CN112517063A - Preparation method of vinyl acetate catalyst - Google Patents
Preparation method of vinyl acetate catalyst Download PDFInfo
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- CN112517063A CN112517063A CN201910878446.7A CN201910878446A CN112517063A CN 112517063 A CN112517063 A CN 112517063A CN 201910878446 A CN201910878446 A CN 201910878446A CN 112517063 A CN112517063 A CN 112517063A
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Abstract
The invention relates to preparation of a vinyl acetate catalyst by an ethylene method, and mainly solves the problems of low activity and low selectivity of the existing catalyst. The technical scheme 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 dissolution type of the palladium and gold containing compound into a precipitation type to obtain a catalyst precursor I; (d) reducing the combined palladium and gold in the catalyst precursor I to 0 valence to obtain a catalyst precursor II; (e) and (3) impregnating the alkali metal acetate by using a catalyst precursor II.
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 resin (EVA), Vinyl Acetate-Vinyl chloride copolymer (EVC) and polypropylene comonomer, is widely applied to the fields of synthetic fibers, leather processing, soil improvement, films, sizing agents, vinylon, adhesives, coatings and the like, and has wide application prospect. Among them, the ethylene gas phase method is one of the most important methods for producing VA industrially at present, and has the advantages of high energy utilization rate, small environmental hazard, and the like. Particularly, in recent years, with the opening of a technical route for preparing ethanol from biomass and further preparing ethylene by dehydration, the synthesis of VAc by an ethylene gas phase method is attracting more attention.
Currently, in the industrial synthesis of VAc by ethylene gas phase method, palladium-gold/potassium acetate/silicon dioxide is mainly used as a catalyst, ethylene, oxygen and acetic acid are used as raw materials, and the VAc is produced by gas phase catalytic reaction to generate vinyl acetate, water and byproduct carbon dioxide, and also generate trace ethyl acetate, acetaldehyde and other acetoxylation products. The temperature of the shell side of the reactor for 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, the industrial preparation of ethylene vinyl acetate catalyst by gas phase method adopts chemical reduction method, such as the patent of Hechester rayon company (CN1226188A), and the activity and selectivity of the catalyst obtained by the method are low. Therefore, in order to solve the above problems, we propose a new method for preparing ethylene vapor phase vinyl acetate catalyst.
Disclosure of Invention
The invention aims to solve the technical problems that the existing catalyst is low in activity and selectivity, and provides a novel preparation method of a vinyl acetate catalyst.
The second technical problem to be solved by the present invention is to provide the catalyst obtained by the above 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 above technical problems, the technical solution of the present 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 dissolution type of the palladium and gold containing compound into a precipitation type to obtain a catalyst precursor I;
(d) reducing the combined palladium and gold in the catalyst precursor I to 0 valence to obtain a catalyst precursor II;
(e) and (3) impregnating the alkali metal acetate by using a catalyst precursor II.
The cationic surfactant and the zwitterionic surfactant in the step (ab) can obviously improve the space-time yield and selectivity of the catalyst.
In the above technical solutions, the steps of the method for obtaining the mixture b in the step (ab) are not particularly limited, and all the steps can achieve comparable technical effects without creative efforts.
In the above technical solution, by way of example only, the step of obtaining the mixture b in the step (ab) includes:
(a) dipping a catalyst carrier in a solution containing a palladium compound and a gold compound to obtain a mixture a;
(b) and mixing the mixture a with a surfactant solution to obtain a mixture b.
In the above technical solutions, the support 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 chloropalladate or chloropalladate, and the gold-containing compound is preferably chloroauric acid or chloropalladate.
In the above technical solution, the palladium content in the solution containing the palladium compound and the gold compound is preferably 1.0 to 12.0g/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, 10 g/L. 10.5g/L, 11g/L, 11.5g/L, and the like.
In the above technical solution, the gold content in the solution containing the palladium compound and the gold compound is preferably 0.1-10.0 g/L, for example, but not limited to, the gold content in the solution containing the palladium compound and the gold compound is 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 bulk 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 bulk 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 surfactant solution is preferably 0.8 to 1.2, and 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, and the like.
In the above technical solution, preferably, the cationic surfactant has the following structure:
R1-N+(RaRbRc)M-wherein R is1Is C12-C18 alkyl, Ra、RbAnd RcIndependently C1-C3 alkyl, M is halide ion Cl, Br or HSO4。
For example, but not limited to, the cationic surfactant is dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and the like.
In the above technical solution, preferably, the zwitterionic surfactant has the following structure:
R2-N+(RdReRf)RgX-(ii) a Wherein R is2Is C12-C18 alkyl, Rd、ReAnd RfIndependently is C1-C3 alkyl, RgIs C1-C2 alkylene, X is COO or SO3。
For example, but not limited to, the zwitterionic surfactant can be dodecyl carboxy betaine, dodecyl sulfobetaine, hexadecyl carboxy betaine, hexadecyl sulfobetaine, and the like.
In the technical scheme, particularly when the surfactant comprises the cationic surfactant and the zwitterionic surfactant, the prepared catalyst has better performance in the aspects of space-time yield and selectivity, and the effect promotion trend is reflected 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 can achieve comparable accelerating effects, but the mass ratio of the cationic surfactant to the zwitterionic surfactant is preferably 0.1 to 10, and for example, but not limited thereto, 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, the total concentration of the cationic surfactant and the zwitterionic surfactant is 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 solution, preferably, the alkali compound is an alkali metal silicate or an alkali metal hydroxide.
In the above technical solution, preferably, the alkali metal acetate is potassium acetate.
In the above technical scheme, the reduction mode of step (d) is not particularly limited, and those commonly used in the art can be adopted, for which, those skilled in the art can reasonably select and do not need to make creative work, and all can achieve comparable technical effects. By way of non-limiting example, the reducing agent used 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 ℃ (for example, but not limited to, 150 ℃, 200 ℃, 250 ℃, etc.).
To solve the second technical problem, the technical solution of the present invention is as follows:
a catalyst obtained by the production method according to any one of the above technical problems.
To solve the third technical problem, the technical scheme of the invention is as follows:
use of a catalyst according to the second of the preceding technical problems or a catalyst obtainable by a preparation process according to any one of the preceding technical solutions for the production of vinyl acetate by gas phase ethylene.
The technical key of the invention is the preparation method of the catalyst and the catalyst obtained by the preparation method, and for the specific process conditions of the application of the catalyst, those commonly used in the field can be adopted without creative labor and can achieve comparable technical effects.
The experimental result shows that the reaction pressure is 0.7MPa, the reaction temperature is 140 ℃, and the reaction gas comprises oxygen in molar ratio: ethylene: nitrogen gas: acetic acid 1: 6.8: 7.2: 1.7, compared with the catalyst in the prior art, the space-time yield of the catalyst is improved to 480g/L from 325g/L, the selectivity is improved to 95.4% from 94.0%, and a better technical effect is achieved.
Detailed Description
Example 1
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1100ml 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 in the solution is 0.625 g/L;
step (b): adding 1100ml of dodecyl trimethyl ammonium bromide solution with the concentration of 20 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml water solution), mixing well and standing for 24 hoursThen drying the catalyst at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
For comparison, the catalyst preparation conditions are shown in table 1.
(2) Catalyst characterization
The contents of the respective elements in the catalyst were measured using an inductively coupled plasma spectrometer (ICP), and the analytical characterization data obtained are shown in table 2.
(3) Catalyst evaluation
The evaluation is carried out by a fixed bed reactor, and the specific conditions are as follows:
catalyst loading volume: 400 ml;
the reaction raw materials comprise (by mol ratio): oxygen: ethylene: nitrogen gas: acetic acid 1: 6.8: 7.2: 1.7;
reaction raw material feeding airspeed: 2000hr-1；
Reaction pressure: 0.7 MPa;
reaction temperature: 140 ℃;
reaction time: 500 hr;
the contents of the components in the reaction product were analyzed by gas chromatography, and then the selectivity of the catalyst to ethylene was calculated, and the obtained experimental data are shown in Table 2.
Example 2
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica 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 in the solution is 0.625 g/L;
step (b): adding 1650ml of dodecyl carboxyl betaine solution with the concentration of 20 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 3
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): adding 1200ml of mixed solution of dodecyl trimethyl ammonium bromide and dodecyl carboxyl betaine, wherein the concentration of a 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 an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 4
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): adding 1200ml of dodecyl trimethyl ammonium chloride solution with the concentration of 15.5 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 5
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): adding 1200ml of dodecyl sulphobetaine solution with the concentration of 24.5 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 6
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): adding 1200ml of mixed solution of dodecyl trimethyl ammonium chloride and dodecyl sulphobetaine, wherein the total concentration of the surfactant is 20g/L, and the mass ratio of the dodecyl trimethyl ammonium chloride to the dodecyl sulphobetaine in the solution is 1: 10;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 7
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): adding 1000ml of hexadecyl trimethyl ammonium bromide solution with the concentration of 20 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 8
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): adding 1500ml hexadecyl carboxyl betaine solution with the concentration of 20 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 9
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): 1200ml of mixed solution of hexadecyl trimethyl ammonium bromide and hexadecyl carboxyl betaine is added, the total concentration of the surfactant is 20g/L, and the mass ratio of dodecyl trimethyl ammonium chloride to dodecyl sulfo betaine in the solution is 1: 1;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 10
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): 1200ml of mixed solution of hexadecyl trimethyl ammonium bromide and hexadecyl carboxyl betaine is added, the total concentration of the surfactant is 20g/L, and the mass ratio of dodecyl trimethyl ammonium chloride to dodecyl sulfo betaine in the solution is 1: 1;
step (ii) of(c) The method comprises the following steps 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 150 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 11
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): 1200ml of mixed solution of hexadecyl trimethyl ammonium bromide and hexadecyl carboxyl betaine is added, the total concentration of the surfactant is 20g/L, and the mass ratio of dodecyl trimethyl ammonium chloride to dodecyl sulfo betaine in the solution is 1: 1;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 250 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 12
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 1.50g/L, and the content of gold in the solution is 0.20 g/L;
step (b): adding 1200ml of hexadecyl trimethyl ammonium chloride solution with the concentration of 20 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Example 13
1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml of mixed aqueous solution of chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 11.50g/L, and the content of gold in the solution is 9.50 g/L;
step (b): adding 1200ml of hexadecyl sulfobetaine solution with the concentration of 20 g/L;
step (c): 100ml of an aqueous sodium silicate solution (27.5g of Na was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (d): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
a step (e): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
Comparative example 1
(1) Preparation of the catalyst
Step (a): soaking 1100ml of spherical silica carrier with the diameter of 4-6 nm in 1200ml 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 in the solution is 0.625 g/L;
step (b): 100ml of an aqueous sodium silicate solution (27.5g Na) was added2SiO3·9H2Preparing O into 100ml of aqueous solution), uniformly mixing, standing for 24 hours, and drying at 80 ℃ for 8 hours to obtain a catalyst precursor I;
step (c): reducing the catalyst precursor I in hydrogen atmosphere at a hydrogen flow rate of 0.2ml/min and a pressure of 0.5MPa at a reduction temperature of 200 ℃ for 2hr to obtain a catalyst precursor II;
step (d): soaking in potassium acetate water solution to make potassium acetate content be 30g/L, drying so as to obtain the invented finished product catalyst.
The other steps were the same as in example 1, and for comparison, the catalyst preparation conditions and the catalyst physical property data are shown in tables 1 and 2, respectively.
TABLE 1 catalyst preparation conditions
TABLE 2 catalyst Properties and evaluation data
Claims (10)
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/or a zwitterionic surfactant, and a solvent;
(c) mixing the mixture b with an alkaline compound solution to convert the dissolution type of the palladium and gold containing compound into a precipitation type to obtain a catalyst precursor I;
(d) reducing the combined palladium and gold in the catalyst precursor I to 0 valence to obtain a catalyst precursor II;
(e) and (3) impregnating the alkali metal acetate by using a catalyst precursor II.
2. The method of claim 1, wherein the step of obtaining the mixture b in step (ab) comprises:
(a) dipping a catalyst carrier in a solution containing a palladium compound and a gold compound to obtain a mixture a;
(b) and mixing the mixture a with a surfactant solution to obtain a mixture b.
3. The method according to claim 2, wherein the solution containing the palladium compound and the gold compound has a palladium content of 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 method according to claim 2, wherein the ratio of the volume of the solution containing the palladium compound and the gold compound to the bulk volume of the carrier 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 method according to claim 2, wherein the basic compound is an alkali metal silicate or an alkali metal hydroxide.
6. The method according to claim 2, wherein the cationic surfactant has the following structure:
R1-N+(RaRbRc)M-；
wherein R is1Is C12-C18 alkyl, Ra、RbAnd RcIndependently C1-C3 alkyl, M is halide ion Cl, Br or HSO4。
7. The method according to claim 2, wherein the zwitterionic surfactant has the following structure:
R2-N+(RdReRf)RgX-；
wherein R is2Is C12-C18 alkyl, Rd、ReAnd RfIndependently is C1-C3 alkyl, RgIs C1-C2 alkylene, X is COO or SO3。
8. The method according to claim 2, wherein the alkali metal acetate is potassium acetate.
9. A catalyst obtained by the production method according to any one of claims 1 to 8.
10. Use of the catalyst according to claim 9 or the catalyst obtained by the preparation method according to any one of claims 1 to 8 in the synthesis of vinyl acetate by the oxidation of vinyl.
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