CN113600208B - CuCoMn/Al 2 O 3 Catalyst, preparation method and application thereof - Google Patents

CuCoMn/Al 2 O 3 Catalyst, preparation method and application thereof Download PDF

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CN113600208B
CN113600208B CN202111003890.8A CN202111003890A CN113600208B CN 113600208 B CN113600208 B CN 113600208B CN 202111003890 A CN202111003890 A CN 202111003890A CN 113600208 B CN113600208 B CN 113600208B
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catalyst
cucomn
inorganic
cobalt
copper
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CN113600208A (en
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王建国
程家旭
邵方君
王潇剑
马帆冬
江文杰
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Zhejiang University of Technology ZJUT
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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
    • B01J23/70—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
    • B01J23/8892—Manganese
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C29/156—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 containing iron group metals, platinum group metals or compounds thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a CuCoMn/Al 2 O 3 Catalyst, preparation method and application thereof, wherein the catalyst takes copper-cobalt-manganese mixed metal as active component, al 2 O 3 The active component copper-cobalt-manganese mixed metal is uniformly dispersed in Al as a carrier 2 O 3 And (3) on a carrier. It is made of Al 2 O 3 And cheap materials such as metal nitrate are used as raw materials, and a simple impregnation method is adopted to load the metal active components on Al 2 O 3 And filtering, washing, drying and calcining the carrier in turn to obtain the copper-cobalt-manganese ternary metal catalyst. The preparation method is simple, the reaction condition is mild, the method can be used for deuteration reaction of higher alcohol, and the method has wide application prospect.

Description

CuCoMn/Al 2 O 3 Catalyst, preparation method and application thereof
Technical Field
The invention relates to the technical field of multi-element metal catalysts, in particular to a CuCoMn/Al catalyst 2 O 3 A catalyst, a preparation method and application thereof.
Background
Deuterated chemicals are a special compound and have important application in the fields of reaction mechanism research, dynamics, drug metabolism, biological structure measurement and the like. Most methods of deuteration involve high temperature, high pressure (deuterium is the deuterium source), strong acids, strong bases or expensive metal catalysts. Compared with hydrogen deuterium catalytic exchange reaction, the deuterium adding reaction (or deuteration reaction) has wider adaptability and higher selectivity of functional groups, and different deuterium adding (or deuteration) catalysts are selected, so that site-specific deuteration on different functional sites can be realized, and the method can be used as an ideal deuteration strategy. However, since deuterium is required for the deuterium adding reaction (or deuteration reaction), and high temperature, high pressure and noble metal catalyst are required, the applicable range of deuterium adding reaction is greatly limited. Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a multi-metal component catalyst and a preparation method thereof, and the catalyst can be applicable to preparing higher alcohols by deuteration reaction under milder conditions by using non-noble metals of copper, cobalt and manganese.
The invention defines a CuCoMn/Al 2 O 3 The catalyst is characterized in that the mixed metal of copper, cobalt and manganese is used as an active component, al 2 O 3 The active component copper-cobalt-manganese mixed metal is uniformly dispersed in Al as a carrier 2 O 3 And (3) on a carrier.
The invention also defines CuCoMn/Al 2 O 3 The preparation method of the catalyst is characterized by comprising the following steps:
1) Dissolving inorganic copper salt, inorganic cobalt salt and inorganic manganese salt in deionized water to obtain a solution A;
2) Al is added with 2 O 3 Adding the powder into the solution A obtained in the step 1), and stirring at a certain temperature;
3) Filtering the solution obtained in the step 2), and sequentially washing with water and alcohol to obtain a solid sample, namely a metal precursor;
4) Drying the metal precursor obtained in the step 3) in air at a certain temperature overnight;
5) Grinding the dried solid into powder, calcining in a muffle furnace, and naturally cooling to obtain CuCoMn/Al 2 O 3 A catalyst.
Furthermore, the invention also defines that in the step 1), the inorganic copper salt is copper nitrate trihydrate, the inorganic cobalt salt is cobalt nitrate hexahydrate, and the inorganic manganese salt is manganese nitrate tetrahydrate; the mol ratio of the inorganic copper salt to the inorganic cobalt salt to the inorganic manganese salt is 0.4-3:0.3-2:0.5-1.5.
Further, the invention also defines that the stirring condition in the step 2) is constant temperature stirring for 10-48 hours at 60-90 ℃.
Further, the present invention also defines that the addition amount of the solution a in the step 2) is larger than the saturation adsorption amount of alumina.
Further, the invention also defines that the temperature of the overnight drying in the air in step 4) is 55-65 ℃, preferably the constant temperature drying is 60 ℃ for 12 hours.
Further, the invention also defines that the calcination process in the step 5) is air calcination for 3-5 hours at the temperature rising rate of 1 ℃/min and the temperature rising rate of 300-500 ℃.
Furthermore, the invention also defines the CuCoMn/Al 2 O 3 Use of a catalyst in the preparation of deuterated higher alcohols.
Further, the invention also defines the application, cuCoMn/Al before reaction 2 O 3 The catalyst is reduced for 5 hours at 400-500 ℃ under the mixed atmosphere of deuterium and nitrogen (5% of deuterium) in a fixed bed, and the reaction space velocity is 5400 hours -1 The space velocity here is the volume space velocity, the ratio of carbon monoxide to deuterium gas being 1:2, the reaction temperature is 220-280 ℃, the reaction pressure is 2.8-4.8 Mpa, and the volume content of deuterium in the deuterium-nitrogen mixed gas is 5%.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
1) The method takes cheap cupric nitrate, cobalt salt, manganese salt and commercial alumina as raw materials, adopts an impregnation method to prepare the ternary metal catalyst, has simple preparation process and operation and low cost, and can be used for industrial production of the catalyst;
2) According to the ternary metal catalyst, the noble metal catalyst used in the traditional deuterium adding reaction is replaced by the non-noble metal, so that the ternary metal catalyst is suitable for the deuterium adding reaction, the deuterium adding reaction can be performed under the condition of low temperature and low pressure, and the requirements on reaction equipment are greatly reduced.
Drawings
FIG. 1 is a view of CuCoMn/Al 2 O 3 A catalyst element profile;
FIG. 2 is an MS diagram of deuterated propanol;
fig. 3 is an NMR chart of deuterated propanol.
Detailed Description
The following describes the technical scheme of the present invention with specific examples, but the scope of the present invention is not limited thereto:
example 1 CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
adding 0.15g of copper nitrate trihydrate, 0.26g of cobalt nitrate hexahydrate and 0.38g of manganese nitrate tetrahydrate into 30ml of deionized water to prepare a mixed solution, weighing 4g of aluminum oxide powder, slowly adding the aluminum oxide powder into the prepared mixed solution to prevent powder from splashing, covering a cup mouth by using a preservative film, and stirring for 12 hours at a constant temperature of 85 ℃. Carrying out suction filtration on the stirred sample, and washing the sample to be neutral by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 400 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 Catalyst, cuCoMn/Al 2 O 3 The SEM characterization result of the catalyst is shown in FIG. 1, and it can be seen from the graph that the Co loading is 8.24wt%; cu loading was 2.93wt%; the Mn loading was 2.00wt%.
Example 2:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
adding 0.36g of copper nitrate trihydrate, 0.44g of cobalt nitrate hexahydrate and 0.38g of manganese nitrate tetrahydrate into 30ml of deionized water to prepare a mixed solution, weighing 4g of aluminum oxide powder, slowly adding the aluminum oxide powder into the prepared mixed solution, covering a cup mouth by using a preservative film, and stirring for 16 hours at the constant temperature of 60 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 350 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Example 3:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
0.73g of copper nitrate trihydrate, 0.61g of cobalt nitrate hexahydrate, and 0.45g of manganese nitrate tetrahydrate were added to 30ml of deionized waterPreparing a mixed solution in water, weighing 4g of aluminum oxide powder, slowly adding the aluminum oxide powder into the prepared mixed solution, covering a beaker by using a preservative film, and stirring for 12 hours at a constant temperature of 75 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 400 ℃ for 3 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Example 4:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
1.01g of copper nitrate trihydrate, 0.79g of cobalt nitrate hexahydrate and 0.83g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, 4g of aluminum oxide powder is weighed and slowly added into the prepared mixed solution, a beaker mouth is covered by a preservative film, and stirring is carried out for 12 hours at a constant temperature of 60 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining the ground sample for 4 hours at 450 ℃ under the air atmosphere at the heating rate of 1 ℃/min to obtain a finished product CuCoMn/Al 2 O 3 A catalyst.
Example 5:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
2.27g of copper nitrate trihydrate, 0.99g of cobalt nitrate hexahydrate and 0.91g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, 4g of aluminum oxide powder is weighed and slowly added into the prepared mixed solution, a beaker mouth is covered by a preservative film, and stirring is carried out for 24 hours at a constant temperature of 85 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 70 c under an air atmosphere for 22 hours. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 500 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Example 6:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
1.31g of copper nitrate trihydrate, 0.79g of cobalt nitrate hexahydrate and 0.68g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, 4g of aluminum oxide powder is weighed and slowly added into the prepared mixed solution, a beaker mouth is covered by a preservative film, and the mixture is stirred for 16 hours at the constant temperature of 80 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 300 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Example 7:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
1.45g of copper nitrate trihydrate, 0.87g of cobalt nitrate hexahydrate and 0.75g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, 4g of aluminum oxide powder is weighed and slowly added into the prepared mixed solution, a beaker mouth is covered by a preservative film, and stirring is carried out for 36 hours at a constant temperature of 60 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 400 ℃ for 4 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Example 8:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
1.45g of copper nitrate trihydrate, 1.31g of cobalt nitrate hexahydrate and 0.75g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, 4g of aluminum oxide powder is weighed and slowly added into the prepared mixed solution, a beaker mouth is covered by a preservative film, and stirring is carried out for 24 hours at a constant temperature of 85 ℃. Stirring the mixtureCarrying out suction filtration on the sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 400 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Example 9:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
1.31g of copper nitrate trihydrate, 0.79g of cobalt nitrate hexahydrate and 1.26g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, 4g of aluminum oxide powder is weighed and slowly added into the prepared mixed solution, a beaker mouth is covered by a preservative film, and stirring is carried out for 24 hours at a constant temperature of 70 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 350 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Example 10:
CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
2.26g of copper nitrate trihydrate, 1.41g of cobalt nitrate hexahydrate and 0.87g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, 4g of aluminum oxide powder is weighed and slowly added into the prepared mixed solution, a beaker mouth is covered by a preservative film, and the mixture is stirred for 14 hours at a constant temperature of 70 ℃. Carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and water; and then dried at 60℃for 12 hours under an air atmosphere. Grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 400 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCoMn/Al 2 O 3 A catalyst.
Comparative example 1:
2.26g of copper nitrate trihydrate and 0.92g of manganese nitrate tetrahydrate are added into 30ml of deionized water to prepare a mixed solution, and then the mixed solution is weighed4g of aluminum oxide powder is slowly added into the prepared mixed solution, a fresh-keeping film is used for covering the mouth of a beaker, and the mixture is stirred for 40 hours under the constant temperature condition of 60 ℃; carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and deionized water; drying at 60 ℃ for 12 hours under an air atmosphere; grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 300 ℃ for 5 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuMn/Al 2 O 3 A catalyst.
Comparative example 2:
adding 2.26g of copper nitrate trihydrate and 0.98g of cobalt nitrate hexahydrate into 30ml of deionized water to prepare a mixed solution, then weighing 4g of aluminum oxide powder, slowly adding the aluminum oxide powder into the prepared mixed solution, covering a cup mouth by using a preservative film, and stirring for 24 hours at a constant temperature of 70 ℃; carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and deionized water; drying at 60 ℃ for 12 hours under an air atmosphere; grinding the dried sample, putting the ground sample into a muffle furnace, and calcining at 500 ℃ for 3 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CuCo/Al 2 O 3 A catalyst.
Comparative example 3:
adding 0.98g of cobalt nitrate hexahydrate and 0.91g of manganese nitrate tetrahydrate into 30ml of deionized water to prepare a mixed solution, weighing 4g of aluminum oxide powder, slowly adding the powder into the prepared mixed solution, covering a cup mouth by using a preservative film, and stirring for 12 hours at the constant temperature of 80 ℃; carrying out suction filtration on the stirred sample, and washing the sample for a plurality of times by using ethanol and deionized water; drying at 60 ℃ for 12 hours under an air atmosphere; grinding the dried sample, placing the ground sample into a muffle furnace, and calcining at 400 ℃ for 4 hours under the air atmosphere at the heating rate of 1 ℃/min to obtain the finished product CoMn/Al 2 O 3 A catalyst.
Example 11:
catalyst Performance test
1g of catalyst and 60-80 mesh quartz sand are mixed according to a proportion of 1:3 is filled in the reaction tube to form a catalyst bed layer with the height of about 3 cm. Before the reaction starts, 5% deuterium gas and nitrogen gas mixture is used forActivating at 400-500 deg.C (2 deg.C/min) for 5 hr, and cooling in nitrogen atmosphere. After the temperature is reduced to normal temperature, a valve for deuterium and carbon monoxide is opened, the flow rate of deuterium is controlled at 60mL/min, the flow rate of carbon monoxide is controlled at 30mL/min, the deuterium and the carbon monoxide are uniformly mixed through a gas mixing tank at 240 ℃, then the catalyst passes through a heated catalyst bed, the catalyst temperature is 260 ℃, and the pressure of a reaction tube is 3.2Mpa. Gaseous product C flowing out of the reaction tube 3 D 8 O is collected by a condenser and a gas-liquid separator. The MS spectrum analyzed by GC-MS after collecting the 96℃purified product by rectification is shown in FIG. 2; the NMR spectrum of the nuclear magnetic analysis is shown in fig. 3, where it can be seen that the hydrogen at the α, β, γ positions are each replaced by a deuterium atom.
The catalysts prepared in examples 1 to 10 and the catalysts prepared in comparative examples 1 to 3 were each subjected to the catalyst performance test by the above procedure, and the experimental results in the continuous reaction for 10 hours were summarized in Table 1.
TABLE 1 evaluation results of catalyst Activity
As can be seen from Table 1, the CuCoMn/Al obtained in the present invention 2 O 3 The catalyst has obviously better catalyst performance than CuMn/Al 2 O 3 Catalyst, cuCo/Al 2 O 3 Catalysts or CoMn/Al 2 O 3 A catalyst.

Claims (9)

1. CuCoMn/Al 2 O 3 The use of a catalyst in the preparation of deuterated higher alcohols characterized in that said CuCoMn/Al 2 O 3 The catalyst takes copper-cobalt-manganese mixed metal as an active component, al 2 O 3 The active component copper-cobalt-manganese mixed metal is uniformly dispersed in Al as a carrier 2 O 3 A carrier; the CuCoMn/Al 2 O 3 A method for preparing a catalyst comprising the steps of:
1) Dissolving inorganic copper salt, inorganic cobalt salt and inorganic manganese salt in deionized water to obtain a solution A;
2) Al is added with 2 O 3 Adding the powder into the solution A obtained in the step 1), and stirring at a certain temperature;
3) Filtering the solution obtained in the step 2), and sequentially washing with water and alcohol to obtain a solid sample, namely a metal precursor;
4) Drying the metal precursor obtained in the step 3) in air at a certain temperature overnight;
5) Grinding the dried solid into powder, calcining in a muffle furnace, and naturally cooling to obtain CuCoMn/Al 2 O 3 A catalyst.
2. The use according to claim 1, characterized in that in step 1) the inorganic copper salt is copper nitrate trihydrate, the inorganic cobalt salt is cobalt nitrate hexahydrate, and the inorganic manganese salt is manganese nitrate tetrahydrate; the molar ratio of the inorganic copper salt to the inorganic cobalt salt to the inorganic manganese salt is 0.4-3:0.3-2:0.5-1.5.
3. Use according to claim 1, characterized in that the stirring conditions in step 2) are constant temperature stirring at 60-90 ℃ for 10-48h.
4. Use according to claim 1, characterized in that the amount of solution a added in step 2) is greater than the saturated adsorption amount of alumina.
5. Use according to claim 1, characterized in that the temperature of the overnight drying in air in step 4) is 55-65 ℃.
6. The method according to claim 5, wherein the air-drying in step 4) is carried out overnight at a constant temperature of 60℃for 12 hours.
7. Use according to claim 1, characterized in that the calcination in step 5) is air calcination for 3-5 hours at a temperature increase rate of 1 ℃/min up to 300-500 ℃.
8. The process according to claim 1, wherein the pre-reaction CuCoMn/Al 2 O 3 The catalyst is reduced for 5 hours at 400-500 ℃ under the mixed atmosphere of deuterium and nitrogen in a fixed bed, and the reaction space velocity is 5400 hours -1 The ratio of carbon monoxide to deuterium is 1:2, the reaction temperature is 220-280 ℃, and the reaction pressure is 2.8-4.8 mpa.
9. Use according to claim 8, characterized in that the volume content of deuterium in the deuterium nitrogen mixture is 5%.
CN202111003890.8A 2021-08-30 2021-08-30 CuCoMn/Al 2 O 3 Catalyst, preparation method and application thereof Active CN113600208B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104056629A (en) * 2014-06-17 2014-09-24 中国天辰工程有限公司 Catalyst used in preparation of low-carbon alcohol by synthesis gas, as well as preparation method and application of catalyst
CN105251505A (en) * 2014-05-27 2016-01-20 中国科学院上海高等研究院 Cobalt-based catalyst for producing C2+ oxygen-containing compound and co-producing olefin through synthetic gas, preparation method and applications thereof
CN111116313A (en) * 2019-12-31 2020-05-08 中国船舶重工集团公司第七一八研究所 Preparation method of deuterated methanol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105251505A (en) * 2014-05-27 2016-01-20 中国科学院上海高等研究院 Cobalt-based catalyst for producing C2+ oxygen-containing compound and co-producing olefin through synthetic gas, preparation method and applications thereof
CN104056629A (en) * 2014-06-17 2014-09-24 中国天辰工程有限公司 Catalyst used in preparation of low-carbon alcohol by synthesis gas, as well as preparation method and application of catalyst
CN111116313A (en) * 2019-12-31 2020-05-08 中国船舶重工集团公司第七一八研究所 Preparation method of deuterated methanol

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