CN113134362B - Heterogeneous catalyst for preparing lactaldehyde by non-ligand hydroformylation of acetaldehyde and synthesis gas and preparation method and application thereof - Google Patents
Heterogeneous catalyst for preparing lactaldehyde by non-ligand hydroformylation of acetaldehyde and synthesis gas and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas, which comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 0.1-5 parts of rhodium, 0-2 parts of ruthenium, 0-5 parts of cobalt and 0-2 parts of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.1-1 part of zinc and 0-0.8 part of cesium, and the balance of the auxiliary catalyst is the active coordination carrier; the active coordination carrier is prepared by modifying any one of active carbon, silicon dioxide, graphene, carbon nano tube and aluminum oxide through hydroxyl. Meanwhile, a preparation method and application of the catalyst are disclosed. When the catalyst is used for preparing the lactaldehyde, the reaction condition is mild, the production cost is low, the loss rate of the catalyst is low, the catalyst is green and environment-friendly, the conversion rate of raw materials is high, and the selectivity of products is high.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a heterogeneous catalyst for preparing lactaldehyde by ligand-free hydroformylation of acetaldehyde and synthesis gas, and a preparation method and application thereof.
Background
Lactaldehyde, also known as 2-hydroxypropanal, alpha-hydroxypropanal or propanolaldehyde. Mainly used for further oxidation or dehydrogenation to obtain lactic acid. Polylactic acid (PLA) is a novel polyester material produced from an organic acid lactic acid as a raw material, and has: good biodegradability, good mechanical property and physical property, good compatibility and degradability, and the like. The novel packaging material is defined by the industry as a novel packaging material with development prospect in the new century, is expected to replace materials such as polyethylene, polypropylene, polystyrene and the like to be used for plastic products in the future, and has wide application prospect.
The method for synthesizing lactaldehyde and lactic acid at home and abroad mainly comprises a fermentation method, a lactonitrile synthesis method, an acrylonitrile method, an acrylic acid method and the like. The fermentation method uses starch raw materials such as corn, rice, sweet potato and the like, and has the problems of high cost, low yield, large three-waste emission and the like; the lactonitrile method is that acetaldehyde and cold hydrocyanic acid are continuously fed into a reactor to generate lactonitrile, the lactonitrile is pumped into a hydrolysis kettle by a pump, sulfuric acid and water are injected to hydrolyze the lactonitrile to obtain crude lactic acid, then the crude lactic acid is fed into an esterification kettle, ethanol is added to esterify, and refined lactic acid is obtained after rectification, concentration and decomposition; has the problems of long process flow, use of highly toxic raw materials and the like; the acrylonitrile method and the propionic acid method have the defects of high raw material price, difficult product separation and purification and the like. Therefore, the search for cheap raw materials for synthesizing lactic acid and a novel pollution-free synthesis process technology are the key points for promoting the application development of lactic acid and polylactic acid.
The development of modern coal chemical industry provides a large amount of cheap synthesis gas resource, ethanol prepared by taking the synthesis gas as a raw material is further dehydrogenated to obtain cheap acetaldehyde, and if the acetaldehyde can be efficiently reacted with CO and H under mild conditions 2 The reaction directionally generates the lactaldehyde and oxidizes the lactaldehyde to prepare the lactic acid, so that the method becomes a new way for converting coal chemical resources into biodegradable materials to be utilized, and also becomes a green preparation process of the coal-to-lactic acid with the most economic value.
Hydroformylation catalysts were the earliest complex catalysts used in industrial production. With olefins and synthesis gas (CO + H) 2 ) In the presence of a catalyst to produce an aldehyde having one more carbon atom. For example, ethylene and propylene are used as raw materials to prepare propionaldehyde and butyraldehyde through hydroformylation (known as oxo synthesis). The hydroformylation process has been carried out in the liquid phase at high temperature and high pressure using cobalt carbonyl complexes as catalysts. In recent years, the carbonyl rhodium phosphine complex catalyst is used, the reaction pressure is reduced to 5MPa from the original 20MPa, the selectivity of normal aldehyde is improved, the energy is saved, and the cost is reduced. However, the main problems of the technology are that the catalyst uses a noble metal homogeneous catalysis system, a large amount of expensive and easily decomposed phosphorus ligands are used, and the loss of noble metal rhodium and the phosphorus ligands is serious, so that the process cost is high, the three wastes are discharged and amplified, and the environmental pollution is serious.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas and a preparation method thereof.
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 0.1-5 parts of rhodium, 0-2 parts of ruthenium, 0-5 parts of cobalt and 0-2 parts of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.1-1 part of zinc and 0-0.8 part of cesium, and the balance is the active coordination carrier; the active coordination carrier is prepared by modifying any one of active carbon, silicon dioxide, graphene, carbon nano tube and aluminum oxide through hydroxyl.
Preferably, the active coordination carrier is prepared by the following method: adding any one of active carbon, silicon dioxide, graphene, carbon nano tube and alumina into a solution containing hydroxyl, soaking for 24-48h under ultrasonic treatment for activation modification, filtering, and drying at 105-115 ℃ for 4-10h to obtain the active coordination carrier.
Preferably, the mass ratio of any one of the activated carbon, the silicon dioxide, the graphene, the carbon nano tube and the aluminum oxide to the solute in the solution containing the hydroxyl is 1 (5-10).
Preferably, the solution containing hydroxyl groups is an aqueous hydrogen peroxide solution or a peracetic acid solution.
Preferably, the mass concentration of the hydrogen peroxide solution is 2-30%; the mass concentration of the peroxyacetic acid solution is 1-5%.
The preparation method of the heterogeneous catalyst comprises the following steps:
(1) Preparing a main catalyst solution: according to the components of the main catalyst in the heterogeneous catalyst, taking sulfate or chloride of the main catalyst to prepare a sulfate solution or chloride solution with the total mass concentration of 5-10% to obtain a main catalyst solution;
(2) Preparing a cocatalyst solution: according to the components of the cocatalyst in the heterogeneous catalyst, taking sulfate or chloride of the cocatalyst to prepare a sulfate solution or chloride solution with the total mass concentration of 2-5% to obtain a cocatalyst solution;
(3) Preparing a catalyst by impregnation: mixing the main catalyst solution and the cocatalyst solution, adding the active coordination carrier, soaking for 24-48h, filtering, washing with deionized water, drying, grinding, sieving and granulating.
Preferably, the drying and drying conditions in step (3) are drying at 110-130 ℃ for 3-6h.
Preferably, the grinding and sieving in step (3) is 200 mesh sieving.
Use of the heterogeneous catalyst for the preparation of lactaldehyde.
Preferably, the application is specifically: filling a catalyst in a bubbling kettle type reactor, controlling the reaction temperature to be 80-120 ℃ and the reaction pressure to be 1-5MPa, mixing acetaldehyde or paraldehyde with synthesis gas to form a reaction raw material, and reacting for 2-10h according to the weight space velocity -1 Feeding the material through a catalyst bed layer; wherein the synthesis gas is CO and H 2 A mixture of (a); during the reaction, paraldehyde is decomposed into acetaldehyde to take part in the reaction.
Preferably, acetaldehyde, CO, H in the reaction system 2 In a molar ratio of 1: (5-10): (5-10).
The invention has the advantages that:
(1) When the catalyst provided by the invention is used for preparing lactaldehyde, synthesis gas and acetaldehyde generated by a cheap coal chemical device are used as raw materials, and the lactaldehyde can be prepared in one step through hydroformylation reaction, so that the process is simple, the reaction condition is mild, the problem that a virulent hydrocyanic acid raw material is used in the traditional lactaldehyde process is avoided, and the product cost is greatly reduced;
(2) When the catalyst is used for preparing lactaldehyde, an acetaldehyde hydroformylation process is adopted, a heterogeneous active coordination carrier loaded metal monoatomic catalysis technology is adopted, expensive and easily-decomposed homogeneous organic phosphorus ligands are not used, the loss of the catalyst is effectively avoided, the reaction cost is greatly reduced, the whole process has no three-waste discharge and zero process pollution, the discharge and treatment of a large amount of precious metal and high-toxicity organic ligand waste liquid in the traditional synthesis technology are avoided, and the zero emission of the environment is realized;
(3) When the catalyst is prepared, the carrier is an active coordination carrier prepared by hydroxyl modification, and because the surface of the active coordination carrier is rich in hydroxyl groups, the hydroxyl groups can be effectively coordinated with active metal particles, and a monoatomic dispersion center with catalytic activity is obtained. The catalytic process of preparing lactaldehyde by the hydroformylation of acetaldehyde with high activity, high conversion rate and high selectivity is realized, the conversion rate of the acetaldehyde is more than 80 percent, and the selectivity of the lactaldehyde is more than 90 percent.
Detailed Description
Example 1
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 5 parts of rhodium, 2 parts of ruthenium, 5 parts of cobalt and 2 parts of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.1 part of zinc and 0.1 part of cesium, and the balance of the auxiliary catalyst is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking activated carbon in 30% hydrogen peroxide solution, performing ultrasonic treatment for 24 hr for activation and modification, filtering, and drying at 105 deg.C for 10 hr; wherein the mass ratio of the activated carbon to hydrogen peroxide in the hydrogen peroxide solution is 1.
The preparation method of the heterogeneous catalyst comprises the following steps:
(1) Preparing a main catalyst solution: according to the components of the main catalyst in the heterogeneous catalyst, sulfate or chloride of the main catalyst is taken to prepare a sulfate solution or a chloride solution with the total mass concentration of 5 percent to obtain a main catalyst solution;
(2) Preparing a cocatalyst solution: according to the components of the cocatalyst in the heterogeneous catalyst, preparing a sulfate solution or a chloride solution with the total mass concentration of 5% from sulfate or chloride of the cocatalyst to obtain a cocatalyst solution;
(3) Preparing a catalyst by impregnation: mixing the main catalyst solution and the auxiliary catalyst solution, adding the active coordination carrier, soaking for 24h, filtering, washing with deionized water, drying at 120 ℃ for 4h, grinding, sieving with a 200-mesh sieve, and granulating.
Example 2
A heterogeneous catalyst for preparing lactaldehyde through ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 1 part of rhodium, 1 part of ruthenium, 1 part of cobalt and 1 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.5 part of zinc and 0.2 part of cesium, and the balance of the auxiliary catalyst is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking aluminum oxide in hydrogen peroxide solution with the mass concentration of 10%, soaking for 48 hours under ultrasonic treatment for activation and modification, filtering, and drying at 115 ℃ for 4 hours; wherein the mass ratio of the aluminum oxide to the hydrogen peroxide in the hydrogen peroxide solution is 1.
The preparation method of the heterogeneous catalyst comprises the following steps:
(1) Preparing a main catalyst solution: according to the components of the main catalyst in the heterogeneous catalyst, sulfate or chloride of the main catalyst is taken to prepare a sulfate solution or a chloride solution with the total mass concentration of 10 percent to obtain a main catalyst solution;
(2) Preparing a cocatalyst solution: according to the components of the cocatalyst in the heterogeneous catalyst, preparing a sulfate solution or a chloride solution with the total mass concentration of 2% from sulfate or chloride of the cocatalyst to obtain a cocatalyst solution;
(3) Preparing a catalyst by impregnation: mixing the main catalyst solution and the cocatalyst solution, adding the active coordination carrier, soaking for 48h, filtering, washing with deionized water, drying at 110 ℃ for 6h, grinding, sieving with a 200-mesh sieve, and granulating.
Example 3
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 4 parts of rhodium, 0 part of ruthenium, 1 part of cobalt and 0 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.2 part of zinc and 0.6 part of cesium, and the balance of the auxiliary catalyst is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking graphene in a hydrogen peroxide solution with the mass concentration of 20%, soaking for 36h under ultrasonic treatment for activation modification, filtering, and drying at 110 ℃ for 6h; the mass ratio of the graphene to hydrogen peroxide in the hydrogen peroxide solution is 1.
The preparation method of the heterogeneous catalyst comprises the following steps:
(1) Preparing a main catalyst solution: according to the components of the main catalyst in the heterogeneous catalyst, sulfate or chloride of the main catalyst is taken to prepare a sulfate solution or a chloride solution with the total mass concentration of 8% to obtain a main catalyst solution;
(2) Preparing a cocatalyst solution: according to the components of the cocatalyst in the heterogeneous catalyst, sulfate or chloride of the cocatalyst is taken to prepare a sulfate solution or chloride solution with the total mass concentration of 3%, so as to obtain a cocatalyst solution;
(3) Preparing a catalyst by impregnation: mixing the main catalyst solution and the cocatalyst solution, adding the active coordination carrier, soaking for 36h, filtering, washing with deionized water, drying at 130 ℃ for 3h, grinding, sieving with a 200-mesh sieve, and granulating.
Example 4
A heterogeneous catalyst for preparing lactaldehyde through ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 3 parts of rhodium, 0 part of ruthenium, 1 part of cobalt and 1 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.5 part of zinc and 0.1 part of cesium, and the balance of the auxiliary catalyst is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking a carbon nano tube in a hydrogen peroxide solution with the mass concentration of 20%, soaking for 24 hours under ultrasonic treatment for activation and modification, filtering, and drying for 10 hours at 105 ℃; wherein the mass ratio of the carbon nano tube to hydrogen peroxide in the hydrogen peroxide solution is 1.
The heterogeneous catalyst was prepared as in example 1.
Example 5
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 1 part of rhodium, 1 part of ruthenium, 2 parts of cobalt and 1 part of iridium according to the weight part of 100 of the catalyst, the auxiliary catalyst comprises 0.4 part of zinc and 0.4 part of cesium, and the balance of the auxiliary catalyst is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking the carbon nano tube in a peroxyacetic acid solution with the mass concentration of 5%, soaking for 24 hours under ultrasonic treatment for activation modification, filtering, and drying at 105 ℃ for 10 hours; wherein the mass ratio of the carbon nano tube to the peroxyacetic acid in the peroxyacetic acid solution is 1.
The heterogeneous catalyst was prepared as described in example 1.
Example 6
A heterogeneous catalyst for preparing lactaldehyde through ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 4 parts of rhodium, 0 part of ruthenium, 2 parts of cobalt and 0 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.1 part of zinc and 0.7 part of cesium, and the balance is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking activated carbon in 5% peracetic acid solution, performing ultrasonic treatment, soaking for 24h for activation modification, filtering, and drying at 105 deg.C for 10h; wherein the mass ratio of the activated carbon to the peroxyacetic acid in the peroxyacetic acid solution is 1.
The heterogeneous catalyst was prepared as in example 1.
Example 7
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 5 parts of rhodium, 0 part of ruthenium, 0 part of cobalt and 0 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.1 part of zinc and 0.8 part of cesium, and the balance of the auxiliary catalyst is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking graphene in a peroxyacetic acid solution with the mass concentration of 5%, soaking for 24 hours under ultrasonic treatment for activation and modification, filtering, and drying at 105 ℃ for 10 hours; wherein the mass ratio of the graphene to the peroxyacetic acid in the peroxyacetic acid solution is 1.
The heterogeneous catalyst was prepared as described in example 1.
Example 8
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 0.5 part of rhodium, 1 part of ruthenium, 1 part of cobalt and 0.1 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.2 part of zinc and 0.4 part of cesium, and the balance is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking activated carbon in hydrogen peroxide solution with the mass concentration of 10%, soaking for 24h under ultrasonic treatment for activation modification, filtering, and drying at 105 ℃ for 10h; wherein the mass ratio of the activated carbon to hydrogen peroxide in the hydrogen peroxide solution is 1.
The heterogeneous catalyst was prepared as in example 1.
Example 9
A heterogeneous catalyst for preparing lactaldehyde through ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 0.2 part of rhodium, 0.1 part of ruthenium, 1 part of cobalt and 0.2 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.2 part of zinc and 0.4 part of cesium, and the balance is the active coordination carrier; the active coordination carrier is prepared by the following method: soaking activated carbon in hydrogen peroxide solution with the mass concentration of 10%, soaking for 24h under ultrasonic treatment for activation modification, filtering, and drying at 105 ℃ for 10h; wherein the mass ratio of the activated carbon to hydrogen peroxide in the hydrogen peroxide solution is 1.
The heterogeneous catalyst was prepared as described in example 1.
Example 10
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 0.2 part of rhodium, 0.5 part of ruthenium, 0.2 part of cobalt and 0.1 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.2 part of zinc and 0.4 part of cesium, and the balance of the active coordination carrier; the active coordination carrier is prepared by the following method: soaking silicon dioxide in 2% hydrogen peroxide solution, performing ultrasonic treatment for 24 hr for activation and modification, filtering, and drying at 105 deg.C for 10 hr; wherein the mass ratio of the silicon dioxide to hydrogen peroxide in the hydrogen peroxide solution is 1.
The heterogeneous catalyst was prepared as in example 1.
Example 11
A heterogeneous catalyst for preparing lactaldehyde by the ligand-free hydroformylation of acetaldehyde and synthesis gas comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 4 parts of rhodium, 0 part of ruthenium, 0 part of cobalt and 0 part of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 1 part of zinc and 0 part of cesium, and the balance of the active coordination carrier; the active coordination carrier is prepared by the following method: soaking silicon dioxide in a peroxyacetic acid solution with the mass concentration of 1%, soaking for 24 hours under ultrasonic treatment for activation modification, filtering, and drying at 105 ℃ for 10 hours; wherein the mass ratio of the silicon dioxide to the peroxyacetic acid in the peroxyacetic acid solution is 1.
The heterogeneous catalyst was prepared as described in example 1.
Application of
Filling a catalyst in a bubbling kettle type reactor, controlling the reaction temperature to be 80-120 ℃ and the reaction pressure to be 1-5MPa, mixing acetaldehyde or paraldehyde with synthesis gas to form a reaction raw material, and reacting for 2-10h according to the weight space velocity -1 Feeding the material through a catalyst bed layer; wherein the synthesis gas is CO and H 2 A mixture of (a);
the reaction conditions and results are shown in Table 1.
TABLE 1 reaction conditions and results
Claims (8)
1. Use of a heterogeneous catalyst for the preparation of lactaldehyde characterized in that: the application specifically comprises the following steps: filling a catalyst in a bubbling kettle type reactor, controlling the reaction temperature to be 80-120 ℃ and the reaction pressure to be 1-5MPa, mixing acetaldehyde or paraldehyde with synthesis gas to form a reaction raw material, and reacting for 2-10h according to the weight space velocity -1 Feeding the material through a catalyst bed layer; wherein the synthesis gas is CO and H 2 A mixture of (a);
the heterogeneous catalyst comprises a main catalyst, an auxiliary catalyst and an active coordination carrier, wherein the main catalyst comprises 0.1-5 parts of rhodium, 0-2 parts of ruthenium, 0-5 parts of cobalt and 0-2 parts of iridium according to 100 parts by weight of the catalyst, the auxiliary catalyst comprises 0.1-1 part of zinc and 0-0.8 part of cesium, and the balance is the active coordination carrier; the active coordination carrier is prepared by modifying any one of active carbon, silicon dioxide, graphene, carbon nano tube and aluminum oxide through hydroxyl.
2. Use according to claim 1, characterized in that: the active coordination carrier is prepared by the following method: adding any one of active carbon, silicon dioxide, graphene, carbon nano tube and alumina into a solution containing hydroxyl, soaking for 24-48h under ultrasonic treatment for activation modification, filtering, and drying at 105-115 ℃ for 4-10h to obtain the active coordination carrier.
3. Use according to claim 2, characterized in that: the mass ratio of any one of the active carbon, the silicon dioxide, the graphene, the carbon nano tube and the aluminum oxide to the solute in the solution containing the hydroxyl is 1 (5-10).
4. Use according to claim 3, characterized in that: the solution containing hydroxyl is hydrogen peroxide solution or peroxyacetic acid solution.
5. The use according to claim 4, wherein: the mass concentration of the hydrogen peroxide solution is 2-30%; the mass concentration of the peroxyacetic acid solution is 1-5%.
6. Use according to claim 5, characterized in that: the preparation method of the heterogeneous catalyst comprises the following steps:
(1) Preparing a main catalyst solution: according to the components of the main catalyst in the heterogeneous catalyst, taking sulfate or chloride of the main catalyst to prepare a sulfate solution or chloride solution with the total mass concentration of 5-10% to obtain a main catalyst solution;
(2) Preparing a cocatalyst solution: according to the components of the cocatalyst in the heterogeneous catalyst, preparing a sulfate solution or a chloride solution with the total mass concentration of 2-5% from sulfate or chloride of the cocatalyst to obtain a cocatalyst solution;
(3) Preparing a catalyst by impregnation: mixing the main catalyst solution and the cocatalyst solution, adding the active coordination carrier, soaking for 24-48h, filtering, washing with deionized water, drying, grinding, sieving and granulating.
7. Use according to claim 6, characterized in that: the drying and drying conditions in the step (3) are drying at 110-130 ℃ for 3-6h; the grinding and sieving are 200 mesh sieves.
8. Use according to any one of claims 1 to 5, characterized in that: acetaldehyde, CO, H in the reaction system 2 In a molar ratio of 1: (5-10): (5-10).
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| CN103648641A (en) * | 2011-01-28 | 2014-03-19 | 日本化药株式会社 | Catalyst for selectively reducing saturated aldehyde, and production method thereof |
| CN108484383A (en) * | 2018-02-07 | 2018-09-04 | 中国科学院兰州化学物理研究所 | A method of preparing hydroxyacetic acid compound |
| CN112473709A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Catalyst for synthesizing succinic acid by aqueous phase catalytic hydrogenation and application thereof |
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