CN114558586A - KCoMnMoOxCatalyst, preparation method and application thereof - Google Patents

KCoMnMoOxCatalyst, preparation method and application thereof Download PDF

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CN114558586A
CN114558586A CN202210189641.0A CN202210189641A CN114558586A CN 114558586 A CN114558586 A CN 114558586A CN 202210189641 A CN202210189641 A CN 202210189641A CN 114558586 A CN114558586 A CN 114558586A
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source compound
catalyst
kcomnmoo
citric acid
aqueous solution
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王如阳
谢威
李文杰
罗雷
李旭
谭猗生
鲍骏
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University of Science and Technology of China USTC
Shanxi Institute of Coal Chemistry of CAS
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University of Science and Technology of China USTC
Shanxi Institute of Coal Chemistry of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides KCoMnMoOxThe catalyst is formed by dispersing K, Co, Mn and Mo metal elements on the surface of a carbon substrate. The invention adopts a sol-gel method to prepare KCoMnMoOxThe catalyst and metal elements are uniformly distributed on the surface of the catalyst, the components are closely contacted, strong interaction is formed between active sites, and the catalyst has excellent performance of preparing low-carbon alcohol by carbon monoxide hydrogenation by adjusting the proportion of the elements.

Description

KCoMnMoOxCatalyst, preparation method and application thereof
Technical Field
The invention relates to the technical field of energy catalysis, in particular to KCoMnMoOxA catalyst, a preparation method and application thereof.
Background
In recent years, with the rapid increase of energy demand and the aggravation of environmental pollution, the rational utilization of resources and the development of green energy have important meanings in the aspects of solving the problem of energy shortage, protecting the environment and the like. The carbon-catalyzed catalyst is generated under the background of two petroleum crises, and opens up a new path for the efficient and clean utilization of energy sources such as coal and the like. Coal, natural gas, biomass, etc. can be converted to syngas (CO + H) by carbon-catalysis2) And then the synthesis gas is catalytically converted into high value-added products such as low-carbon alcohol, various hydrocarbons, acid, ester, ether and the like through different catalysts. Wherein the low carbon alcohol product has wide application, can be directly used as fuel and is cleaner.
The Mo-based catalyst has good catalytic activity on the hydrogenation of carbon monoxide to a low-carbon alcohol product, the performance is more excellent after other active metals or metal additives are added, and the other active metals can improve the total alcohol selectivity or promote the extension of a carbon chain; the auxiliary agent can adjust the electron or geometric structure of the active site, promote the interaction between different active metals or sites, adjust the acidic or basic site on the surface of the catalyst and improve the performance of the catalyst.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a KCoMnMoOxThe catalyst and the preparation method and application thereof, and the prepared catalyst has higher catalytic activity.
One aspect of the invention provides KCoMnMoOxThe catalyst is formed by dispersing K, Co, Mn and Mo metal elements on the surface of a carbon substrate.
The metal elements of K, Co, Mn and Mo are uniformly dispersed on the surface of the carbon substrate.
In the present invention, it is preferable that the molar ratio of the Co element to the Mo element is 0.45 to 0.55: 1.
in the present invention, the molar ratio of the Mn element to the Mo element is preferably 0.05 to 0.25: 1.
in the invention, the molar ratio of the K element to the Mo element is preferably 0.085-0.145: 1.
in the invention, the mole ratio of citric acid to total metal ions used in the preparation process of the catalyst is preferably 0.35-0.45.
The invention also provides KCoMnMoOxThe preparation method of the catalyst comprises the following steps:
s1) mixing a manganese source compound, a cobalt source compound, a molybdenum source compound, a potassium source compound and citric acid in water, and carrying out hydrothermal reaction to form gel;
s2) drying the gel, and calcining at high temperature to obtain KCoMnMoOxA catalyst.
Preferably, the manganese source compound is Mn (NO)3)2。
Preferably, the cobalt source compound is Co (NO)3)2·4H2O。
Preferably, the molybdenum source compound is (NH)4)6Mo7O24·4H2O。
Preferably, the potassium source compound is anhydrous K2CO3。
Preferably, in the present invention, the step S1) is specifically:
mixing an aqueous solution of a cobalt source compound and an aqueous solution of a molybdenum source compound, then adding a manganese source compound, uniformly mixing, then adding citric acid and a potassium source compound to obtain a mixture, and then carrying out hydrothermal reaction to form a gel.
The above addition sequence can avoid the precipitation of metal ions, and the solute can be mixed uniformly.
The molar ratio of the cobalt source compound to the molybdenum source compound is preferably 0.45 to 0.55: 1;
the molar ratio of the manganese source compound to the molybdenum source compound is preferably 0.05 to 0.25: 1;
the molar ratio of the potassium source compound to the molybdenum source compound is preferably 0.085 to 0.145: 1;
the mole ratio of the citric acid to the total metal ions is preferably 0.35-0.45: 1.
specifically, first, Co (NO) is mixed3)2The aqueous solution was slowly added (NH)4)6Mo7O24Adding a proper amount of 50% Mn (NO) into the solution after the solution is uniformly mixed3)2Aqueous solution, followed by separately mixing citric acid solution and K2CO3The solution was slowly added to the above solution.
In the preferred embodiment of the present invention, in the aqueous solution of the molybdenum source compound, the mass-to-volume ratio of the molybdenum source compound to the deionized water is 4.55 to 4.65 (g): 10-15 (ml).
Preferably, in the aqueous solution of the cobalt source compound, the mass volume ratio of the cobalt source compound to the deionized water is 3.45-4.21 (g): 5 to 10 (ml).
In a preferred embodiment of the present invention, the manganese source compound is added in a manner of 50% Mn (NO)3)2An aqueous solution;
the Mn (NO)3)2The mass ratio of the aqueous solution to the molybdenum source compound is preferably 0.45-2.35: 4.55-4.65;
according to the invention, the preferable adding mode of the citric acid is a citric acid aqueous solution, and the mass volume ratio of the citric acid to the deionized water is 3.60-4.20 (g): 8-12 (ml).
In a preferred mode of the invention, the potassium source compound is added as an aqueous solution of the potassium source compound, and the mass-to-volume ratio of the potassium source compound to the deionized water is 0.15-0.27 (g): 8-12 (ml).
In the present invention, preferably, the manganese source compound, the cobalt source compound, the molybdenum source compound, the potassium source compound, and citric acid are mixed in water, and then ammonia water is used to adjust the pH of the mixed solution to 3 to 5, more preferably 3 to 4. The method for adjusting the pH can avoid introducing other metal ions, and the introduced ammonia molecules are convenient to remove. Adjusting the pH to facilitate subsequent gel formation.
In some embodiments of the invention, the preparation method specifically comprises the following steps:
respectively adding appropriate amount of (NH)4)6Mo7O24·4H2O、Co(NO3)2·4H2O, citric acid monohydrate, anhydrous K2CO3Dissolving in deionized water, and mixing the above solutions under stirring. First Co (NO)3)2The aqueous solution was slowly added (NH)4)6Mo7O24·4H2Adding a proper amount of 50 percent Mn (NO) into the O solution after the O solution and the Mn solution are uniformly mixed3)2Aqueous solution, followed by separately mixing citric acid solution and K2CO3The solution was slowly added to the above solution. After adjusting the pH of the mixed solution to a proper value by using ammonia water, the solution is treated in a water bath to form gel. And (3) drying the gel in a drying box, and finally calcining in a tubular furnace to obtain the catalyst.
Preferred, formulation (NH) of the invention4)6Mo7O24(NH) used in solution4)6Mo7O24·4H2The mass-volume ratio of O to deionized water is 4.55-4.65 (g): 10 to 15 (ml); preparation of Co (NO)3)2Co (NO) used in solution3)2·4H2The mass-volume ratio of O to deionized water is 3.45-4.21 (g): 5 to 10 (ml); 50% Mn (NO) added3)2The mass of the aqueous solution is 0.45-2.35 g; preparation K2CO3Anhydrous K for use in solutions2CO3The mass-to-volume ratio of the deionized water is 0.15-0.27 (g): 8-12 (ml).
The proportion of each element is determined by the using amount, so that the catalyst can generate the best performance, has proper concentration and is beneficial to the formation of subsequent gel.
Further, the mass volume ratio of the citric acid monohydrate to the deionized water used in the preparation of the citric acid solution is 3.60-4.20 (g): 8-12 (ml). The dosage ensures the proportion of the total metal ions and the citric acid, and is beneficial to the formation of subsequent gel.
Preferably, the temperature of the hydrothermal reaction is 60-80 ℃; the time of the hydrothermal reaction is 6-9 h, and more preferably 7-8 h. The treatment can ensure that the solution system is heated uniformly, and the temperature of the treatment avoids the rapid evaporation of water, thereby being beneficial to the formation of gel.
According to the invention, the drying temperature of the gel is preferably 100-130 ℃, and the drying time is 12-17 h.
The above drying temperature can completely remove water in the system without damaging the structure of the catalyst.
Then high temperature calcination is carried out, preferably in the present invention, in a tube furnace.
The high-temperature calcination is preferably carried out at 350-450 ℃ for 3-5 h; the high-temperature calcination is preferably performed in a nitrogen atmosphere. The calcination atmosphere can maintain the catalyst structure, and the calcination temperature and time can ensure that the catalyst forms the required active sites.
The invention also provides the KCoMnMoOxCatalyst or KCoMnMoO prepared by the preparation methodxThe catalyst is applied to the reaction of preparing low-carbon alcohol by carbon monoxide hydrogenation.
The stirring method in the present invention is preferably magnetic stirring.
Compared with the prior art, the invention provides KCoMnMoOxThe catalyst is formed by dispersing K, Co, Mn and Mo metal elements on the surface of a carbon substrate. The invention adopts a sol-gel method to prepare KCoMnMoOxThe catalyst and metal elements are uniformly distributed on the surface of the catalyst, the components are closely contacted, strong interaction is formed between active sites, and the catalyst has excellent performance of preparing low-carbon alcohol by carbon monoxide hydrogenation by adjusting the proportion of the elements.
Drawings
FIG. 1 shows KCoMnMoO obtained in example 1 of the present inventionxTransmission electron microscopy images of the catalyst;
FIG. 2 shows KCoMnMoO obtained in example 1 of the present inventionxHigh resolution transmission electron microscope images of the catalyst;
FIG. 3 shows KCoMnMoO obtained in example 1 of the present inventionxSTEM-EDS images of the catalyst;
FIG. 4 shows an embodiment of the present invention1 KCoMnMoOxThe catalyst catalyzes the distribution data of the alcohol products of the carbon monoxide hydrogenation reaction at different temperatures.
Detailed Description
To further illustrate the present invention, the following examples are given to provide KCoMnMoOxThe catalyst, its preparation and use are described in detail.
The various starting materials used in the following examples are all commercially available products known in the art unless otherwise specified.
Example 1
KCoMnMoOxPreparation of the catalyst
Under stirring at room temperature, 4.63g of (NH)4)6Mo7O24·4H2O was dissolved in 12ml of deionized water, and 3.82g of Co (NO) was added3)2·4H2O in 8ml of deionized water, 4.10g of citric acid in 10ml of deionized water, and 0.21g of anhydrous K2CO3Dissolved in 10ml of deionized water. Under stirring, Co (NO) is first mixed3)2The solution was slowly added (NH)4)6Mo7O24To the solution, 2.35g of 50% Mn (NO) was added after mixing well3)2Aqueous solution, slowly adding citric acid solution dropwise into the solution, and adding K2CO3Slowly dripping the solution into the solution, and stirring and mixing the mixed solution uniformly.
The pH of the mixed solution was adjusted to 3.5 using ammonia, and then the solution was treated in a water bath at 75 ℃ for 7.5 hours until a gel was formed. The gel was dried in a drying oven at 120 ℃ for 15 hours. Drying, calcining in a tube furnace in a nitrogen atmosphere at 400 ℃, at a heating rate of 3 ℃/min for 4h to obtain KCoMnMoOxA catalyst.
Through detection, the KCoMnMoO obtained in the embodimentxThe catalyst has the advantages that all elements on the surface of the catalyst are uniformly dispersed, the catalyst has a mesoporous structure, and the ratio of Mo, Co, Mn and K elements is 2:1:0.25: 0.115.
FIG. 1 shows KCoMnMoO prepared in this examplexTransmission electron microscopy images of the catalyst; FIG. 2 shows KCoMnMoO prepared in this examplexHigh resolution transmission electron microscope images of the catalyst; FIG. 3 shows KCoMnMoO prepared in this examplexSTEM-EDS images of the catalyst. As can be seen from FIGS. 1 to 3, the catalyst prepared by the invention has better crystallinity, forms lamellar structure particles with more regular morphology, and all elements are uniformly distributed in the catalyst particles.
Example 2
KCoMnMoOxPreparation of the catalyst
Under stirring at room temperature, 4.59g of (NH)4)6Mo7O24·4H2O was dissolved in 11ml of deionized water, and 3.78g of Co (NO) was added3)2·4H2O was dissolved in 7ml of deionized water, 4.02g of citric acid was dissolved in 9ml of deionized water, and 0.26g of anhydrous K was added2CO3Dissolved in 11ml of deionized water. Under stirring, Co (NO) is first mixed3)2The solution was slowly added (NH)4)6Mo7O24To the solution, 1.86g of 50% Mn (NO) was added after mixing well3)2Aqueous solution, slowly adding citric acid solution dropwise into the solution, and adding K2CO3Slowly dripping the solution into the solution, and stirring and mixing the mixed solution uniformly.
The pH of the mixed solution was adjusted to 3.4 using ammonia, and then the solution was treated in a water bath at 78 ℃ for 7.2 hours until a gel was formed. The gel was dried in a drying oven at 115 ℃ for 14 hours. Placing the dried mixture into a tube furnace for calcination under the nitrogen atmosphere at the temperature of 410 ℃, at the temperature rise rate of 3.2 ℃/min and for 4.2h to obtain KCoMnMoOxA catalyst.
After detection, KCoMnMoO obtained in the embodimentxThe catalyst has the advantages that all elements on the surface of the catalyst are uniformly dispersed, the catalyst has a mesoporous structure, and the ratio of Mo, Co, Mn and K elements is 2:1:0.20: 0.145.
Example 3
KCoMnMoOxPreparation of the catalyst
4.66g (NH) was added under stirring at room temperature4)6Mo7O24·4H2O was dissolved in 13ml of deionized water, and 3.84g of Co (NO) was added3)2·4H2Dissolving O in 9ml deionized water, dissolving 4.01g citric acid in 10ml deionized water, and adding 0.24g anhydrous K2CO3Dissolved in 11ml of deionized water. Under stirring, Co (NO) is first mixed3)2The solution was slowly added (NH)4)6Mo7O24To the solution, 1.70g of 50% Mn (NO) was added after mixing well3)2Aqueous solution, slowly adding citric acid solution dropwise into the solution, and adding K2CO3Slowly dripping the solution into the solution, and stirring and mixing the mixed solution uniformly.
The pH of the mixed solution was adjusted to 3.6 using ammonia, and then the solution was treated in a water bath at 72 ℃ for 7.8 hours until a gel was formed. The gel was dried in a drying oven at 125 deg.C for 16 hours. Placing the dried mixture into a tubular furnace for calcination under the nitrogen atmosphere at 390 ℃, at the temperature rise rate of 2.9 ℃/min for 3.9h to obtain KCoMnMoOxA catalyst.
Through detection, the KCoMnMoO obtained in the embodimentxThe catalyst has the advantages that all elements on the surface of the catalyst are uniformly dispersed, the catalyst has a mesoporous structure, and the ratio of Mo, Co, Mn and K elements is 2:1:0.18: 0.13.
Example 4
KCoMnMoOxPreparation of the catalyst
4.61g of (NH) was added under stirring at room temperature4)6Mo7O24·4H2O was dissolved in 11.5ml of deionized water, and 3.80g of Co (NO) was added3)2·4H2O in 7.5ml deionized water, 3.75g citric acid in 9ml deionized water, 0.18g anhydrous K2CO3Dissolved in 9ml of deionized water. Under stirring, Co (NO) is first mixed3)2The solution was slowly added (NH)4)6Mo7O24To the solution, 0.94g of 50% Mn (NO) was added after mixing well3)2Aqueous solution, slowly adding citric acid solution into the solution, and adding K2CO3Slowly dripping the solution into the solution, and stirring and mixing the mixed solution uniformly.
The pH of the mixed solution was adjusted to 4.2 using ammonia, and then the solution was treated in a water bath at 70 ℃ for 8.0 hours until a gel was formed. The gel was dried in a drying oven at 130 ℃ for 14 hours. Placing the dried mixture into a tubular furnace for calcination under the nitrogen atmosphere at 380 ℃ at the temperature rise rate of 2.7 ℃/min for 4.5h to obtain KCoMnMoOxA catalyst.
Through detection, the KCoMnMoO obtained in the embodimentxThe catalyst has the advantages that all elements on the surface of the catalyst are uniformly dispersed, the catalyst has a mesoporous structure, and the ratio of Mo, Co, Mn and K elements is 2:1:0.10: 0.10.
Example 5
KCoMnMoOxTesting of catalytic Performance of the catalyst
KCoMnMoO prepared in the inventive example 1 was usedxThe catalyst is used for testing the catalytic performance of the reaction of preparing the low carbon alcohol by carbon monoxide hydrogenation.
The catalytic reaction is carried out in a fixed bed reactor, and the whole device mainly comprises four parts, namely a gas circuit system, a reaction system, a separation system and a detection system. The reduction gas circuit and the reaction gas circuit jointly form a gas circuit system. The filter is used for removing impurities in the gas and preventing other fittings of the gas path from being blocked. H2The synthesis gas/CO 2 (molar ratio) is filtered by a filter, the pressure is regulated by a pressure reducing and stabilizing valve, the flow is regulated by a mass flow meter, and then the synthesis gas enters the reaction tube through a one-way valve for reaction. The function of check valve is exactly to prevent the gas refluence, damages mass flowmeter. The reaction tube consisted of a stainless steel tube of about 60ml length and about 8mm internal diameter. The reaction pressure is regulated and controlled by a pressure stabilizing valve and a back pressure valve, the pressure transmitter can display the real-time reaction pressure, and the reaction temperature is detected by a K-type thermocouple inserted into the catalyst bed layer. The separation system is mainly composed of a set of cold trapThe structure is arranged, and the inside of the structure contains an ice-water mixture. The gas after reaction passes through a cold trap filled with an ice-water mixture, a liquid-phase product is separated, and an uncondensed gas-phase product enters a gas chromatograph through a six-way valve. The detection system comprises a TCD gas chromatograph and a FID gas chromatograph, and can perform off-line analysis on separated liquid phase product and uncondensed gas such as CO2、CH4CO and light hydrocarbons, etc. were analyzed on-line. In order to prevent the condensation of the reaction products from blocking the pipeline, the pipeline from the outlet of the cold trap until the gas chromatography is entered needs to be wound with a heating tape for heating.
The reaction results are shown in table 1:
TABLE 1 KCoMnMoO obtained in example 1xPerformance data of catalyst catalyzed carbon monoxide hydrogenation reaction at different temperatures
Figure BDA0003524062160000071
Figure BDA0003524062160000081
Reduction conditions pure H2,T＝450℃；
Reaction conditions H2/CO＝2/1,P＝5.0MPa,GHSV＝6000h-1；
FIG. 4 shows KCoMnMoO obtained in example 1 of the present inventionxThe distribution data of alcohol products of the catalytic carbon monoxide hydrogenation reaction at different temperatures are calculated, and CO is removed when the selectivity of the products is calculated2。
From the above results, it can be seen that KCoMnMoO was obtained in example 1xThe catalyst has higher CO conversion rate, total alcohol selectivity and total alcohol STY for catalyzing the carbon monoxide hydrogenation reaction in a larger temperature range. In general, the catalyst has excellent catalytic performance for preparing low-carbon alcohol by carbon monoxide hydrogenation.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. KCoMnMoOxThe catalyst is characterized in that K, Co, Mn and Mo metal elements are dispersed on the surface of the carbon substrate.
2. KCoMnMoO according to claim 1xThe catalyst is characterized in that the molar ratio of the Co element to the Mo element is 0.45-0.55: 1;
the molar ratio of the Mn element to the Mo element is 0.05-0.25: 1;
the molar ratio of the K element to the Mo element is 0.085-0.145: 1.
3. KCoMnMoOxThe preparation method of the catalyst comprises the following steps:
s1) mixing a manganese source compound, a cobalt source compound, a molybdenum source compound, a potassium source compound and citric acid in water, and carrying out hydrothermal reaction to form gel;
s2) drying the gel, and calcining at high temperature to obtain KCoMnMoOxA catalyst.
4. The method according to claim 3, wherein the manganese source compound is Mn (NO)3)2；
The cobalt source compound is Co (NO)3)2·4H2O；
The molybdenum source compound is (NH)4)6Mo7O24·4H2O；
The potassium source compound is anhydrous K2CO3。
5. The preparation method according to claim 3, wherein the step S1) is specifically:
mixing an aqueous solution of a cobalt source compound and an aqueous solution of a molybdenum source compound, then adding a manganese source compound, uniformly mixing, then adding citric acid and a potassium source compound to obtain a mixture, and then carrying out hydrothermal reaction to form gel.
6. The preparation method according to claim 5, wherein the mass-to-volume ratio of the molybdenum source compound to the deionized water in the aqueous solution of the molybdenum source compound is 4.55 to 4.65 (g): 10 to 15 (ml);
in the aqueous solution of the cobalt source compound, the mass-to-volume ratio of the cobalt source compound to deionized water is 3.45-4.21 (g): 5 to 10 (ml);
the manganese source compound is added in a manner of 50% of Mn (NO)3)2An aqueous solution;
the Mn (NO)3)2The mass ratio of the aqueous solution to the molybdenum source compound is 0.45-2.35: 4.55-4.65;
the citric acid is added in a citric acid water solution mode, and the mass volume ratio of the citric acid to the deionized water is 3.60-4.20 (g): 8-12 (ml);
the potassium source compound is added into an aqueous solution of a potassium source compound, and the mass-to-volume ratio of the potassium source compound to deionized water is 0.15-0.27 (g): 8-12 (ml).
7. The method according to claim 3, wherein the manganese source compound, the cobalt source compound, the molybdenum source compound, the potassium source compound, and citric acid are mixed in water, and then ammonia water is used to adjust the pH of the mixed solution to 3 to 5.
8. The preparation method according to claim 3, wherein the temperature of the hydrothermal reaction is 60-80 ℃; the time of the hydrothermal reaction is 6-9 h;
drying the gel at the temperature of 100-130 ℃ for 12-17 h;
the high-temperature calcination is carried out at the temperature of 350-450 ℃ for 3-5 h;
the high temperature calcination is carried out in a nitrogen atmosphere.
9. The production method according to claim 3, wherein the molar ratio of the cobalt source compound to the molybdenum source compound is 0.45 to 0.55: 1;
the molar ratio of the manganese source compound to the molybdenum source compound is 0.05-0.25: 1;
the molar ratio of the potassium source compound to the molybdenum source compound is 0.085-0.145: 1;
the molar ratio of the citric acid to the total metal ions is 0.35-0.45: 1.
10. KCoMnMoO as set forth in any one of claims 1 to 2xCatalyst or KCoMnMoO prepared by the preparation method of any one of claims 3 to 9xThe catalyst is applied to the reaction of preparing low-carbon alcohol by carbon monoxide hydrogenation.
CN202210189641.0A 2022-02-28 2022-02-28 KCoMnMoOxCatalyst, preparation method and application thereof Pending CN114558586A (en)

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CN103599788A (en) * 2013-11-01 2014-02-26 中国石油化工股份有限公司 Cobalt-based catalyst for CO hydrogenation and preparation method and application thereof
CN106607040A (en) * 2015-10-21 2017-05-03 中国石油化工股份有限公司 Synthesis gas-to-low carbon mixed alcohol catalyst, preparation method and applications thereof

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CN101733135A (en) * 2009-12-07 2010-06-16 中国科学院山西煤炭化学研究所 Sulfur-tolerant low-carbon alcohol catalyst and preparing method and application thereof
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