CN112517065B - Preparation method of catalyst for vinyl acetate process by ethylene gas phase method - Google Patents
Preparation method of catalyst for vinyl acetate process by ethylene gas phase method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000005977 Ethylene Substances 0.000 title claims abstract description 20
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 239000010931 gold Substances 0.000 claims abstract description 25
- 229910052737 gold Inorganic materials 0.000 claims abstract description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- -1 alkali metal acetate Chemical class 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 230000004048 modification Effects 0.000 claims description 27
- 238000012986 modification Methods 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 229920002125 Sokalan® Polymers 0.000 claims description 11
- 150000002344 gold compounds Chemical class 0.000 claims description 11
- 239000004584 polyacrylic acid Substances 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 150000002941 palladium compounds Chemical class 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 75
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 56
- 239000007864 aqueous solution Substances 0.000 description 43
- 238000006722 reduction reaction Methods 0.000 description 30
- 230000009467 reduction Effects 0.000 description 29
- 239000002253 acid Substances 0.000 description 28
- 239000001257 hydrogen Substances 0.000 description 28
- 229910052739 hydrogen Inorganic materials 0.000 description 28
- 235000011056 potassium acetate Nutrition 0.000 description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 238000001035 drying Methods 0.000 description 15
- 239000011734 sodium Substances 0.000 description 14
- 239000004115 Sodium Silicate Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 13
- 238000007598 dipping method Methods 0.000 description 13
- 238000002791 soaking Methods 0.000 description 13
- 229910052911 sodium silicate Inorganic materials 0.000 description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000000704 physical effect Effects 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 8
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 8
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 8
- 239000002994 raw material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
- C07C67/05—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation
- C07C67/055—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds with oxidation in the presence of platinum group metals or their compounds
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a catalyst for vinyl acetate technology by an ethylene gas phase method, which mainly solves the problems of low activity and low selectivity of the existing catalyst. The invention provides a preparation method of a catalyst for vinyl acetate technology by an ethylene gas phase method, which comprises the following steps: (abc) obtaining a mixture c comprising: a catalyst carrier, a palladium-containing compound, a gold-containing compound, a solvent and an auxiliary agent, wherein the auxiliary agent comprises an electronegative water-soluble hydrophobic modified polymer and/or a nonionic water-soluble low molecular weight polymer; (d) Mixing the mixture c with an alkaline compound solution to convert the dissolved form of the palladium and gold containing compound into a precipitate form to obtain a catalyst precursor I; (e) Reducing the palladium and gold in the compound state in the catalyst precursor I to 0 valence to obtain a catalyst precursor II; (f) The technical scheme of impregnating alkali metal acetate by the catalyst precursor II better solves the problem, and can be used in the production of vinyl acetate by an ethylene gas phase method.
Description
Technical Field
The invention relates to a preparation method of a catalyst for vinyl acetate technology by an ethylene gas phase method.
Background
Vinyl acetate (Vinyl Acetate VAc) is an important organic monomer, is an important raw material for synthesizing chemical products such as polyvinyl alcohol (PVA), polyvinyl acetate (PVA), ethylene-vinyl acetate copolymer (EVA), vinyl acetate-vinyl chloride copolymer (EVC), polypropylene comonomer and the like, is widely applied to fields such as synthetic fibers, leather processing, soil improvement, films, sizing agents, vinylon, adhesives, coatings and the like, and has wide application prospects. Among them, ethylene gas phase method is one of the most main methods for producing VA in industry at present, and has the advantages of high energy utilization rate, small environmental hazard and the like. In particular, in recent years, as the technological route for producing ethanol from biomass and further producing ethylene by dehydration is opened, the synthesis of VAc by an ethylene gas phase method has been attracting more attention.
Currently, the industrial ethylene gas phase method for synthesizing VAc mainly uses palladium-gold/potassium acetate/silicon dioxide as a catalyst, uses ethylene, oxygen and acetic acid as raw materials, and performs gas phase catalytic reactionIt should be produced that produces vinyl acetate, water and by-product carbon dioxide, as well as trace amounts of ethyl acetate, acetaldehyde and additional acetoxylation products. The temperature at the shell side of the reactor of the reaction can be about 100 to 180 ℃, the reaction pressure is about 0.5 to 1.0MPa, and the gas volume space velocity is about 500 to 3000hr -1 。
At present, chemical reduction methods, such as patent of Hermite rayon company (CN 1226188A), are mostly adopted for preparing vinyl acetate catalysts by an industrial ethylene gas phase method, and the activity and the selectivity of the catalysts obtained by the methods are low. Therefore, in order to solve the problems, a new preparation method of a vinyl acetate catalyst by an ethylene gas phase method is provided.
Disclosure of Invention
The invention aims to solve the technical problem that the catalyst prepared by the prior art has low reaction activity and selectivity, and provides a novel preparation method of the catalyst for the vinyl acetate process by the ethylene gas phase method.
The second technical problem to be solved by the invention is to provide the catalyst obtained by the preparation method.
The third technical problem to be solved by the invention is to provide the application of the catalyst.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
the preparation method of the catalyst for the vinyl acetate process by an ethylene gas phase method comprises the following steps:
(abc) obtaining a mixture c comprising: a catalyst carrier, a palladium-containing compound, a gold-containing compound, a solvent and an auxiliary agent, wherein the auxiliary agent comprises an electronegative water-soluble hydrophobic modified polymer and/or a nonionic water-soluble low molecular weight polymer;
(d) Mixing the mixture c with an alkaline compound solution to convert the dissolved form of the palladium and gold containing compound into a precipitate form to obtain a catalyst precursor I;
(e) Reducing the palladium and gold in the compound state in the catalyst precursor I to 0 valence to obtain a catalyst precursor II;
(f) The catalyst precursor II is impregnated with alkali metal acetate.
The catalyst obtained by the process of the present invention increases the space-time yield and selectivity thanks to the inclusion in the above mixture c of electronegative water-soluble hydrophobically modified polymers and/or nonionic water-soluble low molecular weight polymers.
In the above technical solution, the mixture c is preferably obtained by a method comprising the following steps:
(a) Immersing the catalyst carrier in a solution containing a palladium compound and a gold compound to obtain a mixture a;
(b) Adding electronegative water-soluble hydrophobic modified polymer solution to obtain a mixture b;
(c) Adding a nonionic water-soluble low molecular weight polymer solution to obtain a mixture c.
In the above technical solutions, the carrier is selected from those well known in the art, such as, but not limited to, at least one selected from silica, alumina and titania.
In the above technical solution, preferably, the palladium-containing compound is chlorpalladate or chlorpalladate, and the gold-containing compound is chloroauric acid or chloroauric acid salt.
In the above technical solution, preferably, the electronegative water-soluble hydrophobically modified polymer is at least one selected from the group consisting of hydrophobically modified polyacrylic acid, hydrophobically modified hydroxymethyl cellulose, hydrophobically modified hydroxyethyl cellulose, and hydrophobically modified hydroxypropyl cellulose; more preferably, the electronegative water-soluble hydrophobically modified polymer has a number average molecular weight of 5000 to 50000, such as, but not limited to, the electrically water-soluble hydrophobically modified polymer has a number average molecular weight of 5000, 10000, 15000, 20000, 25000, 30000, 35000, 40000, 45000, 50000, etc.; more preferably, the electronegative water-soluble hydrophobically modified polymer has a degree of hydrophobic modification of 5% to 10%, such as, but not limited to, a degree of water transport modification of 5%, 6%, 7%, 8%, 9%, 10%, etc. of the electrically water-soluble hydrophobically modified polymer.
In the above technical solution, preferably, the nonionic water-soluble low molecular weight polymer is polyvinylpyrrolidone and/or polyacrylamide; more preferably, the number average molecular weight of the nonionic water-soluble low molecular weight polymer is 4000 to 10000, for example, but not limited to, 4000, 5000, 6000, 7000, 8000, 9000, 10000, etc.
In the above technical scheme, the electronegative water-soluble hydrophobic modified polymer content in the electronegative water-soluble hydrophobic modified polymer solution is preferably 0.1-2.0 g/L, for example, but not limited to, 0.1g/L, 0.15g/L, 0.2g/L, 0.25g/L, 0.3g/L, 0.35g/L, 0.4g/L, 0.45g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1.0g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L, 1.5g/L, 1.6g/L, 1.7g/L, 1.8g/L, 1.9g/L, 2.0g/L and the like.
In the above technical scheme, the nonionic water-soluble low molecular weight polymer content in the nonionic water-soluble low molecular weight polymer solution is preferably 0.1-2.0 g/L, for example, but not limited to, 0.1g/L, 0.15g/L, 0.2g/L, 0.25g/L, 0.3g/L, 0.35g/L, 0.4g/L, 0.45g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1.0g/L, 1.1g/L, 1.2g/L, 1.3g/L, 1.4g/L, 1.5g/L, 1.6g/L, 1.7g/L, 1.8g/L, 1.9g/L, 2.0g/L, etc.
In the above technical scheme, the palladium content in the solution containing the palladium compound and the gold compound is preferably 1.0-12.0 g/L, for example, but not limited to, the palladium content in the solution containing the palladium compound and the gold compound is 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, 3.5g/L, 4.0g/L, 4.5g/L, 5.0g/L, 5.5g/L, 6.0g/L, 6.5g/L, 7.0g/L, 7.5g/L, 8.0g/L, 8.5g/L, 9.0g/L, 9.5g/L, 10g/L. 10.5g/L, 11g/L, 11.5g/L, etc.
In the above technical scheme, the gold content in the solution of the palladium-containing compound and the gold compound is preferably 0.1-10.0 g/L, for example, but not limited to, 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1.0g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, 3.5g/L, 4.0g/L, 4.5g/L, 5.0g/L, 5.5g/L, 6.0g/L, 6.5g/L, 7.0g/L, 7.5g/L, 8.0g/L, 8.5g/L, 9.0g/L, 9.5g/L, and the like.
In the above technical solution, the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the carrier stack is preferably 1.0 to 1.5, for example, but not limited to, the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the carrier stack is 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, and the like.
In the above technical solution, the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the auxiliary solution is preferably 0.25 to 0.75, for example, but not limited to, the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the auxiliary solution is 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, etc.
In the above-mentioned technical scheme, the ratio of the volume of the nonionic water-soluble low molecular weight polymer solution to the volume of the electronegative water-soluble hydrophobically modified polymer solution is preferably 0.25 to 0.75, for example, but not limited to, the ratio of the volume of the nonionic water-soluble low molecular weight polymer solution to the volume of the electronegative water-soluble hydrophobically modified polymer solution is 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, etc.
In the above technical scheme, preferably, the alkaline compound is alkali metal silicate or alkali metal hydroxide.
In the above technical solution, preferably, the alkali metal acetate is potassium acetate.
In the above technical solution, the steps (d) to (f) are not particularly limited, and those commonly used in the art can be adopted, and for this purpose, those skilled in the art can reasonably select and do not need to pay creative effort and can obtain comparable technical effects.
As a non-limiting example of step (e), the reducing agent that can be used for the reduction is hydrogen, and when the reduction is performed using hydrogen as the reducing agent, the reduction temperature can be, but is not limited to, 100 to 300 ℃ (e.g., but not limited to, 150 ℃, 200 ℃, 250 ℃, etc.).
In the technical scheme, the number average molecular weight of the polymer is determined by gel permeation chromatography, the mobile phase is tetrahydrofuran, and the stationary phase is styrene-divinylbenzene copolymer.
In the above technical solution, (the degree of hydrophobic modification refers to the percentage of the number of hydrophobic modification units on the polymer molecular chain to the total number of units of the polymer) (for example, when the number of hydrophobic units of the hydrophobic modification polymer is defined as Na and the number of hydrophilic units is defined as Nb:
degree of hydrophobic modification= [ Na/(na+nb)) ] ×100%.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
a catalyst obtainable by the process according to any one of the above technical solutions.
In order to solve the third technical problem, the technical scheme of the invention is as follows:
the catalyst described in the second technical problem or the catalyst obtained by the preparation method according to any one of the technical schemes in the second technical problem is applied to the production of vinyl acetate by an ethylene gas phase method.
The technical key of the invention is the preparation method of the catalyst and the catalyst obtained according to the preparation method, and for the specific process conditions of the application of the catalyst, those commonly used in the art can be adopted, and the technical effects can be achieved without creative labor.
The experimental result shows that the reaction pressure is 0.7MPa, the reaction temperature is 140 ℃, and the reaction gas is oxygen in a molar ratio: ethylene: nitrogen gas: acetic acid=1: 6.8:7.2:1.7, compared with the prior art, the space-time yield of the catalyst is improved from 325g/L to 488g/L, the selectivity is improved from 94.0% to 95.8%, and a better technical effect is obtained.
Detailed Description
Example 1
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 300ml of an aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 5000, degree of hydrophobically modification: 5%) was added to give a total concentration of 0.15g/L;
step (c): 300ml of an aqueous polyvinylpyrrolidone (number average molecular weight 4000) solution was added at a concentration of 2.0g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
For comparison, the preparation conditions of the catalyst are listed in table 1.
(2) Characterization of the catalyst
The content of each element in the catalyst was measured using an inductively coupled plasma spectroscope (ICP), and the analytical characterization data obtained are shown in table 2.
(3) Catalyst evaluation
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 400ml;
the reaction raw material composition (in mole ratio): oxygen: ethylene: nitrogen gas: acetic acid=1: 6.8:7.2:1.7;
space velocity of the feed of the reaction raw materials: 2000hr -1 ；
Reaction pressure: 0.7MPa;
reaction temperature: 140 ℃;
reaction time: 500hr;
the reaction product was analyzed for the content of each component by gas chromatography, and then the selectivity of the catalyst to ethylene was calculated, and the test data obtained are shown in Table 2.
Example 2
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of an aqueous solution of hydrophobically modified hydroxymethyl cellulose (number average molecular weight 25000, degree of hydrophobic modification 10%) was added at a total concentration of 0.1g/L;
step (c): 900ml of an aqueous solution of polyvinylpyrrolidone (number average molecular weight: 10000) was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 3
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 900ml of an aqueous solution of hydrophobically modified hydroxyethyl cellulose (number average molecular weight: 50000, degree of hydrophobic modification: 8%) was added, with a total concentration of 0.15g/L;
step (c): 600ml of an aqueous solution of polyacrylamide (number average molecular weight: 5000) was added at a concentration of 2.0g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is configured to 100mlAqueous solution), standing for 24 hours after uniformly mixing, and then drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 4
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of an aqueous solution of hydrophobically modified hydroxypropyl cellulose (number average molecular weight 25000, degree of hydrophobic modification 8%) was added at a total concentration of 0.1g/L;
step (c): 600ml of an aqueous solution of polyacrylamide (number average molecular weight: 5000) was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 5
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxymethyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous polyvinylpyrrolidone (number average molecular weight: 5000) solution was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 6
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxyethyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous polyvinylpyrrolidone (number average molecular weight: 5000) solution was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 7
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxypropyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous polyvinylpyrrolidone (number average molecular weight: 5000) solution was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 8
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxypropyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous solution of polyacrylamide (number average molecular weight: 5000) was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 9
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxypropyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous polyvinylpyrrolidone (number average molecular weight: 5000) solution was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 150 ℃ and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 10
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxypropyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous polyvinylpyrrolidone (number average molecular weight: 5000) solution was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 250 ℃ and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 11
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 1.5g/L, and the content of gold is 0.2g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxypropyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous polyvinylpyrrolidone (number average molecular weight: 5000) solution was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Example 12
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 11.5g/L, and the content of gold is 9.5g/L;
step (b): 600ml of a mixed aqueous solution of hydrophobically modified polyacrylic acid (number average molecular weight: 25000, degree of hydrophobic modification: 8%) and hydrophobically modified hydroxypropyl cellulose (number average molecular weight: 25000, degree of hydrophobic modification: 8%) was added at a mass ratio of 1:1, and a total concentration of 0.15g/L;
step (c): 600ml of an aqueous polyvinylpyrrolidone (number average molecular weight: 5000) solution was added at a concentration of 0.15g/L;
step (d): 100ml of aqueous sodium silicate solution (27.5 g of Na was added 2 SiO 3 ·9H 2 O is prepared into 100ml of water solution), and after uniform mixing, the mixture is kept stand for 24 hours and then dried at 80 ℃ for 8 hours, so as to obtain a catalyst precursor I;
step (e): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (f): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
Comparative example 1
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladic acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L, and the content of gold is 0.625g/L;
step (b): adding 100ml of sodium silicate aqueous solution with the concentration of 118g/L, uniformly mixing, standing for 24 hours, and then drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (c): reducing the catalyst precursor I in a hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa, wherein the reduction temperature is 200 ℃, and the reduction time is 2hr to obtain a catalyst precursor II;
step (d): dipping the aqueous solution of potassium acetate to make the content of potassium acetate be 30g/L, and drying to obtain the finished catalyst.
The other steps were the same as in example 1, and for comparison, the preparation conditions of the catalyst and the physical property data of the catalyst are shown in tables 1 and 2, respectively.
TABLE 1 catalyst preparation conditions
TABLE 2 catalyst Properties and evaluation data
Claims (9)
1. The preparation method of the catalyst for the vinyl acetate process by an ethylene gas phase method comprises the following steps:
(1) Obtaining a mixture c, said mixture c comprising: the catalyst comprises a catalyst carrier, a palladium-containing compound, a gold-containing compound, a solvent and an auxiliary agent, wherein the auxiliary agent comprises an electronegative water-soluble hydrophobic modified polymer and a nonionic water-soluble low molecular weight polymer; the electronegative water-soluble hydrophobically modified polymer is hydrophobically modified polyacrylic acid; the nonionic water-soluble low molecular weight polymer is selected from polyvinylpyrrolidone and/or polyacrylamide;
the catalyst carrier is selected from at least one of silicon dioxide, aluminum oxide and titanium oxide;
the number average molecular weight of the electronegative water-soluble hydrophobically modified polymer is 5000-50000; the number average molecular weight of the nonionic water-soluble low molecular weight polymer is 4000-10000; the volume ratio of the nonionic water-soluble low molecular weight polymer solution to the electronegative water-soluble hydrophobic modified polymer solution is 0.25-0.75;
(2) Mixing the mixture c with an alkaline compound solution to convert the dissolved form of the palladium and gold containing compound into a precipitate form to obtain a catalyst precursor I;
(3) Reducing the palladium and gold in the compound state in the catalyst precursor I to 0 valence to obtain a catalyst precursor II;
(4) The catalyst precursor II is impregnated with alkali metal acetate.
2. The preparation method according to claim 1, characterized in that the mixture c is obtained by a method comprising the steps of:
(a) Immersing the catalyst carrier in a solution containing a palladium compound and a gold compound to obtain a mixture a;
(b) Adding electronegative water-soluble hydrophobic modified polymer solution to obtain a mixture b;
(c) Adding a nonionic water-soluble low molecular weight polymer solution to obtain a mixture c.
3. The preparation method according to claim 1, wherein the hydrophobically modified polymer has a degree of hydrophobically modification of 5% to 10%.
4. The preparation method according to claim 2, wherein the electronegative water-soluble hydrophobically modified polymer content in the electronegative water-soluble hydrophobically modified polymer solution is 0.1-2.0 g/L.
5. The method according to claim 2, wherein the nonionic water-soluble low molecular weight polymer content in the nonionic water-soluble low molecular weight polymer solution is 0.1 to 2.0 g/L.
6. The preparation method according to claim 2, wherein the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the carrier stack is 1.0 to 1.5.
7. The preparation method according to claim 2, wherein the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the auxiliary agent solution is 0.25 to 0.75.
8. The catalyst obtained by the production method according to any one of claims 1 to 7.
9. Use of the catalyst of claim 8 or the catalyst obtained by the preparation method of any one of claims 1 to 7 in the production of ethylene-gas phase process vinyl acetate.
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| US6074979A (en) * | 1997-05-23 | 2000-06-13 | Celanese Gmbh | Polybetaine-stabilized, palladium-containing nanoparticles, a process for preparing them and also catalysts prepared from them for producing vinyl acetate |
| CN102740964A (en) * | 2009-12-16 | 2012-10-17 | 莱昂德尔化学技术公司 | Preparation of palladium-gold catalyst |
| CN103878022A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing allyl acetate |
| CN104549515A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
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| US6074979A (en) * | 1997-05-23 | 2000-06-13 | Celanese Gmbh | Polybetaine-stabilized, palladium-containing nanoparticles, a process for preparing them and also catalysts prepared from them for producing vinyl acetate |
| CN102740964A (en) * | 2009-12-16 | 2012-10-17 | 莱昂德尔化学技术公司 | Preparation of palladium-gold catalyst |
| CN103878022A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing allyl acetate |
| CN104549515A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
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