CN115672399A - Organic amine catalyst, preparation method thereof and preparation method of diquat dichloride - Google Patents
Organic amine catalyst, preparation method thereof and preparation method of diquat dichloride Download PDFInfo
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- CN115672399A CN115672399A CN202211293508.6A CN202211293508A CN115672399A CN 115672399 A CN115672399 A CN 115672399A CN 202211293508 A CN202211293508 A CN 202211293508A CN 115672399 A CN115672399 A CN 115672399A
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- 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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- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides an organic amine catalyst and a preparation method thereof, and a preparation method of diquat dichloride, belonging to the technical field of chemical production, wherein the organic amine catalyst comprises a carrier and chain organic amine loaded on the carrier, and the load capacity of the chain organic amine is 2-30%. The preparation method of the organic amine catalyst comprises the steps of dissolving chain organic amine in an organic solvent, adding a carrier under the condition of stirring, continuously stirring until suspension is obtained, and then evaporating the organic solvent of the suspension to obtain the organic amine catalyst. The preparation method of the diquat dichloride is characterized in that 2,2' -bipyridyl and 1, 2-dibromoethane are used as raw materials, and the diquat dichloride is synthesized through catalytic reaction of an organic amine catalyst. The organic amine catalyst of the invention directly catalyzes 2,2' -bipyridyl and dichloroethane to react and synthesize diquat dichloride, and solves the problems of complex process, low product yield and the like of the existing synthesis method.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to an organic amine catalyst and a preparation method thereof.
Background
The diquat is a contact desiccant or herbicide with certain internal absorbability developed by the Chengda company in 1958, has the action mechanism of destroying plant cells by generating superoxide, takes effect quickly, has a wide weed control spectrum, and is a non-selective contact herbicide.
The chemical name of diquat is 1,1' -ethylene-2, 2' -bipyridine dibromide salt which is mainly prepared by cyclization reaction of 2,2' -bipyridine and 1, 2-dibromoethane (U.S. Pat. No. 2823987), and the prior art also indicates that the anion of diquat is changed and the herbicidal activity is not damaged, and that chloride ion is a relatively cheap resource, and counter ion for diquat cation is suitable.
The method for synthesizing the diquat dichloride (1, 1 '-ethylene-2, 2' -bipyridyl dichloride) in the prior art mainly uses the diquat dibromide salt as a raw material to prepare the diquat dichloride, particularly adopts chlorine direct connection, and then prepares the diquat dichloride through oxidation-reduction reaction.
Disclosure of Invention
Based on the background problems, the invention aims to provide an organic amine catalyst which has good stability and can catalyze 2,2' -bipyridyl and dichloroethane to directly react to synthesize diquat dichloride; it is another object of the present invention to provide a method for preparing an organic amine catalyst; the third purpose of the invention is to provide a preparation method of diquat dichloride, which takes 2,2' -bipyridine and dichloroethane as raw materials for direct synthesis, and has the advantages of simple process flow, remarkably reduced production cost and high product conversion rate.
In order to achieve the above object, in one aspect, the embodiment of the present invention provides a technical solution:
the organic amine catalyst comprises a carrier and chain organic amine loaded on the carrier, wherein the loading amount of the chain organic amine is 2-30%.
Further, the carrier is one of active carbon, diatomite and hydrotalcite.
Further, the chain organic amine is one or more of polyethyleneimine, triethylenediamine, hexamethyleneimine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
On the other hand, the embodiment of the invention provides a preparation method of an organic amine catalyst, which comprises the steps of dissolving chain organic amine in an organic solvent, adding a carrier under the condition of stirring, continuously stirring until a suspension is obtained, and then evaporating the organic solvent of the suspension to obtain the organic amine catalyst.
Further, the mass ratio of the chain organic amine to the organic solvent is 1-10, and the organic solvent is selected from one or more of methanol, ethanol, propanol, acetone and isopropanol.
Further, evaporating the suspension at a temperature of more than or equal to 85 ℃ to remove the organic solvent until the organic solvent is completely volatilized.
In a third aspect, an embodiment of the present invention provides a preparation method of diquat dichloride, which uses 2,2' -bipyridine and 1, 2-dibromoethane as raw materials, and synthesizes the diquat dichloride through a catalytic reaction of the organic amine catalyst, wherein a reaction equation of the diquat dichloride is shown as formula (I).
Further, nitrogen is filled in the reaction as protective gas, the reaction pressure is controlled to be 0.5-3MPa, the reaction temperature is controlled to be 150-250 ℃, and the reaction time is 5-8h.
Further, the molar ratio of the 2,2 '-bipyridine to the 1, 2-dibromoethane is 1, and the mass ratio of the 2,2' -bipyridine to the organic amine catalyst is 1.
Further, the particle size of the organic amine catalyst is 200-500 meshes.
Compared with the prior art, the embodiment of the invention at least has the following effects:
1. the invention provides an organic amine catalyst, which comprises a carrier and chain-shaped organic amine loaded on the carrier, has higher stability, and can realize the separation and the recycling of the organic amine catalyst by adopting the carrier to load the chain-shaped organic amine; the organic amine catalyst can catalyze 2,2 '-bipyridyl and dichloroethane to directly react to synthesize the diquat dichloride, and the conversion rate of the 2,2' -bipyridyl and the dichloroethane is high, and the selectivity of the diquat dichloride is high.
2. The invention provides a preparation method of diquat dichloride, which is directly synthesized by taking 2,2' -bipyridyl and dichloroethane as raw materials and has the advantages of simple process flow, capability of obviously reducing the production cost and high product conversion rate.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete description of the technical solutions in the embodiments of the present invention, it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to solve the problems of complex process conditions and difficult guarantee of product purity and stability of the existing method for preparing the diquat dichloride by using the diquat dibromide salt as the raw material, the invention provides the invention concept of directly synthesizing the diquat dichloride by using 2,2' -bipyridine and dichloroethane as the raw materials, which has the advantages of simple process flow, remarkably reduced production cost and high product conversion rate.
In order to realize the inventive concept, the invention provides an organic amine catalyst which can catalyze the reaction of 2,2 '-bipyridyl and dichloroethane, has high conversion rate of the 2,2' -bipyridyl and the dichloroethane, and has high selectivity of diquat dichloride.
It should be noted that the carriers used in the following examples all had specific surface areas of 100 to 1000m 2 Per gram of powder.
In addition, the loading amount in the invention is the mass percentage of the chain organic amine to the organic amine catalyst (total mass of the carrier and the chain organic amine).
The technical solution of the present invention will be described by specific examples.
Example 1
The organic amine catalyst comprises activated carbon and polyethyleneimine loaded on the activated carbon, wherein the loading amount of the polyethyleneimine is 2%.
The preparation method of the organic amine catalyst comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 20g of ethanol, heating to 50 ℃, adding 98g of activated carbon under the stirring condition, and continuously stirring for 3 hours under the heat preservation condition to obtain a suspension;
(2) And raising the temperature to 85 ℃, continuously stirring and steaming to remove the ethanol in the suspension, and obtaining the organic amine catalyst after the ethanol is completely volatilized.
Example 2
The organic amine catalyst comprises activated carbon and polyethyleneimine loaded on the activated carbon, wherein the loading amount of the polyethyleneimine is 4%.
The preparation method of the organic amine catalyst comprises the following steps:
(1) Dissolving 2g of polyethyleneimine in 20g of ethanol, heating to 50 ℃, adding 48g of activated carbon under the condition of stirring, and continuously stirring for 3 hours at the same time to obtain a suspension;
(2) And raising the temperature to 85 ℃, continuously stirring and steaming to remove the ethanol in the suspension, and obtaining the organic amine catalyst after the ethanol is completely volatilized.
Example 3
The organic amine catalyst comprises activated carbon and polyethyleneimine loaded on the activated carbon, wherein the loading amount of the polyethyleneimine is 10%.
The preparation method of the organic amine catalyst comprises the following steps:
(1) Dissolving 10g of polyethyleneimine in 150g of ethanol, heating to 50 ℃, adding 90g of activated carbon under the condition of stirring, and continuously stirring for 3 hours at the same time to obtain a suspension;
(2) And raising the temperature to 85 ℃, continuously stirring and steaming to remove the ethanol in the suspension, and obtaining the organic amine catalyst after the ethanol is completely volatilized.
Example 4
The organic amine catalyst comprises activated carbon and polyethyleneimine loaded on the activated carbon, wherein the loading amount of the polyethyleneimine is 20%.
The preparation method of the organic amine catalyst comprises the following steps:
(1) Dissolving 20g of polyethyleneimine in 150g of ethanol, heating to 50 ℃, adding 80g of activated carbon under the condition of stirring, and continuously stirring for 3 hours at the same time to obtain a suspension;
(2) And raising the temperature to 85 ℃, continuously stirring and steaming to remove the ethanol in the suspension, and obtaining the organic amine catalyst after the ethanol is completely volatilized.
Example 5
The organic amine catalyst comprises activated carbon and polyethyleneimine loaded on the activated carbon, wherein the loading amount of the polyethyleneimine is 30%.
The preparation method of the organic amine catalyst comprises the following steps:
(1) Dissolving 30g of polyethyleneimine in 150g of ethanol, heating to 50 ℃, adding 70g of activated carbon under the condition of stirring, and continuously stirring for 3 hours at the same time to obtain a suspension;
(2) And raising the temperature to 85 ℃, continuously stirring and steaming to remove the ethanol in the suspension, and obtaining the organic amine catalyst after the ethanol is completely volatilized.
Example 6
The organic amine catalyst comprises diatomite and diethylenetriamine loaded on the diatomite, wherein the loading amount of the diethylenetriamine is 5%.
The preparation method of the organic amine catalyst comprises the following steps:
(1) Dissolving 5g of diethylenetriamine in 50g of methanol, heating to 50 ℃, adding 95g of diatomite while stirring, and continuously stirring for 3 hours at the same time to obtain a suspension;
(2) And raising the temperature to 85 ℃, continuously stirring and steaming to remove the methanol in the suspension, and obtaining the organic amine catalyst after the methanol is completely volatilized.
Example 7
The organic amine catalyst comprises hydrotalcite and tetraethylenepentamine loaded on the hydrotalcite, and the loading amount of the tetraethylenepentamine is 10%.
The preparation method of the organic amine catalyst comprises the following steps:
(1) Dissolving 10g of diethylenetriamine in 100g of acetone, heating to 50 ℃, adding 90g of hydrotalcite under the stirring condition, and continuously stirring for 3 hours under the heat preservation condition to obtain a suspension;
(2) And raising the temperature to 85 ℃, continuously stirring and steaming to remove the acetone in the suspension, and obtaining the organic amine catalyst after the acetone is completely volatilized.
Example 8
The preparation method of the diquat dichloride comprises the following steps:
(1) Grinding the organic amine catalyst in the embodiment 1 to a particle size of 500 meshes, then weighing 1g of the ground organic amine catalyst, putting the organic amine catalyst into a high-pressure reaction kettle, then adding 10g of 2,2' -bipyridine and 6.3g of dichloroethane, filling nitrogen as protective gas, maintaining the reaction pressure at 2.5MPa and the reaction temperature at 200 ℃, and reacting for 6 hours under the condition that the dichloroethane can be maintained in a liquid state;
(2) After the reaction is finished, after the reaction kettle is cooled to room temperature, adding a proper amount of deionized water into the reaction kettle, stirring for 30min, filtering, separating an organic phase of the filtrate for reuse as a raw material, separating a water phase of the filtrate to obtain a diquat dichloride solution, and evaporating the diquat dichloride solution to dryness of the solvent to obtain a diquat dichloride solid.
Example 9
The difference from example 8 in the preparation method of diquat dichloride salt is that the catalyst of this example is the organic amine catalyst of example 2.
Example 10
The difference between the preparation method of the diquat dichloride and the preparation method of the example 8 is that the catalyst of the example is the organic amine catalyst in the example 3.
Example 11
The difference from example 8 in the preparation method of diquat dichloride salt is that the catalyst of this example is the organic amine catalyst of example 4.
Example 12
The difference from example 8 in the preparation method of diquat dichloride salt is that the catalyst of this example is the organic amine catalyst in example 5.
The yield of diquat dichloride salt in examples 8-12 was calculated as shown in Table 1.
TABLE 1 yield of diquat dichloride salt in examples 8-12
As can be seen from table 1: in a given load range of the chain organic amine, the higher the load of the chain organic amine in the organic amine catalyst is, the higher the yield of the diquat dichloride is when the diquat dichloride is catalyzed to be synthesized. When the loading amount of the organic amine exceeds the above-mentioned limit range, a large amount of free amine is caused, which is unfavorable for recycling.
Example 13
The preparation method of the diquat dichloride comprises the following steps:
(1) Grinding the organic amine catalyst in the embodiment 2 to a particle size of 450 meshes, then weighing 1g of the ground organic amine catalyst, putting the organic amine catalyst into a high-pressure reaction kettle, then adding 10g of 2,2' -bipyridyl and 6.3g of dichloroethane, and filling nitrogen as a protective gas, wherein the reaction pressure is maintained at 2.5MPa, the reaction temperature is 200 ℃, and the reaction time is 6 hours;
(2) After the reaction is finished, after the reaction kettle is cooled to room temperature, adding a proper amount of deionized water into the reaction kettle, stirring for 30min, filtering, separating an organic phase of the filtrate for reuse as a raw material, separating a water phase of the filtrate to obtain a diquat dichloride solution, and evaporating the diquat dichloride solution to dryness of the solvent to obtain a diquat dichloride solid.
Example 14
The difference from example 13 in the preparation method of diquat dichloride, the particle size of the organic amine catalyst in this example is 400 meshes.
Example 15
The difference from example 13 in the preparation method of diquat dichloride salt is that the particle size of the organic amine catalyst in this example is 300 meshes.
Example 16
The difference from example 13 in the preparation method of diquat dichloride, the particle size of the organic amine catalyst in this example is 200 meshes.
The yield of diquat dichloride salt in examples 13-16 was calculated as shown in table 2.
TABLE 2 yield of diquat dichloride salt in examples 9, 13-16
As can be seen from table 2: within a given particle size range, the yield of the diquat dichloride increases and then decreases with the increase of the particle size of the organic amine catalyst, and the yield of the diquat dichloride is optimal when the particle size is 300 meshes.
Example 17
The preparation method of the diquat dichloride comprises the following steps:
(1) Grinding the organic amine catalyst in the embodiment 2 to the particle size of 450 meshes, then weighing 1g of the ground organic amine catalyst, putting the organic amine catalyst into a high-pressure reaction kettle, then adding 10g of 2,2' -bipyridine and 6.3g of dichloroethane, filling nitrogen as protective gas, maintaining the reaction pressure at 2.5MPa, the reaction temperature at 250 ℃ and the reaction time at 6h;
(2) After the reaction is finished, after the reaction kettle is cooled to room temperature, adding a proper amount of deionized water into the reaction kettle, stirring for 30min, filtering, separating an organic phase of the filtrate for reuse as a raw material, separating a water phase of the filtrate to obtain a diquat dichloride solution, and evaporating the diquat dichloride solution to dryness of the solvent to obtain a diquat dichloride solid.
Example 18
The preparation method of the diquat dichloride comprises the following steps:
(1) Grinding the organic amine catalyst in the embodiment 2 to the particle size of 450 meshes, then weighing 1g of the ground organic amine catalyst, putting the organic amine catalyst into a high-pressure reaction kettle, then adding 10g of 2,2' -bipyridine and 6.3g of dichloroethane, filling nitrogen as protective gas, maintaining the reaction pressure at 2.5MPa, the reaction temperature at 250 ℃ and the reaction time at 8h;
(2) After the reaction is finished, after the reaction kettle is cooled to room temperature, adding a proper amount of deionized water into the reaction kettle, stirring for 30min, filtering, separating an organic phase of the filtrate for reuse as a raw material, separating a water phase of the filtrate to obtain a diquat dichloride solution, and evaporating the diquat dichloride solution to dryness of the solvent to obtain a diquat dichloride solid.
Comparative example 1
The difference from example 17 in the preparation of diquat dichloride salt is that the reaction temperature is 150 ℃.
Comparative example 2
The difference from example 17 in the preparation of diquat dichloride salt is that the reaction temperature is 120 ℃.
Comparative example 3
The difference from example 18 in the preparation method of diquat dichloride is that the reaction time in this example is 5h.
Comparative example 4
The difference between the preparation method of the diquat dichloride and the preparation method of the example 18 is that the reaction time in the example is 3 hours.
The yield of diquat dichloride in examples 17-18 and comparative examples 1-4 was calculated and the results are shown in table 5.
TABLE 5 yield of diquat dichloride in examples 17-18 and comparative examples 1-4
As can be seen from table 5: as can be seen by comparing example 17 with comparative examples 1-2, when the reaction temperature does not exceed 150 ℃, the yield of diquat dichloride is significantly reduced because the temperature below 150 ℃ does not reach the activation temperature of the catalyst, thereby resulting in a significant reduction in yield; as can be seen by comparing example 18 with comparative examples 3 to 4, the yield of diquat dichloride was also significantly reduced when the reaction time did not exceed 5 hours.
It should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications belong to the protection scope of the present invention.
Claims (10)
1. The organic amine catalyst is characterized by comprising a carrier and chain organic amine loaded on the carrier, wherein the loading amount of the chain organic amine is 2-30%.
2. The organic amine catalyst according to claim 1, wherein the carrier is one of activated carbon, diatomaceous earth, and hydrotalcite.
3. The organic amine catalyst according to claim 1, wherein the chain organic amine is one or more selected from the group consisting of polyethyleneimine, triethylenediamine, hexamethyleneimine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.
4. A method for preparing an organic amine catalyst as claimed in any one of claims 1 to 3, wherein the organic amine catalyst is obtained by dissolving a chain organic amine in an organic solvent, adding the carrier while stirring, continuing stirring until a suspension is obtained, and then evaporating the organic solvent of the suspension.
5. The method for preparing the organic amine catalyst according to claim 4, wherein the mass ratio of the chain organic amine to the organic solvent is 1 to 2-10, and the organic solvent is one or more selected from methanol, ethanol, propanol, acetone and isopropanol.
6. The method for preparing organic amine catalyst according to claim 4, wherein the organic solvent is distilled off from the suspension at a temperature of 85 ℃ or higher until the organic solvent is completely volatilized.
7. A process for preparing diquat dichloride, characterized in that 2,2' -bipyridine and 1, 2-dibromoethane are used as raw materials, and the diquat dichloride is synthesized by the catalytic reaction of the organic amine catalyst according to any one of claims 1 to 3.
8. The method for preparing diquat dichloride according to claim 7, wherein nitrogen is filled in the reaction as a protective gas, the reaction pressure is controlled to be 0.5-3MPa, the reaction temperature is controlled to be 150-250 ℃, and the reaction time is 5-8h.
9. The method for producing diquat dichloride according to claim 7, wherein the molar ratio of the 2,2' -bipyridine to the 1, 2-dibromoethane is 1.
10. The method of claim 7, wherein the organic amine catalyst has a particle size of 200-500 mesh.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116984027A (en) * | 2023-08-02 | 2023-11-03 | 江苏诺恩作物科学股份有限公司 | Transition metal doped molecular sieve@organic amine catalyst and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116984027A (en) * | 2023-08-02 | 2023-11-03 | 江苏诺恩作物科学股份有限公司 | Transition metal doped molecular sieve@organic amine catalyst and preparation method and application thereof |
| CN116984027B (en) * | 2023-08-02 | 2024-03-12 | 江苏诺恩作物科学股份有限公司 | Transition metal doped molecular sieve@organic amine catalyst and preparation method and application thereof |
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Application publication date: 20230203 |