CN114177947B - Vinyl acetate catalyst and preparation method thereof - Google Patents

Vinyl acetate catalyst and preparation method thereof Download PDF

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CN114177947B
CN114177947B CN202010958276.6A CN202010958276A CN114177947B CN 114177947 B CN114177947 B CN 114177947B CN 202010958276 A CN202010958276 A CN 202010958276A CN 114177947 B CN114177947 B CN 114177947B
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catalyst
content
solution
carrier
vinyl acetate
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CN114177947A (en
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刘军晓
杨运信
刘燕
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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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Abstract

The invention relates to a vinyl acetate catalyst, a preparation method and application thereof, which mainly solves the problems of low catalyst activity and short service life in vinyl acetate process products by an ethylene method in the prior art, and the invention adopts the vinyl acetate catalyst which comprises a carrier, main catalyst metal palladium, promoter metal and alkali metal acetate, wherein the promoter is one or more of Au, sn and Cu, and the catalyst carrier comprises SiO 2 And as SiO 2 ZrO of modifier 2 The method is characterized in that when SEM-EDS is adopted to carry out line scanning of Zr element on the catalyst section along the radial direction, the maximum value of Zr signal intensity appears in the range of 0-0.8 mm of h, wherein h is the technical scheme from the surface of the catalyst to the distance below the surface of the catalyst, so that the technical problem is better solved, and the method can be used in the industrial production of vinyl acetate.

Description

Vinyl acetate catalyst and preparation method thereof
Technical Field
The invention relates to a vinyl acetate catalyst, a preparation method and application thereof, in particular to a vinyl acetate catalyst for an ethylene acetyl oxidation method, a preparation method and application thereof.
Background
Vinyl acetate is an important chemical raw material and is widely used for manufacturing polyvinyl alcohol, vinyl copolymer resin, adhesive, paint, textile processing, paper coating and the like. The production process route of the vinyl acetate mainly comprises two methods, namely an ethylene method and an acetylene method, wherein the ethylene method is dominant due to good manufacturability and economy, and the vinyl acetate production capacity of the method accounts for 82% of the total production capacity. At present, the method for increasing the yield of vinyl acetate in most countries is to carry out reconstruction and expansion on original devices and update and generation of catalysts, and the development trend of an ethylene method route mainly has the following directions: (1) the production apparatus tends to be large in scale. Such as VAC units from USI and Hoechst, are achieved primarily by increasing the space velocity of the unit and using highly active catalysts; (2) The VAC flow of ethylene method is improved in the direction of reducing unit consumption and energy consumption; wherein, the vinyl acetate process kit and the related catalyst of the Shanghai petrochemical institute have strong competitive advantages in the industry. The acetylene method has higher investment on process devices and higher environmental protection difficulty, but still maintains quite competitive advantages in areas with lack of petroleum resources for a certain period of time, and directly promotes the research and development of the C1 chemical method.
The main method for producing vinyl acetate in the world today is to produce vinyl acetate, water and by-product carbon dioxide by gas phase catalytic reaction using ethylene, oxygen and acetic acid as raw materials and palladium-gold-potassium acetate/silicon dioxide as catalysts, and also to produce trace amounts of ethyl acetate, methyl acetate, acetaldehyde and other acetoxylation products. The temperature of the reactor shell side of the apparatus may be from about 100 to about 180 ℃, the reaction pressure from about 0.5 to 1.0MPa, and the gas volume space velocity from about 500 to about 3000hr -1 。
The herchester rayon company patent (CN 1226188A, palladium-gold catalyst for vinyl acetate production) provides a method for producing a catalyst carrying a noble metal, a promoter metal and an alkali metal or alkaline earth metal compound as main catalysts. The patent mainly adopts a potassium salt fixing agent to fix palladium-gold active components on the surface of a carrier, and the distribution of palladium-gold is mainly related to the adsorption position of the potassium salt; the catalyst obtained by the method has insufficient activity and service life, and needs further improvement.
Disclosure of Invention
The invention provides an ethylene-process vinyl acetate catalyst, which solves the problems of low catalyst activity and short service life in ethylene-process vinyl acetate process products in the prior art, and has higher activity and longer service life.
The second technical problem to be solved by the invention is to provide a catalyst preparation method of the catalyst.
The third technical problem to be solved by the invention is to provide the application of the catalyst.
The fourth technical problem to be solved by the invention is to provide a synthesis method of vinyl acetate by adopting the catalyst.
In order to solve one of the above technical problems, the present invention provides a first aspect of the technical solution as follows:
technical solution of the first aspect
The vinyl acetate catalyst comprises a carrier, main catalyst metal palladium, promoter metal and alkali metal acetate, wherein the promoter is one or more of Au, sn and Cu, and the catalyst carrier comprises SiO 2 And as SiO 2 ZrO of modifier 2 When the SEM-EDS is used for carrying out line scanning of Zr element on the catalyst section along the radial direction, the maximum value of Zr signal intensity appears in the range of 0-0.8 mm of h, wherein h is the distance from the catalyst surface to the position below the catalyst surface.
Compared with the prior art, zr is uniformly or relatively uniformly distributed in the whole catalyst particles, and when Zr element is distributed in the catalyst shell layer, the catalyst has better space-time yield and longer service life compared with the catalyst in the prior art.
In the first aspect, the catalyst carrier of the present invention is selected from the group consisting of SiO 2 And as SiO 2 ZrO of modifier 2 。
In the above-described first aspect, as a non-limiting example, when the line scanning of Zr element is performed on the catalyst section in the radial direction by SEM-EDS according to the present invention, specific examples of the distance h from the catalyst surface to the position below the catalyst surface may be 0.05mm, 0.10mm, 0.15mm, 0.20mm, 0.25mm, 0.30mm, 0.35mm, 0.40mm, 0.45mm, 0.50mm, 0.55mm, 0.60mm, 0.65mm, 0.70mm, 0.75mm, and so on.
In the above-mentioned first aspect, the Pd content of the main catalyst of the present invention is preferably 1.0 to 10.0g/L, such as, but not limited to, 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, 9.0g/L, 9.5g/L, etc.
In the above-described first aspect, the promoter metal content is preferably 0.1 to 10g/L, such as, 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-described first aspect, the content of the alkali metal acetate is preferably 10 to 100g/L, for example, but not limited to, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, 55g/L, 60g/L, 65g/L, 70g/L, 75g/L, 80g/L, 85g/L, 90g/L, 95g/L, etc.
In the above-mentioned first aspect, the content of Zr element is preferably 0.5 to 18g/L, for example, but not limited to, 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, 10.0g/L, 10.5g/L, 11.0g/L, 11.5g/L, 12.0g/L, 12.5g/L, 13.0g/L, 13.5g/L, 14.0g/L, 14.5g/L, 15.0g/L, 15.5g/L, 16.5g/L, 17.5g/L, etc.
In the first aspect, the alkali metal acetate preferably includes potassium acetate.
In the first aspect, siO in the catalyst carrier 2 Preferably comprising amorphous silica.
In the above-described first aspect, the catalyst support is preferably spherical or spheroid in shape; preferably 4 to 8mm in diameter, such as, but not limited to, 4.5mm, 5.0mm, 5.5mm, 6.0mm, 7.0mm, 7.5mm, etc.
In the first aspect, the specific surface area of the catalyst carrier is preferably 50 to 260m 2 Preferably 120 to 260m 2 /g, for example, but not limited to 130m 2 /g、140m 2 /g、150m 2 /g、160m 2 /g、170m 2 /g、180m 2 /g、190m 2 /g、200m 2 /g、210m 2 /g、220m 2 /g、230m 2 /g、240m 2 /g、250m 2 /g, etc.
In the first aspect, the following is preferableThe pore volume of the catalyst carrier is 0.4-1.5 cm 3 /g, for example but not limited to 0.5cm 3 /g、0.6cm 3 /g、0.7cm 3 /g、0.8cm 3 /g、0.9cm 3 /g、1.0cm 3 /g、1.1cm 3 /g、1.2cm 3 /g、1.3cm 3 /g、1.4cm 3 /g, etc.
In order to solve the second technical problem, the present invention provides a second technical solution as follows:
second aspect of the technical solution
(1) Mixing a solution for dissolving Zr-containing compounds and an alkali solution i with a spherical silica carrier, standing, calcining and washing to obtain a catalyst carrier;
(2) Mixing a solution dissolved with a palladium-containing compound and an additive element-containing compound with a catalyst carrier to obtain a catalyst precursor I;
(3) Treating the catalyst precursor I by adopting an alkali solution II to convert the palladium-containing compound and the additive element-containing compound into a precipitate, and washing and drying the precipitate to obtain the catalyst precursor II;
(4) Reducing the palladium in the compound state in the catalyst precursor II to zero-valent palladium by adopting a reducing agent to obtain a catalyst precursor III;
(5) Impregnating the catalyst precursor III with an alkali metal acetate solution to obtain a catalyst precursor IV, and drying to obtain the catalyst.
In the second aspect, the Zr-containing compound is selected from the group consisting of water-soluble zirconium compounds including, but not limited to ZrOCl 2 ·8H 2 O, zirconium nitrate, zirconium sulfate, etc.
In the second aspect, the embodiment of step (1) is preferably any one of the following modes:
firstly, mixing a solution for dissolving a Zr compound with a spherical silica carrier to obtain a mixture, and then mixing the mixture with an alkali solution i;
and in the second mode, firstly mixing the alkaline solution i with the spherical silica carrier to obtain a mixture, and then mixing the mixture with a solution for dissolving the Zr-containing compound.
In the second aspect described above, the alkali solution i is added in the step (1) to convert the Zr-containing compound into a precipitate form.
In the second aspect described above, the Zr content in the solution of the Zr compound is preferably 0.1 to 2.0mol/L, such as, but not limited to, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, 1.6mol/L, 1.7mol/L, 1.8mol/L, etc.
In the second aspect, the alkaline solution i and the alkaline solution ii are independently preferably at least one of a sodium silicate solution and/or aqueous ammonia.
In the second aspect, the calcination temperature in the step (1) is preferably 300 to 900 ℃, for example, but not limited to, 350 ℃, 400 ℃, 450 ℃,500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, and the like.
In the second aspect, the calcination time in the step (1) is preferably 1 to 9 hours, for example, but not limited to, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, 5.0 hours, 5.5 hours, 6.0 hours, 6.5 hours, 7.0 hours, 7.5 hours, 8.0 hours, 8.5 hours, etc.
In the second aspect described above, the diameter of the catalyst carrier is preferably 3 to 8mm, for example, but not limited to, the diameter of the spherical silica carrier may be 3.5mm, 4mm, 4.5mm, 5mm, 5.5mm, 6mm, 6.5mm, 7mm, 7.5mm, etc.
In the second aspect, the specific surface area of the catalyst carrier is preferably 50 to 260m 2 /g, for example but not limited to, the spherical silica support has a specific surface area of 60m 2 /g、70m 2 /g、80m 2 /g、90m 2 /g、100m 2 /g、110m 2 /g、120m 2 /g、130m 2 /g、140m 2 /g、150m 2 /g、160m 2 /g、170m 2 /g、180m 2 /g、190m 2 /g、200m 2 /g、210m 2 /g、220m 2 /g, etc.
In the second aspect, the pore volume of the catalyst carrier is preferably 0.4-1.5 cm 3 /g, e.g. but not limited to the spherical dioxygenThe pore volume of the silicon carbide carrier is 0.55cm 3 /g、0.6cm 3 /g、0.65cm 3 /g、0.7cm 3 /g、0.75cm 3 /g、0.8cm 3 /g、0.85cm 3 /g、0.9cm 3 /g、0.95cm 3 /g、1.0cm 3 /g、1.1cm 3 /g、1.2cm 3 /g、1.3cm 3 /g, etc.
In the second aspect, a non-limiting example of the palladium-containing compound in the step (2) may be chloropalladac acid.
In the above-described second aspect, a non-limiting example of the compound containing a promoter metal element in the step (2) may be chloroauric acid.
In the second aspect, the reducing agent in step (4) is not particularly limited, and the reducing agent may be a gas or a liquid independently, and preferably at least one of hydrogen and hydrazine hydrate independently.
In the second aspect, the alkali metal in step (5) independently preferably includes potassium.
In the second aspect, the drying temperature in the step (5) is independently preferably 60℃to 120℃such as, but not limited to, 65℃70℃75℃80℃85℃90℃95℃100℃105℃110℃115℃and the like, preferably 70℃to 90 ℃.
In the second aspect, the drying time of step (5) is independently preferably 1 to 8 hours, such as but not limited to 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, etc.
In order to solve the third technical problem of the present invention, a third technical scheme of the present invention is as follows:
third aspect of the invention
Use of the catalyst according to any one of the above-mentioned first aspect or the catalyst obtained according to the preparation method according to any one of the above-mentioned second aspect in the synthesis of vinyl acetate by the ethylene acyl oxidation process.
In order to solve the fourth technical problem of the present invention, a fourth technical scheme of the present invention is as follows:
fourth aspect of the invention
A process for the synthesis of vinyl acetate comprising reacting a feed gas comprising oxygen, ethylene, nitrogen and acetic acid in the presence of a catalyst according to any one of the above-described first aspects or a catalyst obtainable by a process according to any one of the above-described second aspects to obtain vinyl acetate.
In the fourth aspect, the composition of the raw material gas is preferably oxygen in a molar ratio: ethylene: nitrogen gas: acetic acid=1: a: b: c, a=5 to 7, b=4 to 8,c =1 to 2.
In the above-mentioned fourth aspect, a may be, by way of non-limiting example, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, etc.
In the above-mentioned fourth aspect, b may be, by way of non-limiting example, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, etc.
In the above-described fourth aspect, c may be, by way of non-limiting example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, etc.
In the fourth aspect, the reaction pressure is preferably 0.5 to 0.9MPa, for example, but not limited to, 0.55MPa, 0.6MPa, 0.65MPa, 0.70MPa, 0.75MPa, 0.8MPa, 0.85MPa, etc.
In the fourth aspect, the reaction temperature is preferably 130 to 200℃such as, but not limited to, 135℃140℃145℃150℃155℃160℃165℃170℃175℃180℃185℃190℃195 ℃.
In the fourth aspect, the raw material gas volume space velocity is preferably 1600 to 3000hr -1 Such as, but not limited to 1700hr -1 、1800hr -1 、1900hr -1 、2000hr -1 、2100hr -1 、2200hr -1 、2300hr -1 、2400hr -1 、2500hr -1 、2600hr -1 、2700hr -1 、2800hr -1 、2900hr -1 Etc.
Catalyst physical property evidence and data processing
1. Sampling method
Of the catalysts to be tested, 50 catalysts were randomly selected, and each catalyst was numbered 1,2 … …, i, … …,49, 50 in sequence, and the cross sections of the 50 catalysts were tested individually.
2. SEM-EDS measurement
The SEM-EDS parameters were set as: the SEM acceleration voltage was 20kV, the emission current was 10. Mu.A, the probe current mode was "High", and the working distance was 15mm.
3. Calculation of maximum value h of Zr element line scanning intensity
The position (distance from the catalyst surface to the position below the catalyst surface) where the intensity maximum value of the Zr line scanning signal of the ith catalyst appears is determined to be h by the thickness meter of the shell of each catalyst particle i The calculation formula of the catalyst h is as follows:
experimental results show that the catalyst has higher catalyst activity and longer catalyst service life in vinyl acetate production, and achieves better technical effect.
The invention is described in detail below with reference to the drawings and the detailed description
Drawings
FIG. 1 is an SEM-EDS spectrum of Zr along the radial direction of the catalyst particles according to example 1.
FIG. 2 is an SEM-EDS spectrum of Zr in the radial direction of the catalyst particles according to comparative example 2.
Detailed Description
[ example 1 ]
1. Catalyst preparation
(1)80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 1mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, regulating the pH value to 10.0, standing for 24 hours, calcining for 5 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
3. Catalyst evaluation
The evaluation was performed using a fixed bed reactor under the following specific conditions:
catalyst loading volume: 40ml;
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: 100hr;
the reaction product was analyzed for the content of each component by gas chromatography, and then the space-time yield of the catalyst was calculated, and the test data are shown in Table 1.
[ example 2 ]
1. Catalyst preparation
(1) At 110ml, the diameter was 5mm (specific surface was 180m 2 Per g, pore volume of 0.8cm 3 Adding ZrOCl to the spherical silica carrier of/g) 2 ·8H 2 And (3) 100ml of O aqueous solution, wherein the Zr content is 1mol/L, adding an ammonia water solution with the concentration of 1.5mol/L, adjusting the pH value to 10.0, standing for 24h, calcining at 500 ℃ for 5h, washing with water for 12h, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 3 ]
1. Catalyst preparation
(1) At 110ml, the diameter was 5mm (specific surface was 180m 2 Per g, pore volume of 0.8cm 3 Adding ZrOCl to the spherical silica carrier of/g) 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 1mol/L, adding sodium silicate nonahydrate solution, wherein the concentration of sodium silicate is 40g/L, adjusting the pH to 10.0, standing for 24h, calcining for 5h at 500 ℃, washing for 12h, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 4 ]
1. Catalyst preparation
(1) 80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 0.1mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, regulating the pH value to 10.0, standing for 24 hours, calcining for 5 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 5 ]
1. Catalyst preparation
(1) 80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 2.0mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, regulating the pH value to 10.0, standing for 24 hours, calcining for 5 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 6 ]
1. Catalyst preparation
(1) 80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 1.0mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, adjusting the pH value to 8.5, standing for 24 hours, calcining for 1 hour at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 7 ]
1. Catalyst preparation
(1) 80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 1.0mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, regulating the pH value to 12.0, standing for 24 hours, calcining for 9 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 8 ]
1. Catalyst preparation
(1) 80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 1.0mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, regulating the pH value to 10.0, standing for 24 hours, calcining for 5 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 9.17g/L and the content of gold is 10.18g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 9 ]
1. Catalyst preparation
(1) 80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 1.0mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, regulating the pH value to 10.0, standing for 24 hours, calcining for 9 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 0.92g/L and the content of gold is 0.11g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ example 10 ]
1. Catalyst preparation
(1) 80ml of sodium silicate nonahydrate solution, in which the concentration of sodium silicate was 40g/L, was taken, and 110ml of a solution having a diameter of 5mm (specific surface area of 180m was added 2 Per g, pore volume of 0.8cm 3 The spherical silica carrier of/g) to obtain a material i; adding ZrOCl into the material i 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content is 1.0mol/L, to prepare a material ii; adding ammonia water solution with the concentration of 1.5mol/L into the material ii, regulating the pH value to 10.0, standing for 24 hours, calcining for 9 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing palladium chloride acid and copper chloride is taken, wherein the content of palladium in the solution is 2.75g/L, the content of copper is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
Comparative example 1
1. Catalyst preparation
(1) Taking and containing120ml of a solution of chloropalladate and chloroauric acid, wherein the content of palladium in the solution was 2.75g/L and the content of gold was 0.60g/L, was added in a volume of 110ml and a diameter of 5mm (specific surface: 180m 2 Per g, pore volume of 0.8cm 3 The spherical silica support of/g) to give the catalyst precursor I;
(2) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(3) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(4) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
Comparative example 2
1. Catalyst preparation
(1) 380g of amorphous silica gel powder was taken together with 12g of conventional commercial ZrO 2 And 10g of methylcellulose are ground into an intimate mixture by a ball mill, the resulting mixture is absorbed with water and processed into a dough by a mixer, the dough is formed into a spherical shaped body by a tablet press under pressure, and calcined at 600℃for 5 hours to give a spherical support a having a diameter of 5 mm;
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and a spherical carrier a with the volume of 110ml is added to obtain a catalyst precursor I;
(2) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(3) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(4) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ comparative example 3 ]
1. Catalyst preparation
(1) 120ml of a solution containing palladium chloride acid and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, was added to a volume of 110ml of a solution having a diameter of 5mm (specific surface: 180m 2 Per g, pore volume of 0.8cm 3 The spherical silica support of/g) to give the catalyst precursor I;
(2) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(3) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(4) Addition of ZrOCl to catalyst precursor III 2 ·8H 2 100ml of O aqueous solution, wherein the Zr content in the aqueous solution is 1mol/L, calcining for 5 hours at 500 ℃, washing for 12 hours, and drying to obtain a catalyst precursor IV;
(5) The catalyst precursor IV is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
[ comparative example 4 ]
1. Catalyst preparation
(1) At a volume of 110ml, a diameter of 5mm (specific surface 180m 2 Per g, pore volume of 0.8cm 3 Adding ZrOCl to the spherical silica carrier of/g) 2 ·8H 2 And (3) 100ml of O aqueous solution, wherein the Zr content is 1mol/L, standing for 24 hours, calcining for 5 hours at 500 ℃, washing for 12 hours, and drying to obtain the catalyst carrier.
(2) 120ml of a solution containing chloropalladate and chloroauric acid, wherein the content of palladium in the solution is 2.75g/L and the content of gold is 0.60g/L, and 110ml of the catalyst carrier is added to obtain a catalyst precursor I;
(3) Adding 2.75g of sodium silicate nonahydrate into 100ml of water solution, uniformly mixing, standing for 24hr, and drying at 80deg.C for 8hr to obtain catalyst precursor II;
(4) Reducing the catalyst precursor II in a hydrogen atmosphere, wherein the flow rate of the hydrogen is 0.2ml/min, the pressure is 0.5MPa, the reduction temperature is 150 ℃, and the reduction time is 2 hours, so as to obtain a catalyst precursor III;
(5) The catalyst precursor III is immersed in a potassium acetate aqueous solution to make the content of potassium acetate 30g/L, and dried at 80 ℃ for 2 hours to obtain the finished catalyst.
2. Characterization of the catalyst
Adopting SEM-EDS to perform radial line scanning of Zr element on the catalyst section;
the grain sizes of the catalysts before and after evaluation are analyzed and calculated by XRD;
the element content in the catalyst was quantitatively analyzed by XRF.
The remaining procedure was the same as in example 1, and for convenience of comparison, catalyst supports and catalyst preparation process conditions are shown in Table 1. The reaction products were analyzed for the content of each component by gas chromatography, and then the space-time yields of the catalysts were calculated, and the test data obtained are shown in Table 1.
The present invention has found that ZrO is distributed in eggshells 2 /SiO 2 The composite carrier of (2) can obviously improve the activity and service life of the catalyst, wherein the service life of the catalyst can be characterized by the grain growth rate of the catalyst before and after 100hr evaluation, and the smaller the grain growth rate of the catalyst after 100hr evaluation, the longer the service life of the catalyst is generally considered.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
TABLE 1 characterization of catalytic Properties and evaluation of Activity
/>
Note that:
a is the grain size of the catalyst before evaluation;
b is the catalyst grain size after 100hr evaluation;
the grain growth rate = [ (b-a)/a ] ×100%.

Claims (12)

1. The vinyl acetate catalyst comprises a carrier, main catalyst metal palladium, promoter metal and alkali metal acetate, wherein the promoter is one or more of Au, sn and Cu, and the catalyst carrier comprises SiO 2 And as SiO 2 ZrO of modifier 2 The method is characterized in that when SEM-EDS is adopted to carry out line scanning of Zr element on the catalyst section along the radial direction, the maximum value of Zr signal intensity appears in the range of 0-0.8 mm of h, wherein h is the distance from the surface of the catalyst to the position below the surface of the catalyst; the content of Zr element is 0.5-18 g/L; the diameter of the catalyst carrier is 4-8 mm.
2. The vinyl acetate catalyst according to claim 1, characterized in that the Pd content of the main catalyst is 1.0-10.0 g/L; and/or the content of the cocatalyst is 0.1-10 g/L.
3. The catalyst according to claim 1, wherein the specific surface area of the catalyst carrier is 50 to 260m 2 /g; and/or the pore volume of the carrier is 0.4-1.5 cm 3 /g。
4. The catalyst according to claim 3, wherein the specific surface area of the catalyst carrier is 120 to 260m 2 /g。
5. The method for preparing a vinyl acetate catalyst according to any one of claims 1 to 4, comprising:
(1) Mixing a solution for dissolving Zr-containing compounds and an alkali solution i with a spherical silica carrier, standing, calcining and washing to obtain a catalyst carrier;
(2) Mixing a solution dissolved with a palladium-containing compound and an additive element-containing compound with a catalyst carrier to obtain a catalyst precursor I;
(3) Treating the catalyst precursor I by adopting an alkali solution II to convert the palladium-containing compound and the additive element-containing compound into a precipitate, and washing and drying the precipitate to obtain the catalyst precursor II;
(4) Reducing the palladium in the compound state in the catalyst precursor II to zero-valent palladium by adopting a reducing agent to obtain a catalyst precursor III;
(5) Impregnating a catalyst precursor III with an alkali metal acetate solution to obtain a catalyst precursor IV, and drying to obtain the catalyst;
the Zr content in the Zr compound solution is 0.1-2.0 mol/L.
6. The method for preparing a catalyst according to claim 5, wherein the calcination temperature is 300 to 900 ℃; and/or calcining for 1-9 h.
7. Use of the catalyst according to any one of claims 1 to 4 or the catalyst obtained by the preparation method according to claim 5 or 6 in synthesizing vinyl acetate by an ethylene acyl oxidation method.
8. A method for synthesizing vinyl acetate, wherein raw material gases comprising oxygen, ethylene, nitrogen and acetic acid are reacted in the presence of the catalyst according to any one of claims 1 to 4 or the catalyst obtained by the preparation method according to claim 5 or 6 to obtain vinyl acetate.
9. The synthesis method according to claim 8, wherein the feed gas composition is oxygen in molar ratio: ethylene: nitrogen gas: acetic acid=1: a: b: c, a=5 to 7, b=4 to 8,c =1 to 2.
10. The synthesis method according to claim 8, wherein the reaction pressure is 0.5 to 0.9MPa.
11. The synthesis method according to claim 8, wherein the reaction temperature is 130 to 200 ℃.
12. The synthesis process according to claim 8, wherein the volume space velocity of the feed gas is 1600 to 3000hr -1 。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1185145A (en) * 1995-05-23 1998-06-17 人造丝有限公司 Process and catalyst for producing vinyl acetate
CN106423128A (en) * 2015-08-10 2017-02-22 中国石油化工股份有限公司 Catalyst for producing vinyl acetate through acetylene method
CN106582825A (en) * 2015-10-19 2017-04-26 中国石油化工股份有限公司 Catalyst for preparation of allyl acetate
CN106582869A (en) * 2015-10-19 2017-04-26 中国石油化工股份有限公司 Catalyst for preparing vinyl acetate by ethylene method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1185145A (en) * 1995-05-23 1998-06-17 人造丝有限公司 Process and catalyst for producing vinyl acetate
CN106423128A (en) * 2015-08-10 2017-02-22 中国石油化工股份有限公司 Catalyst for producing vinyl acetate through acetylene method
CN106582825A (en) * 2015-10-19 2017-04-26 中国石油化工股份有限公司 Catalyst for preparation of allyl acetate
CN106582869A (en) * 2015-10-19 2017-04-26 中国石油化工股份有限公司 Catalyst for preparing vinyl acetate by ethylene method

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