CN112517063B - Preparation method of vinyl acetate catalyst - Google Patents
Preparation method of vinyl acetate catalyst Download PDFInfo
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- CN112517063B CN112517063B CN201910878446.7A CN201910878446A CN112517063B CN 112517063 B CN112517063 B CN 112517063B CN 201910878446 A CN201910878446 A CN 201910878446A CN 112517063 B CN112517063 B CN 112517063B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 53
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 28
- 239000010931 gold Substances 0.000 claims abstract description 27
- 229910052737 gold Inorganic materials 0.000 claims abstract description 27
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- -1 alkali metal acetate Chemical class 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000002888 zwitterionic surfactant Substances 0.000 claims abstract description 13
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical group [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 62
- 235000011056 potassium acetate Nutrition 0.000 claims description 31
- 150000002344 gold compounds Chemical class 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 150000002941 palladium compounds Chemical class 0.000 claims description 12
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 150000007514 bases Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 78
- 238000006722 reduction reaction Methods 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 239000001257 hydrogen Substances 0.000 description 30
- 229910052739 hydrogen Inorganic materials 0.000 description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 29
- 239000002253 acid Substances 0.000 description 29
- 239000007864 aqueous solution Substances 0.000 description 28
- 239000000377 silicon dioxide Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000004115 Sodium Silicate Substances 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 14
- 238000007598 dipping method Methods 0.000 description 14
- 235000012239 silicon dioxide Nutrition 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- 229910052911 sodium silicate Inorganic materials 0.000 description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 13
- 238000002791 soaking Methods 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 9
- 229960003237 betaine Drugs 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 7
- IZWSFJTYBVKZNK-UHFFFAOYSA-N lauryl sulfobetaine Chemical compound CCCCCCCCCCCC[N+](C)(C)CCCS([O-])(=O)=O IZWSFJTYBVKZNK-UHFFFAOYSA-N 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 4
- 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
- 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
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 238000012512 characterization method Methods 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
- 229940117986 sulfobetaine Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 238000006555 catalytic reaction Methods 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
- 229920001577 copolymer Polymers 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
- 150000002431 hydrogen Chemical class 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
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 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
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to preparation of an ethylene-process vinyl acetate catalyst, which mainly solves the problems of low activity and low selectivity of the existing catalyst. The technical proposal is as follows: the preparation method of the vinyl acetate catalyst is characterized by comprising the following steps: the preparation method of the vinyl acetate catalyst is characterized by comprising the following steps: (ab) obtaining a mixture b comprising a catalyst support, a palladium-containing compound, a gold-containing compound, a surfactant comprising a cationic surfactant and/or a zwitterionic surfactant, and a solvent; (c) Mixing the mixture b 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; (d) Reducing the palladium and gold in the compound state in the catalyst precursor I to 0 valence to obtain a catalyst precursor II; (e) The catalyst precursor II is impregnated with alkali metal acetate.
Description
Technical Field
The invention relates to a preparation method of a vinyl acetate catalyst.
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, industrial ethylene gas phase synthesis of VAc mainly uses palladium-gold/potassium acetate/silica as a catalyst, uses ethylene, oxygen and acetic acid as raw materials, and produces vinyl acetate, water and by-product carbon dioxide through gas phase catalytic reaction, and also produces trace amounts of ethyl acetate, acetaldehyde and other acetoxylation products. Reactor for the reactionThe shell side temperature may be about 100 to 180℃and the reaction pressure about 0.5 to 1.0MPa, and the gas volume space velocity about 500 to 3000hr -1 。
At present, chemical reduction methods are mostly adopted for preparing vinyl acetate catalysts by an industrial ethylene gas phase method, such as patent of Herchester rayon company (CN 1226188A), and the activity and 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
One of the technical problems to be solved by the invention is the problem of low activity and low selectivity of the existing catalyst, and the invention provides a novel preparation method of the vinyl acetate catalyst.
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 vinyl acetate catalyst is characterized by comprising the following steps:
(ab) obtaining a mixture b comprising a catalyst support, a palladium-containing compound, a gold-containing compound, a surfactant comprising a cationic surfactant and/or a zwitterionic surfactant, and a solvent;
(c) Mixing the mixture b 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;
(d) Reducing the palladium and gold in the compound state in the catalyst precursor I to 0 valence to obtain a catalyst precursor II;
(e) The catalyst precursor II is impregnated with alkali metal acetate.
The cationic surfactant and the zwitterionic surfactant in the step (ab) can obviously improve the space-time yield and the selectivity of the catalyst.
In the above-described technical solution, the steps of the method for obtaining the mixture b in the step (ab) are not particularly limited, and comparable technical effects can be obtained without the need for creative efforts.
In the above technical solution, the step (ab) of obtaining the mixture b includes, by way of example only:
(a) Immersing the catalyst carrier in a solution containing a palladium compound and a gold compound to obtain a mixture a;
(b) The mixture a is mixed with a surfactant solution to obtain a mixture b.
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, the palladium-containing compound is preferably chlorpalladate or chlorpalladate, and the gold-containing compound is preferably chloroauric acid or chloroauric acid salt.
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-described embodiments, the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the surfactant solution is preferably 0.8 to 1.2, 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 surfactant solution is 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, or the like.
In the above technical solution, preferably, the cationic surfactant has the following structure:
R 1 -N + (R a R b R c )M - wherein R is 1 Is C12-C18 alkyl, R a 、R b And R is c Independently C1-C3 alkyl, M is halogen ion Cl, br or HSO 4 。
Such as, but not limited to, dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, and the like.
In the above technical solution, preferably, the zwitterionic surfactant has the following structure:
R 2 -N + (R d R e R f )R g X - the method comprises the steps of carrying out a first treatment on the surface of the Wherein R is 2 Is C12-C18 alkyl, R d 、R e And R is f Independently C1-C3 alkyl, R g Is C1-C2 alkylene, X is COO or SO 3 。
For example, but not limited to, the zwitterionic surfactant may be dodecyl carboxyl betaine, dodecyl sulfobetaine, cetyl carboxyl betaine, cetyl sulfobetaine, and the like.
In the technical scheme, particularly when the surfactant comprises a cationic surfactant and a zwitterionic surfactant, the prepared catalyst has better performance in terms of space-time yield and selectivity, and the tendency of promoting effect is shown between the cationic surfactant and the zwitterionic surfactant. In this case, the ratio of the cationic surfactant to the zwitterionic surfactant is not particularly limited, and comparable accelerating effects can be obtained, but the mass ratio of the cationic surfactant to the zwitterionic surfactant is preferably 0.1 to 10, for example, but not limited to, the mass ratio of the cationic surfactant to the zwitterionic surfactant is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2, 3, 4, 5, 6, 7, 8, 9, and the like.
In the above technical scheme, the total concentration of the cationic surfactant and the zwitterionic surfactant in the surfactant solution in the step (b) is preferably 15-25 g/L, for example, but not limited to, 15.5g/L, 16g/L, 16.5g/L, 17g/L, 17.5g/L, 18g/L, 18.5g/L, 19g/L, 19.5g/L, 20g/L, 20.5g/L, 21g/L, 21.5g/L, 22g/L, 22.5g/L, 23g/L, 23.5g/L, 24g/L, 24.5g/L, and the like.
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 manner of the reduction in the step (d) is not particularly limited, and those commonly used in the art can be adopted, for which the person skilled in the art can reasonably select and do not need to pay creative effort and can obtain comparable technical effects. By way of non-limiting example, the reducing agent that may be employed in the reduction is hydrogen, and when the reduction is performed using hydrogen as the reducing agent, the reduction temperature may be, but is not limited to, 100 to 300 ℃ (e.g., but not limited to, 150 ℃, 200 ℃, 250 ℃, etc.).
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 480g/L, the selectivity is improved from 94.0% to 95.4%, and a better technical effect is obtained.
Detailed Description
Example 1
(1) Preparation of the catalyst
Step (a): immersing 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1100ml 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): 1100ml of dodecyltrimethylammonium bromide solution are added, with a concentration of 20g/L;
step (c): 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 (d): 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 (e): 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): immersing 1100ml of spherical silicon dioxide carrier with the diameter of 4-6 nm in 1650ml of mixed aqueous solution of chloropalladate 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): 1650ml of dodecyl carboxyl betaine solution with the concentration of 20g/L is added;
step (c): 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 (d): 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 (e): 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): 1200ml of mixed solution of dodecyl trimethyl ammonium bromide and dodecyl carboxyl betaine is added, the concentration of the surfactant is 20g/L, and the mass ratio of the dodecyl trimethyl ammonium bromide to the dodecyl carboxyl betaine in the solution is 10:1;
step (c): 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 (d): 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 (e): 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): 1200ml of dodecyl trimethyl ammonium chloride solution with a concentration of 15.5g/L are added;
step (c): 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 (d): 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 (e): 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): 1200ml of dodecyl sulfobetaine solution is added, the concentration of which is 24.5g/L;
step (c): 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 (d): 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 (e): 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): 1200ml of a mixed solution of dodecyl trimethyl ammonium chloride and dodecyl sulfobetaine is added, the total concentration of the surfactant is 20g/L, and the mass ratio of the dodecyl trimethyl ammonium chloride to the dodecyl sulfobetaine in the solution is 1:10;
step (c): 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 (d): 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 (e): 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): 1000ml of cetyltrimethylammonium bromide solution was added at a concentration of 20g/L;
step (c): 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 (d): 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 (e): 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): 1500ml of hexadecyl carboxyl betaine solution with the concentration of 20g/L is added;
step (c): 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 (d): 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 (e): 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): 1200ml of mixed solution of cetyl trimethyl ammonium bromide and cetyl carboxyl betaine is added, the total concentration of the surfactant is 20g/L, and the mass ratio of the dodecyl trimethyl ammonium chloride to the dodecyl sulfobetaine in the solution is 1:1, a step of;
step (c): 100ml of aqueous sodium silicate solution (to be 27) were added.5g Na 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 (d): 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 (e): 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): 1200ml of mixed solution of cetyl trimethyl ammonium bromide and cetyl carboxyl betaine is added, the total concentration of the surfactant is 20g/L, and the mass ratio of the dodecyl trimethyl ammonium chloride to the dodecyl sulfobetaine in the solution is 1:1, a step of;
step (c): 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 (d): 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 (e): 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 2.75g/L, and the content of gold is 0.625g/L;
step (b): 1200ml of mixed solution of cetyl trimethyl ammonium bromide and cetyl carboxyl betaine is added, the total concentration of the surfactant is 20g/L, and the mass ratio of the dodecyl trimethyl ammonium chloride to the dodecyl sulfobetaine in the solution is 1:1, a step of;
step (c): 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 (d): 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 (e): 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 1.50g/L, and the content of gold is 0.20g/L;
step (b): 1200ml of cetyltrimethylammonium chloride solution was added at a concentration of 20g/L;
step (c): 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, standing for 24 hours, and then drying at 80 ℃ for 8 hours to obtain the catalyst precursorA precursor I;
step (d): 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 (e): 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 13
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 11.50g/L, and the content of gold is 9.50g/L;
step (b): 1200ml of cetyl sulfobetaine solution was added at a concentration of 20g/L;
step (c): 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 (d): 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 (e): 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): 100ml of aqueous sodium silicate solution (27.5 g Na) 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 (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 (8)
1. The preparation method of the vinyl acetate catalyst is characterized by comprising the following steps:
(ab) obtaining a mixture b comprising a catalyst support, a palladium-containing compound, a gold-containing compound, a surfactant comprising a cationic surfactant and a zwitterionic surfactant, and a solvent;
(c) Mixing the mixture b 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;
(d) Reducing the palladium and gold in the compound state in the catalyst precursor I to 0 valence to obtain a catalyst precursor II;
(e) Impregnating alkali metal acetate by a catalyst precursor II impregnation method;
the cationic surfactant has the following structure:
R 1 -N + (R a R b R c ) M - ；
wherein R is 1 Is C12-C18 alkyl, R a 、R b And R is c Independently C1-C3 alkyl, M is halogen Cl or Br;
the zwitterionic surfactant has the following structure:
R 2 -N + (R d R e R f ) R g X - ；
wherein R is 2 Is C12-C18 alkyl, R d 、R e And R is f Independently C1-C3 alkyl, R g Is C1-C2 alkylene, X is COO or SO 3 。
2. The preparation method according to claim 1, characterized in that the step of obtaining the mixture b of step (ab) comprises:
(a) Immersing the catalyst carrier in a solution containing a palladium compound and a gold compound to obtain a mixture a;
(b) The mixture a is mixed with a surfactant solution to obtain a mixture b.
3. The preparation method according to claim 2, characterized in that the palladium content in the solution containing the palladium compound and the gold compound is 1.0 to 12.0 g/L; and/or the gold content in the solution containing the palladium compound and the gold compound is 0.1-10.0 g/L.
4. 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; and/or the ratio of the volume of the solution containing the palladium compound and the gold compound to the volume of the surfactant solution is 0.8 to 1.2.
5. The preparation method according to claim 2, characterized in that the basic compound is an alkali metal silicate or an alkali metal hydroxide.
6. The method according to claim 2, wherein the alkali metal acetate is potassium acetate.
7. The catalyst obtained by the production method according to any one of claims 1 to 6.
8. Use of the catalyst of claim 7 or the catalyst obtained by the preparation method of any one of claims 1 to 6 in synthesizing vinyl acetate by ethylene acyl oxidation.
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