CN117983270B - A catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application. - Google Patents
A catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application.Info
- Publication number
- CN117983270B CN117983270B CN202211361805.XA CN202211361805A CN117983270B CN 117983270 B CN117983270 B CN 117983270B CN 202211361805 A CN202211361805 A CN 202211361805A CN 117983270 B CN117983270 B CN 117983270B
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- butanediol
- hydroxybutyraldehyde
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本申请公开了一种用于4‑羟基丁醛加氢制备1,4‑丁二醇的催化剂及其制备方法和应用，采用金属和酸配位法得到3DOM氧化镍，后采用氨化法将部分3DOM氧化镍转化成氮化镍，得到所述3DOM氮化镍/氧化镍催化剂。本申请还公开了使用所述催化剂进行4‑羟基丁醛加氢反应制备1,4‑丁二醇的方法。This application discloses a catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method, and its application. 3DOM nickel oxide is obtained using a metal-acid coordination method, followed by a partial conversion of the 3DOM nickel oxide to nickel nitride using an ammoniation method, resulting in the 3DOM nickel nitride/nickel oxide catalyst. This application also discloses a method for using the catalyst to perform the hydrogenation reaction of 4-hydroxybutyraldehyde to prepare 1,4-butanediol.
Description
Technical Field
The application relates to a catalyst for preparing 1, 4-butanediol by 4-hydroxybutanal hydrogenation, and a preparation method and application thereof, and belongs to the field of chemical industry.
Background
1,4 Butanediol (BDO for short) is an important organic and fine chemical raw material, and is widely applied to the fields of medicine, chemical industry, textile, papermaking, automobiles, daily chemical industry and the like. Tetrahydrofuran (THF), polybutylene terephthalate (PBT), gamma Butyl Lactone (GBL), polyurethane Resin (PU Resin), paint, plasticizer, etc. can be produced from 1,4 butanediol, and as a solvent, a brightening agent for the electroplating industry, etc.
Prior to the second world war, germany had adopted Lei Peifa to synthesize 1, 4-butanediol from acetylene and formaldehyde. The method solves the problem that more processes are researched at present, and the acetylene is dangerous to operate under high pressure, so far, the method is still the most main production method of the 1, 4-butanediol. In the 60 s, mitsubishi oil company of japan developed a process for preparing 1,4 butanediol by catalytic hydrogenation of maleic anhydride, and in the 70 s, developed a new process for the acetoxylation of butadiene. In 1971, the industrial company of Toyoda, japan established a production facility for the butadiene chlorination process. In addition, various synthesis methods using propylene or ethylene as a raw material have been studied successively in the united states and japan.
1,4 Butanediol is a chemical product with higher added value. In the existing industrial production, the propylene method route developed by Coleus company (GB 1493154A, US 4465873A) is mainly used in the present process and mainly comprises the steps of Liande (LYONDELL) (CN 101084175B, WO2006068680A1, US2002111520A 1) and Taiwan Dalian chemical company (US 5426250A, TW 432037B), and the method has the advantages of small investment, low energy consumption, flexible capacity adjustment and the like. However, this route typically forms 2 methyl 3 hydroxy propanal (MPA) during the carbonylation of allyl alcohol, which is subsequently hydrogenated to 2 methyl 1,3 propanediol. Therefore, the propylene method is adopted to synthesize the 1,4 butanediol, and the byproduct 2 methyl 1,3 propanediol is generated, so that the 2 methyl 1,3 propanediol has fewer applications and limited demand compared with the 1,4 butanediol product. Therefore, due to the existence of the byproduct 2 methyl 1,3 propylene glycol in the production process, the scale and the efficiency of the propylene process route are greatly limited, and the economy of synthesizing the 1,4 butanediol by the propylene process route is reduced.
Disclosure of Invention
The catalyst prepared in the patent is applied to the reaction of preparing 1, 4-butanediol by hydrogenation, and has good catalyst activity, high 4-hydroxybutyraldehyde conversion rate and 1, 4-butanediol selectivity and good stability.
According to one aspect of the present application, there is provided a catalyst for the hydrogenation of 4-hydroxybutyraldehyde to produce 1, 4-butanediol, which is capable of improving the 4-hydroxybutyraldehyde conversion and 1, 4-butanediol selectivity;
the catalyst comprises an active component and a carrier;
The active component is nickel nitride;
The carrier is three-dimensional ordered macroporous (3 DOM for short) nickel oxide.
According to another aspect of the present application, there is provided a method for preparing the catalyst for preparing 1, 4-butanediol by hydrogenating 4-hydroxybutyraldehyde, comprising the steps of:
The catalyst is prepared by a metal and acid coordination method:
And 3DOM nickel oxide is obtained, and the 3DOM nickel oxide is nitrided to obtain the catalyst.
The process for obtaining the 3DOM nickel oxide comprises the following steps:
mixing raw materials containing a nickel source, citric acid and a solvent to obtain a mixed solution, immersing polystyrene spheres in the mixed solution, drying and calcining to obtain the 3DOM nickel oxide.
The method comprises mixing citric acid and nickel source in solvent to obtain solution A, placing polystyrene spheres in a vacuum container, vacuumizing, dropping solution A onto polystyrene spheres with Buchner funnel to submerge, drying, and repeating for several times;
the nickel source is at least one selected from nickel nitrate, nickel sulfate and nickel acetate;
the solvent is selected from water and/or ethanol;
The mass ratio of the citric acid to the nickel source is 1 (1-3);
Optionally, the mass ratio of the citric acid to the nickel source is any value or a range of values between any two of 1:1, 1:2, 1:3.
The ratio of the total mass of the citric acid and the nickel source to the volume of the solvent is 1 (2-4) g/ml;
Optionally, the ratio of the total mass of the citric acid to the nickel source to the volume of the solvent is any value or range between any two values of 1:2, 1:3, 1:4.
The solid-liquid ratio of the polystyrene spheres to the mixed solution is 1 (50-70) g/ml.
Optionally, the solid-to-liquid ratio of the polystyrene spheres to the mixed solution is any value or a range of values between any two of 1:50g/ml, 1:60g/ml, 1:70 g/ml.
The drying temperature is 50-80 ℃;
optionally, the temperature of the drying is any value or range of values between any two of 50 ℃, 60 ℃, 70 ℃, 80 ℃.
The drying time is 1-3 hours;
Optionally, the drying time is any value or a range of values between any two of 1h, 2h, 3h.
The calcining temperature is 450-650 ℃;
Optionally, the temperature of the calcination is any value or range of values between any two of 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃.
The calcination time is 1-6 h.
Optionally, the calcination time is any value or range of values between any two of 1h, 2h, 3h, 4h, 5h, 6 h.
The nitriding atmosphere is an ammonia atmosphere;
the nitriding temperature is 300-350 ℃;
Optionally, the nitriding temperature is any value or range of values between any two of 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃.
The nitriding time is 1-3 h.
Optionally, the nitriding time is any value or range of values between any two of 1h, 2h, 3h.
According to another aspect of the present application, there is provided a method for preparing 1, 4-butanediol by hydrogenating 4-hydroxybutyraldehyde, comprising the steps of:
Introducing a raw material containing hydrogen and 4-hydroxybutanal solution into a reactor, and carrying out contact reaction on the raw material and a catalyst to obtain a product containing 1, 4-butanediol;
the catalyst is selected from the catalysts described above or the catalysts prepared by the preparation method described above.
The reactor is a fixed bed reactor.
The mass fraction of the 4-hydroxybutyraldehyde solution is 20-50wt%;
Optionally, the mass fraction of the 4-hydroxybutyraldehyde solution is any value or range of values between any two of 20wt%, 30wt%, 40wt%, 50 wt%.
The mass airspeed of the 4-hydroxybutyraldehyde solution is 2-4 h -1;
Optionally, the mass space velocity of the 4-hydroxybutyraldehyde solution is any value or a range of values between any two of 2h -1、3h-1、4h-1.
And the mass airspeed of the hydrogen is 80-120 h -1.
Optionally, the mass space velocity of the hydrogen is any value or a range of values between any two of 80h -1、90h-1、100h-1、110h-1、120h-1.
The reaction temperature is 70-180 ℃;
Alternatively, the temperature of the reaction is any value or range of values between any two of 70 ℃,80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃.
The reaction time is 1-4 hours;
alternatively, the reaction time is any value or range of values between any two of 1h, 2h, 3h, 4h.
The pressure of the reaction is 1-11 MPa.
Alternatively, the pressure of the reaction is any value or range of values between any two of 1MPa, 2MPa, 3MPa, 4MPa, 5MPa, 6MPa, 7MPa, 8MPa, 9MPa, 10MPa, 11 MPa.
The application has the beneficial effects that:
1) The catalyst provided by the application can be applied to the reaction of preparing 1, 4-butanediol by 4-hydroxybutyraldehyde hydrogenation, and can improve the conversion rate of 4-hydroxybutyraldehyde and the selectivity of the generated 1, 4-butanediol.
2) The preparation method of the catalyst provided by the application is stable, controllable and good in reproducibility.
3) The method for preparing the 1, 4-butanediol by 4-hydroxybutyraldehyde hydrogenation provided by the application adopts the catalyst provided by the application, has high reaction speed and high yield, and can be applied to large-scale production.
Drawings
FIG. 1 Scanning Electron Microscope (SEM) (JSM-7800F) was used to perform morphology testing on catalyst 1 # DOM nickel nitride/nickel oxide catalyst.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, unless otherwise specified. Wherein the gas chromatograph is 7890B type gas chromatograph of Agilent company.
Example 1
Preparation of the catalyst
Taking the serial number 1 in the table 1 as an example, mixing citric acid and nickel nitrate hexahydrate with the mass ratio of 1:2 in deionized water to form a solution A (the total mass of the citric acid and the nickel source and the volume of the solvent are 1:2 g/ml), placing the polystyrene spheres and the mixed solution in a vacuum container for vacuumizing, dropwise adding the solution A onto the polystyrene spheres by using a Buchner funnel to submerge the polystyrene spheres, drying at 70 ℃ for 2 hours, repeating the steps for several times, and calcining at 550 ℃ for 3 hours in a calciner to obtain the 3DOM nickel oxide. And nitriding the 3DOM nickel oxide in an ammonia gas atmosphere at 325 ℃ for 2 hours to obtain the 3DOM nickel nitride/nickel oxide catalyst. Denoted catalyst 1#.
The types, the amounts and the reaction parameters of the raw materials were adjusted according to the following steps to obtain a series of 3DOM nickel nitride/nickel oxide catalysts with the serial numbers of 1 to 28, which were designated as hierarchical pore molecular sieves 1 to 28, as shown in the following Table 1:
TABLE 1
The columns in Table 1 above are described as follows:
Nickel source is nickel nitrate hexahydrate (Ni 1), nickel sulfate hexahydrate (Ni 2), nickel acetate tetrahydrate (Ni 3).
Solvent deionized water (solution 1), ethanol (solution 2), ethanol and deionized water mixed solution (solution 3).
The conversion and selectivity in the examples of the present application were calculated as follows (with 4-hydroxybutyraldehyde conversion as an evaluation index):
Conversion of 4-hydroxybutyraldehyde= (initial carbon number of 4-hydroxybutyraldehyde-carbon number of 4-hydroxybutyraldehyde in product) ×100/initial mole number of 4-hydroxybutyraldehyde
1, 4-Butanediol selectivity = carbon number of 1, 4-butanediol 100/Σ (carbon number of 1, 4-butanediol + carbon number of other products)
Example 2
The catalyst is used for hydrogenation reaction for preparing 1, 4-butanediol.
The catalyst 1 # to catalyst 28 # with the serial numbers of 1 to 28 prepared in the embodiment 1 is used for preparing 1, 4-butanediol by hydrogenation, the catalyst is filled in a fixed bed reactor, H 2 and raw materials are introduced, the mass fraction of a raw material 4-hydroxybutanal aqueous solution is 40wt%, the reaction temperature is 100 ℃, the reaction time is 2H, the mass space velocity of the raw materials is 3H -1,H2, the mass space velocity is 100H -1, the reaction pressure is 8Mpa, and the 1, 4-butanediol is produced by hydrogenation.
After the reaction is stable (i.e. when the reaction profile data is not abnormal), the reaction raw materials and the products are all analyzed by utilizing gas online chromatography. The reaction results are shown in Table 3.
TABLE 2
It can be seen from the table that the catalysts prepared were used for hydrogenation reactions, the reaction conversion and selectivity did not differ significantly.
Example 3
The catalyst 1 # prepared in Table 2 was used for hydrogenation to prepare 1, 4-butanediol, the reaction parameters were changed, and after the reaction was stable (i.e. when the data of the reaction profile was not abnormal), the reaction raw materials and the products were analyzed by gas online chromatography. The reaction results are shown in Table 4.
TABLE 3 Table 3
It can be seen from the table that the reaction temperature and reaction pressure have a large influence on the reaction conversion.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (8)
1.A method for preparing 1, 4-butanediol by 4-hydroxybutanal hydrogenation is characterized in that,
The method comprises the following steps:
Introducing a raw material containing hydrogen and 4-hydroxybutanal solution into a reactor, and carrying out contact reaction on the raw material and a catalyst to obtain a product containing 1, 4-butanediol;
the reaction temperature is 70-150 ℃;
the pressure of the reaction is 1-10 MPa;
the mass fraction of the 4-hydroxybutyraldehyde solution is 20-50wt%;
the catalyst comprises an active component and a carrier;
The active component is nickel nitride;
the carrier is three-dimensional ordered macroporous nickel oxide;
The preparation method of the catalyst comprises the following steps:
and (3) obtaining three-dimensional ordered macroporous nickel oxide, and nitriding the three-dimensional ordered macroporous nickel oxide to obtain the catalyst.
2. A process for the hydrogenation of 4-hydroxybutyraldehyde to produce 1, 4-butanediol as claimed in claim 1,
The process for obtaining the three-dimensional ordered macroporous nickel oxide comprises the following steps:
mixing raw materials containing a nickel source, citric acid and a solvent to obtain a mixed solution, immersing polystyrene spheres in the mixed solution, drying and calcining to obtain the three-dimensional ordered macroporous nickel oxide.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
The nickel source is at least one selected from nickel nitrate, nickel sulfate and nickel acetate;
the solvent is selected from water and/or ethanol;
The mass ratio of the citric acid to the nickel source is 1 (1-3);
The ratio of the total mass of the citric acid and the nickel source to the volume of the solvent is 1 (2-4) g/ml;
The solid-liquid ratio of the polystyrene spheres to the mixed solution is 1 (50-70) g/ml.
4. The method of claim 2, wherein the step of determining the position of the substrate comprises,
The drying temperature is 50-80 ℃;
the drying time is 1-3 hours;
the calcining temperature is 450-650 ℃;
The calcination time is 1-6 h.
5. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The nitriding atmosphere is an ammonia atmosphere;
the nitriding temperature is 300-350 ℃;
The nitriding time is 1-3 h.
6. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The reactor is a fixed bed reactor.
7. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The mass airspeed of the 4-hydroxybutyraldehyde solution is 2-4 h -1;
And the mass airspeed of the hydrogen is 80-120 h -1.
8. The method of claim 1, wherein the step of determining the position of the substrate comprises,
The reaction time is 1-4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211361805.XA CN117983270B (en) | 2022-11-02 | 2022-11-02 | A catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211361805.XA CN117983270B (en) | 2022-11-02 | 2022-11-02 | A catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117983270A CN117983270A (en) | 2024-05-07 |
| CN117983270B true CN117983270B (en) | 2025-11-14 |
Family
ID=90889486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211361805.XA Active CN117983270B (en) | 2022-11-02 | 2022-11-02 | A catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application. |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117983270B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087595A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Method for preparing alcohol compound by hydrogenation of carbonyl-containing compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014034004A1 (en) * | 2012-08-27 | 2014-03-06 | パナソニック株式会社 | Photochemical electrode for carbon dioxide reduction and method for reducing carbon dioxide using photochemical electrode for carbon dioxide reduction |
| CN107970940A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | Nickel system hydroxy pivalin aldehyde Hydrogenation for neopentyl glycol catalyst and preparation method |
-
2022
- 2022-11-02 CN CN202211361805.XA patent/CN117983270B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113087595A (en) * | 2020-01-08 | 2021-07-09 | 万华化学集团股份有限公司 | Method for preparing alcohol compound by hydrogenation of carbonyl-containing compound |
Non-Patent Citations (2)
| Title |
|---|
| A mesoporous Ni3N/NiO composite with a core–shell structure for room temperature, selective and sensitive NO2 gas sensing;Mingming Zou等;《RSC Adv.》;20160425;第6卷;第42917–42922页 * |
| Mingming Zou等.A mesoporous Ni3N/NiO composite with a core–shell structure for room temperature, selective and sensitive NO2 gas sensing.《RSC Adv.》.2016,第6卷第42917–42922页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117983270A (en) | 2024-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114433100B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic anhydride by maleic anhydride hydrogenation | |
| EP0319116B1 (en) | Hydrogenation catalyst | |
| CN107721821B (en) | Method for preparing 1, 3-propylene glycol | |
| EP0404408A1 (en) | Use of coated catalysts for the hydrogenation of maleic anhydride to tetrahydrofuran and gammabutyrolactone | |
| CN105363438B (en) | Synthesizing of glycolate ester catalyst, preparation method and its usage | |
| CN114702434A (en) | Continuous synthesis method of tetramethyl piperidinol | |
| JPH06501875A (en) | Hydrogenation catalyst and method for producing tetrahydrofuran | |
| CN106423284A (en) | Vinyl acetate catalyst and preparing method thereof | |
| CN117983270B (en) | A catalyst for the hydrogenation of 4-hydroxybutyraldehyde to 1,4-butanediol, its preparation method and application. | |
| CN108144618B (en) | Hydrogenation catalyst, preparation method and application thereof | |
| CN104974045B (en) | A kind of method for preparing aminated compounds | |
| KR20010095500A (en) | Preparation method of gamma butyrolactone using maleic anhydride | |
| CN116768700A (en) | Method for preparing 1, 4-butanediol by maleic anhydride hydrogenation | |
| CN102600847B (en) | Catalyst for use in synthesis of methyl formate and preparation method and application thereof | |
| CN112742432B (en) | Method for preparing gamma-butyrolactone by maleic anhydride hydrogenation | |
| TWI471296B (en) | A heterogeneous catalyst and a method of producing 1,4-butanediol, γ-butyrolactone and tetrahydrofuran | |
| CN112536041B (en) | Catalyst for preparing methyl isobutyl carbinol and preparation method thereof | |
| CN110862302A (en) | Method for preparing 1, 4-butanediol by combining slurry bed hydrogenation and fixed bed hydrogenation | |
| CN116139899B (en) | Catalyst, preparation method thereof and application of catalyst in preparation of 1, 3-butanediol by hydrogenation | |
| CN116139864B (en) | Catalyst, preparation method thereof and application of catalyst in preparation of 1, 3-butanediol by hydrogenation of 3-hydroxybutyraldehyde | |
| CN112717940B (en) | Catalyst for preparing gamma-butyrolactone, and preparation method and application thereof | |
| CN108409517B (en) | Method for preparing isobutene by catalytic cracking of methyl tert-butyl ether | |
| CN118022793B (en) | Cobalt-based catalyst and preparation method and application thereof | |
| CN109647472B (en) | Hydrogenation catalyst, preparation method thereof and preparation method of tetrahydrofurfuryl alcohol | |
| CN109647429B (en) | Hydrogenation catalyst, preparation method thereof and preparation method of tetrahydrofurfuryl alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |