and thiourea into water according to the mol ratio Mo: S =1, 2-4, and dissolving to prepare a solution A; (2) Adding the solution A into a hydrothermal reaction kettle, reacting at 220 ℃, washing and drying a product to obtain a precipitate A, namely petal-shaped MoS 2 (ii) a (3) And mechanically grinding the precipitate A and potassium carbonate according to the molar ratio of Mo to K = 1. The catalyst has the advantages of simple preparation method, good sulfur resistance, and total alcohol and C of the product 2+ High alcohol selectivity and the like, and has good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of chemical catalysts, in particular to a preparation method and reaction conditions of a molybdenum sulfide-based catalyst for preparing low-carbon alcohol from synthesis gas, and especially relates to a molybdenum sulfide-based catalyst prepared by a hydrothermal synthesis method.
Background
Energy shortage and environmental deterioration are major problems facing mankind at present. With the increasing consumption of petroleum resources, the development of efficient and clean 'green energy' has not only broad application prospects, but also very important strategic significance. Among them, the production of clean liquid fuels and other high value-added chemicals from coal or biomass-derived syngas is an important way for clean and efficient utilization of energy resources.
At present, the ethanol gasoline (E10) for vehicles sold in China is gasoline blended by adding 10 percent (volume fraction) of denatured fuel ethanol. Due to the restriction of raw material supply and production cost, ethanol produced by using grains as raw materials cannot meet the ever-increasing consumption demands of industrial ethanol and fuel ethanol. The novel non-grain ethanol technology, including the ethanol preparation by acetic acid (acetate) hydrogenation, the ethanol preparation by cellulose, the ethanol preparation by synthesis gas and the like, can impact the traditional grain ethanol technology, and bring a revolution to the ethanol industry. According to statistics, the yield of the Chinese gasoline in 2016 is 12932 ten thousand tons. With a 10% addition according to national regulations, the fuel ethanol requirement is 1293.2 million tons, and considering the production of ethanol by biological methods (200 million tons per year), the synthesis gas fuel ethanol has a market space of about 1000 million tons. China's huge potential consumption demand for fuel ethanol and the limited supply capacity of fuel ethanol bring great market opportunity for preparing ethanol from synthesis gas.
The direct synthesis of ethanol from synthesis gas is a popular subject for domestic and foreign research departments, and has not been industrialized, but results are not few. The key problem is that no catalyst which has high selectivity, high activity, high stability, low price and easy obtaining is suitable for large-scale industrialized operation at present. At present, the research on the catalyst for preparing low carbon alcohol from synthesis gas mainly focuses on noble metal rhodium-based catalysts, modified fischer-tropsch catalysts, modified methanol catalysts and modified molybdenum-based catalysts. Although the selectivity of the alcohols of the rhodium-based catalyst is high, rhodium is a noble metal and is expensive, so that the rhodium-based catalyst is not suitable for industrial production. Although the modified Fischer-Tropsch catalyst and the modified methanol catalyst have the advantages of mild reaction conditions and the like, the synthetic gas produced by coal gasification usually contains S element, which has a poisoning effect on the catalyst, and the desulfurization of the synthetic gas can further increase the production cost. The modified molybdenum-based catalyst, especially the alkali-modified molybdenum sulfide catalyst, has good sulfur resistance, high alcohol selectivity and potential research and development value. The application of molybdenum sulfide-based catalyst in the preparation of low carbon alcohol from synthesis gas is first reported in the patent of Dow Chemical company in the United states in 1987, the catalytic system has good sulfur resistance, the low carbon alcohol product has low water content, C 2+ The alcohol selectivity is higher. The domestic patents on the low-carbon alcohol molybdenum sulfide-based catalyst prepared from the synthesis gas are less, but it is worth mentioning that the auxiliary agents such as Ni, fe, mn, K and the like are added into the molybdenum sulfide catalyst by the Sunyuan rarely-problem group of Shanxi coal chemistry research institute of Chinese academy of sciences, so that the low-carbon alcohol catalyst prepared from the synthesis gas with excellent performance is obtained, and the total alcohol selectivity can reach more than 60%. The main product of the catalytic system is methanol. The traditional molybdenum sulfide-based catalyst prepared by a pyrolysis method has fewer catalytic active sites and lower activity due to high-temperature roasting. The molybdenum sulfide prepared by hydrothermal synthesis has lower crystallinity and thinner lamella, and is beneficial to exposing more catalytic active sites, so that the molybdenum sulfide prepared by hydrothermal synthesis has higher catalytic activity on preparing low carbon alcohol from synthesis gas.
Disclosure of Invention
The invention aims to provide a method for preparing low carbon from synthesis gasThe new preparation process of alcohol high efficiency molybdenum sulfide catalyst is hydrothermal synthesis process of preparing molybdenum sulfide catalyst. The catalyst has excellent total alcohol selectivity and C for preparing low-carbon alcohol from synthesis gas 2+ The method has the advantages of alcohol selectivity, low cost, simple process and good practical application value.
The method mainly comprises the steps of preparation of an active component molybdenum sulfide, addition of an auxiliary agent, reaction evaluation of a catalyst and the like. The following are the operational steps and a schematic illustration of the present invention:
(1) Dissolving ammonium heptamolybdate tetrahydrate and thiourea in water, transferring the solution to a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene substrate, reacting for 24 hours in a constant-temperature drying oven at 220 ℃, repeatedly centrifuging, washing with water and ethanol, washing the obtained precipitate after the reaction is finished, and drying at 60 ℃ to obtain petal-shaped MoS 2 And (3) solid powder.
(2) Flower petal-shaped MoS 2 And mechanically grinding the solid powder and potassium carbonate for 1h, tabletting and granulating the obtained solid powder under 12MPa, sieving, and collecting particles of 40-60 meshes, namely the modified molybdenum sulfide catalyst.
The invention also provides the reaction condition of the catalyst in the reaction of synthesizing alcohol by hydrogenation.
The invention has the advantages that:
(1) The catalyst has simple preparation process and mild condition, and is suitable for industrial production;
(2) The synthesized catalyst has high total alcohol selectivity and C 2+ High alcohol selectivity, good sulfur resistance and the like.
Drawings
FIG. 1 is an XRD spectrum of molybdenum sulfide synthesized by hydrothermal method
FIG. 2 is an SEM photograph of a hydrothermal method for synthesizing molybdenum sulfide
FIG. 3 is a HRTEM photograph of molybdenum sulfide synthesized by hydrothermal method
Detailed Description
Example 1
1.2359g of ammonium heptamolybdate tetrahydrate and 1.0657g of thiourea (Mo: S: 1: 2) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle is arranged in an oven 2Reacting for 24h at 20 ℃, cooling to room temperature, washing the solid product with water for 3 times, washing with ethanol for 1 time, and drying for 12h at 60 ℃. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions are that the temperature is 300 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 2
1.2359g of ammonium heptamolybdate tetrahydrate and 1.0657g of thiourea (Mo: S: 1: 2) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24 hours, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12 hours. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation in a stainless steel fixed bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, mixed quartz sand of 40-60 meshes is filled in the constant temperature section, and quartz sand is filled in both the upper preheating section and the lower heat preservation section. The reaction conditions are that the temperature is 330 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 3
1.2359g of ammonium heptamolybdate tetrahydrate and 1.0657g of thiourea (Mo: S is 1. The reaction kettle reacts in an oven at 220 ℃ for 24h, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12h. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The above method is carried outPrepared K-MoS 2 The catalyst is subjected to catalytic performance evaluation in a stainless steel fixed bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, mixed quartz sand of 40-60 meshes is filled in the constant temperature section, and quartz sand is filled in both the upper preheating section and the lower heat preservation section. The reaction conditions are that the temperature is 350 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 4
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S is 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24h, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12h. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions comprise the temperature of 300 ℃, the pressure of 10MPa and the space velocity of 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 5
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S is 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24 hours, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12 hours. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower partAnd (5) sand. The reaction conditions are that the temperature is 330 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 6
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S: 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24 hours, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12 hours. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions are that the temperature is 350 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 7
1.2359g of ammonium heptamolybdate tetrahydrate and 2.1314g of thiourea (Mo: S is 1. The reaction kettle reacts in an oven at 220 ℃ for 24h, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12h. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions are that the temperature is 300 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 8
1.2359g of ammonium heptamolybdate tetrahydrate and 2.1314g of thiourea (Mo: S is 1. The reaction kettle reacts in an oven at 220 ℃ for 24h, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12h. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions are that the temperature is 330 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 9
1.2359g of ammonium heptamolybdate tetrahydrate and 2.1314g of thiourea (Mo: S: 1, 4) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24 hours, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12 hours. 0.7g of the product was mixed with 0.3g of potassium carbonate (Mo: K = 1), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions comprise 350 ℃ of temperature, 10MPa of pressure and 3000h of space velocity -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 10
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S is 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle is driedReacting at 220 ℃ for 24h in the box, cooling to room temperature, washing the solid product with water for 3 times, washing with ethanol for 1 time, and drying at 60 ℃ for 12h. 0.7g of the product was mixed with 0.15g of potassium carbonate (Mo: K =1: 0.5), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions comprise the temperature of 300 ℃, the pressure of 10MPa and the space velocity of 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 11
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S is 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24 hours, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12 hours. 0.7g of the product was mixed with 0.15g of potassium carbonate (Mo: K = 1. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions comprise 330 ℃ of temperature, 10MPa of pressure and 3000h of space velocity -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 12
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S: 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24h, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12h. 0.7g of the product was mixed with 0.15g of potassium carbonate (Mo: K =1: 0.5), mechanically ground for 1h, tableted and sieved, and the 40-60 mesh catalyst was collected. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation in a stainless steel fixed bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, mixed quartz sand of 40-60 meshes is filled in the constant temperature section, and quartz sand is filled in both the upper preheating section and the lower heat preservation section. The reaction conditions are that the temperature is 350 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The products of the reaction were analyzed by gas chromatography using a capillary column equipped with a capillary. The test results are shown in Table 1.
Example 13
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S is 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24h, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12h. 0.7g of the product was mixed with 0.21g of potassium carbonate (Mo: K =1: 0.7), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation in a stainless steel fixed bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, mixed quartz sand of 40-60 meshes is filled in the constant temperature section, and quartz sand is filled in both the upper preheating section and the lower heat preservation section. The reaction conditions are that the temperature is 300 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 14
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S is 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24 hours, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12 hours. 0.7g of the product was mixed with 0.21g of potassium carbonate (Mo: K =1: 0.7), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation in a stainless steel fixed bed reactor. The inner diameter of the reactor is 8mm, the loading amount of the catalyst is 0.4g, mixed quartz sand of 40-60 meshes is filled in a constant temperature section, and the upper part is preheatedQuartz sand is filled in both the section and the lower heat preservation section. The reaction conditions are that the temperature is 330 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Example 15
1.2359g of ammonium heptamolybdate tetrahydrate and 1.5986g of thiourea (Mo: S: 1: 3) were weighed into 75ml of water, the solution was charged into a 100ml polytetrafluoroethylene reaction kettle, and sealed in a stainless steel shell. The reaction kettle reacts in an oven at 220 ℃ for 24h, after the reaction kettle is cooled to room temperature, the solid product is washed with water for 3 times, washed with ethanol for 1 time, and dried at 60 ℃ for 12h. 0.7g of the product was mixed with 0.21g of potassium carbonate (Mo: K =1: 0.7), mechanically ground for 1h, tableted and sieved, and the catalyst was collected for 40-60 mesh. The K-MoS prepared by the method 2 The catalyst is subjected to catalytic performance evaluation 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 quartz sand of 40-60 meshes is mixed and filled in the constant temperature section, and the quartz sand is filled in the preheating section at the upper part and the heat preservation section at the lower part. The reaction conditions are that the temperature is 350 ℃, the pressure is 10MPa, and the space velocity is 3000h -1 Synthesis gas H 2 1/CO = 1. The reaction product was analyzed using a gas chromatograph equipped with a capillary column. The test results are shown in Table 1.
Watch (A)
Evaluation result of catalytic performance of catalyst on synthesis gas to prepare low-carbon alcohol
From table 1, it can be seen that the molar ratio of Mo to S is 1, the molar ratio of Mo 2+ The alcohol selectivity is as high as 79.4%, which shows that the catalyst shows good total alcohol selectivity and C 2+ The alcohol selectivity is an excellent catalyst for preparing low-carbon alcohol from synthesis gas. And when the molar ratio of Mo to S is 1, the molar ratio of Mo,CO conversion rate can reach 14.4%, total alcohol selectivity can reach 80.9%, C 2+ The alcohol selectivity reaches 51.6 percent, and the ethanol accounts for 37.1 percent in the total alcohol, which shows that the catalyst shows good total alcohol selectivity and C 2+ The catalyst is also excellent in alcohol selectivity and ethanol selectivity, and is also an excellent catalyst for preparing ethanol from synthesis gas.
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 H 2 /CO =1: 1; CO conversion rate up to 23.4%, total alcohol selectivity up to 75.6%, C 2+ The alcohol selectivity reaches 79.4 percent, and the good total alcohol selectivity and C are shown 2+ 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 MoS 2 A solid powder; 0.7g of petaloid MoS 2 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810212023.7A CN108325548B (en) | 2018-03-15 | 2018-03-15 | Molybdenum sulfide-based catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
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| CN111420684B (en) * | 2020-03-26 | 2022-09-13 | 内蒙古大学 | Catalyst for directly preparing ethanol from synthesis gas and application thereof |
| CN111420689B (en) * | 2020-03-26 | 2022-09-13 | 内蒙古大学 | Preparation method and application of catalyst for preparing low-carbon alcohol from synthesis gas |
| CN112206788B (en) * | 2020-10-15 | 2023-08-29 | 内蒙古大学 | Composition, preparation method and application of catalyst for preparing isobutanol from synthesis gas |
| CN112844418B (en) * | 2020-12-30 | 2022-04-29 | 内蒙古大学 | Mesoporous NiO-Al with alkaline carrier material2O3Molybdenum-based catalyst for preparing low-carbon alcohol from synthesis gas as carrier and preparation method thereof |
| CN114797903B (en) * | 2021-01-21 | 2024-04-02 | 国家能源投资集团有限责任公司 | Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method and application thereof |
| CN113797939B (en) * | 2021-08-31 | 2024-01-05 | 宁夏大学 | ZnZrO (zinc ZrO-rich alloy) x /MoS 2 Composite catalyst, preparation and application thereof |
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