CN114177939B - Catalyst for synthesizing vinyl acetate by acetylene method - Google Patents

Catalyst for synthesizing vinyl acetate by acetylene method Download PDF

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Publication number
CN114177939B
CN114177939B CN202010958280.2A CN202010958280A CN114177939B CN 114177939 B CN114177939 B CN 114177939B CN 202010958280 A CN202010958280 A CN 202010958280A CN 114177939 B CN114177939 B CN 114177939B
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catalyst
cucurbituril
zinc acetate
acetylene
vinyl acetate
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CN114177939A (en
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邱鹏远
刘燕
杨运信
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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0249—Ureas (R2N-C(=O)-NR2)
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0254—Nitrogen containing compounds on mineral substrates
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention relates to a catalyst for synthesizing vinyl acetate by an acetylene method and a preparation method thereof, and mainly solves the problem of high benzene content of byproducts in the prior art. The invention provides a catalyst for synthesizing vinyl acetate by an acetylene method, which comprises the following components: a carrier, and the following components supported on the carrier per liter of catalyst: 160-240 g/L zinc acetate; cucurbituril 1.0-10 g/L; the carrier is the technical scheme of the active carbon, so that the problem is well solved, and the carrier can be used in the industrial production of the acetylene-method vinyl acetate.

Description

Catalyst for synthesizing vinyl acetate by acetylene method
Technical Field
The invention relates to a vinyl acetate catalyst prepared by an acetylene gas phase method, a preparation method of the catalyst and a synthesis method of vinyl acetate.
Background
Vinyl acetate, abbreviated as Vinyl Acetate (VAM), is one of important organic chemical raw materials, and is mainly used for producing polyvinyl alcohol, polyvinyl acetate, vinyl acetate-ethylene copolymer emulsion or copolymer resin and other derivatives, and along with the increase of the demand of human society for high-performance resin materials, the market demand of vinyl acetate and downstream derivatives thereof is still steadily increasing.
At present, the world vinyl acetate productivity is about 900 ten thousand tons/year, and the vinyl acetate productivity in China reaches 320 ten thousand tons/year. The main production process routes include an ethylene process and an acetylene process, and the ethylene process is mainly adopted in European and American countries, and the acetylene process is still mainly adopted in China at present. In recent years, with the rise of domestic civil petrochemical enterprises, the demand for high-quality VAM is rapidly increased, the product quality is higher, and an ethylene process route with lower impurity content is more and more favored by the market.
However, about 80% of domestic VAM capacity still adopts an acetylene method production process, and at present, one of the biggest problems of the process is that trace impurity benzene in the product VAM affects the quality of the product, and prevents the product from being applied as a monomer of food-grade polymer materials (such as food packaging materials, cigarette adhesive and the like). However, since the benzene content in the product is extremely low (. Ltoreq.5 ppm), it is difficult to conduct effective separation by separation purification techniques such as rectification. Therefore, the academic world also considers the methods of modifying the catalyst carrier, adding auxiliary agents, optimizing the formula and the like to improve the selectivity of the catalyst and inhibit side reactions to generate benzene. Some success has been achieved over the years of effort, but there is still a significant difference compared to the product VAC using the ethylene process.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem of high benzene content in products in the prior art, and provide a novel vinyl acetate catalyst which has the characteristic of low benzene content as a byproduct.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to one of the above technical problems.
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 method for synthesizing vinyl acetate by adopting the catalyst in one of the technical problems.
In order to solve one of the technical problems, the technical scheme of the invention is as follows:
a catalyst for acetylene-process vinyl acetate synthesis, the catalyst comprising: a carrier, and the following components supported on the carrier per liter of catalyst:
160-240 g/L zinc acetate;
cucurbituril 1.0-10 g/L;
the carrier is activated carbon.
In the catalyst in the prior art, the benzene content in the obtained vinyl acetate product is very high. The applicant has surprisingly found that the benzene content of the vinyl acetate product is greatly reduced by the addition of cucurbituril to the catalyst of the invention. Cucurbiturils are highly symmetrical cucurbiturils with large ring cavities and two open ends, and are commonly used in the fields of molecular assembly, molecular motors and the like. Cyclodextrin also has a large annular cavity, but does not have the effect of reducing the benzene content of the product.
In the above technical scheme, the cucurbituril preferably comprises at least one of the group consisting of cucurbituril [6] urea, cucurbituril [7] urea and cucurbituril [8] urea.
In the above technical scheme, as non-limiting examples, examples of the zinc acetate content in the catalyst can be, but not limited to, 170g/L, 180g/L, 190g/L, 200g/L, 210g/L, 220g/L, 230g/L, etc.
In the above technical scheme, as non-limiting examples, the cucurbituril content in the catalyst can be 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 embodiments, the activated carbon support is not particularly limited in geometry, and may be, for example, cylindrical activated carbon. In this case the diameter may be 1.5 to 3.5mm and/or the length may be 3.0 to 5.0mm. For convenience of comparison, columnar activated carbon with the diameter of 2.7mm and the length of 4.0mm is adopted in the specific embodiment of the invention.
In the technical proposal, the specific surface area of the carrier is 1000-2000 m 2 By way of non-limiting example, the specific surface area of the support may be 1050m 2 /g，1100m 2 /g，1150m 2 /g，1200m 2 /g，1250m 2 /g，1300m 2 /g，1350m 2 /g，1400m 2 /g，1450m 2 /g，1500m 2 /g，1550m 2 /g，1600m 2 /g，1650m 2 /g，1700m 2 /g，1750m 2 /g，1800m 2 /g，1850m 2 /g，1900m 2 /g，1950m 2 /g, etc.
In the technical proposal, the total pore volume of the carrier adsorption is 0.2 cm to 0.8cm 3 By way of non-limiting example, the total pore volume of the carrier adsorption may be 0.25cm 3 /g，0.30cm 3 /g，0.35cm 3 /g，0.40cm 3 /g，0.45cm 3 /g，0.50cm 3 /g，0.55cm 3 /g，0.60cm 3 /g，0.65cm 3 /g，0.70cm 3 /g，0.75cm 3 /g, etc.
In order to solve the second technical problem, the technical scheme is as follows:
a method for preparing a catalyst comprising the steps of:
(1) Loading zinc acetate and cucurbituril on the activated carbon to obtain a catalyst precursor;
(2) And drying the catalyst precursor to obtain the catalyst.
In the technical scheme, the cucurbituril in the step (1) comprises at least one of cucurbituril [6] uril, cucurbituril [7] uril and cucurbituril [8] uril.
In the above technical solution, the embodiment of step (1) may be selected from any one of the following methods:
method a: mixing and impregnating the impregnating solution containing zinc acetate and cucurbituril with activated carbon;
method b: the cucurbituril is loaded by an impregnation method, and zinc acetate is loaded by the impregnation method;
method c: zinc acetate is loaded by the impregnation method, and cucurbituril is loaded by the impregnation method.
In the above technical scheme, the method a, the method b and the method c in the step (1) in the catalyst preparation method can all achieve the purpose of the invention, but we find that the catalyst obtained by the method a has the lowest benzene content and the highest space-time yield.
In the above technical scheme, the temperature of the impregnation in the step (1) is preferably 20-50 ℃. Such as, but not limited to, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, and the like.
In the above technical solution, the dipping time in the step (1) is preferably 1 to 8 hours, for example, but not limited to, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, etc.
In the above technical solution, the concentration of cucurbituril in the impregnating solution in step (1) is 0.5-5.0g/L, for example, but not limited to, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, etc.
In the above technical solution, the concentration of zinc acetate in the impregnating solution in step (1) is 80.0-120.0g/L, for example, but not limited to, 85g/L, 90g/L, 95g/L, 100g/L, 105g/L, 110g/L, 115g/L, etc.
In the above technical scheme, the drying temperature in the step (2) is preferably 100-120 ℃. Such as, but not limited to, 105 ℃,110 ℃, 115 ℃, and the like. The drying time is preferably 1 to 3 hours, such as, but not limited to, 1.5 hours, 2.0 hours, 2.5 hours, and the like.
In order to solve the third technical problem, the technical scheme of the invention is as follows: use of the catalyst according to any one of the technical solutions of the above technical problems or the catalyst obtained by the preparation method according to any one of the technical solutions of the second technical problems in the synthesis of vinyl acetate by acetylene method.
In order to solve the fourth technical problem, the technical scheme of the invention is as follows: the synthesis method of vinyl acetate comprises the steps of taking acetic acid and acetylene as raw materials, and reacting in the presence of the catalyst according to any one of the technical schemes of the technical problems or the catalyst obtained by the preparation method according to any one of the technical schemes of the second technical problems of the technical problems.
The technical key of the invention is the catalyst, and for the specific process conditions adopted by the synthesis method, the technical key can be reasonably selected by the skilled in the art and can obtain comparable technical effects. However:
in the above technical scheme, the molar ratio of acetylene to acetic acid is preferably 5-12, such as but not limited to 6, 7, 8, 9, 10, 11, etc.
In the above technical scheme, the reaction pressure is preferably 0.1 to 0.5atm, such as, but not limited to, 0.15atm, 0.2atm, 0.25atm, 0.3atm, 0.35atm, 0.4atm, 0.45atm, and the like.
In the above-mentioned technical scheme, the reaction temperature is preferably 160 to 220 ℃, for example, but not limited to 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, and the like.
In the technical proposal, the volume space velocity of the raw materials (the sum of acetic acid and acetylene) is 250 to 350h -1， 。
The reaction pressures are gauge pressures.
The conversion per pass of acetylene according to the invention is calculated by the following formula:
acetylene single pass conversion= (reaction inlet acetylene amount-reaction outlet acetylene amount)/(reaction inlet acetylene amount) ×100%;
the acetylene amount at the reaction inlet is controlled by a mass flowmeter, in the patent, the acetylene flow is selected to be 200ml/min, and the acetylene amount at the reaction outlet is measured by a rotameter.
Detailed Description
[ example 1 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) 0.5g of cucurbit [6]]Urea (C) 36 H 36 N 24 O 12 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L, and the concentration of cucurbituril is 2.5g/L; mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 2 ]
(I) Catalyst preparation
(1) Weighing 0.5g of calabash [6]]Urea (C) 36 H 36 N 24 O 12 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the cucurbituril concentration is 2.5g/L, mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) Placing the catalyst precursor A in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain a catalyst precursor B;
(3) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) mixing with pure water to prepare 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L; mixing 100ml of catalyst precursor B with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor C;
(4) And (3) placing the catalyst precursor C in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 3 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) is mixed with pure water to prepare 200ml of a mixed solution asMixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) Placing the catalyst precursor A in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain a catalyst precursor B;
(3) Weighing 0.5g of calabash [6]]Urea (C) 36 H 36 N 24 O 12 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the cucurbituril concentration is 2.5g/L; mixing 100ml of catalyst precursor B with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor C;
(4) And (3) placing the catalyst precursor C in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 4 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 16g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) 0.1g of calabash [6]]Urea (C) 36 H 36 N 24 O 12 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solutionThe concentration of zinc acetate in the feed is 80g/L, and the concentration of cucurbituril is 0.5g/L; mixing 100ml of active carbon with the impregnating solution, and impregnating for 1h at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=5:1;
volume space velocity of reaction raw materials: 250h -1 ；
Reaction pressure: 0.1atm;
reaction temperature: 160 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 5 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 24g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) 1.0g of calabash [6]]Urea (C) 36 H 36 N 24 O 12 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 120g/L, and the concentration of cucurbituril is 5.0g/L; mixing 100ml of active carbon with the impregnating solution, and impregnating for 8 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=12:1;
volume space velocity of reaction raw materials: 350h -1 ；
Reaction pressure: 0.5atm;
reaction temperature: 220 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 6]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) 0.5g of calabash [7]]Urea (C) 42 H 42 N 28 O 14 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L, and the concentration of cucurbituril is 2.5g/L; mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 7]
(I) Catalyst preparation
(1) Weighing 0.5g of calabash [7]]Urea (C) 42 H 42 N 28 O 14 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the cucurbituril concentration is 2.5g/L, mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) Placing the catalyst precursor A in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain a catalyst precursor B;
(3) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) mixing with pure water to prepare 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L; mixing 100ml of catalyst precursor B with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor C;
(4) And (3) placing the catalyst precursor C in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 8]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 Mixing O) with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L, mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) Placing the catalyst precursor A in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain a catalyst precursor B;
(3) Weighing 0.5g of calabash [7]]Urea (C) 42 H 42 N 28 O 14 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the cucurbituril concentration is 2.5g/L; mixing 100ml of catalyst precursor B with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor C;
(4) And (3) placing the catalyst precursor C in a blast drying oven, drying at 110 ℃ for 3 hours, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 9 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) 0.5g of calabash [8]]Urea (C) 48 H 48 N 32 O 16 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L, and the concentration of cucurbituril is 2.5g/L; mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ example 10 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 24g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O) 1.0g of calabash [8]]Urea (C) 48 H 48 N 32 O 16 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solutionWherein the concentration of zinc acetate is 120g/L, and the concentration of cucurbituril is 5.0g/L; mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ comparative example 1 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 Mixing O) with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L, mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
[ comparative example 2 ]
(I) Catalyst preparation
(1) Zinc acetate dihydrate (C) containing 20g of zinc acetate was weighed out 4 H 6 O 4 Zn·2H 2 O), 0.5g of beta-cyclodextrin (C) 42 H 70 O 35 ) Mixing with pure water to obtain 200ml of mixed solution as impregnating solution, wherein the concentration of zinc acetate is 100g/L, and the concentration of beta-cyclodextrin is 2.5g/L; mixing 100ml of active carbon with the impregnating solution, and impregnating for 4 hours at the room temperature of 25 ℃ to obtain a catalyst precursor A;
(2) And (3) placing the catalyst precursor A in a blast drying oven, drying for 3 hours at 110 ℃, and cooling to obtain the catalyst.
The preparation conditions and catalyst composition of the catalyst are shown in Table 1.
(II) evaluation of catalyst Performance
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): acetylene acetic acid=6:1;
volume space velocity of reaction raw materials: 300h -1 ；
Reaction pressure: 0.3atm;
reaction temperature: 180 ℃;
reaction time: and 100h.
The vinyl acetate content of the reaction product was analyzed by gas chromatography, and the space-time yield of the catalyst was calculated. The reaction products were analyzed for benzene content by GC-MS, and the main conditions are shown in Table 2 for comparison.
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 catalyst preparation and characterization
Note that: in the impregnation mode, -a represents co-impregnation, b represents impregnation of cucurbituril first and then impregnation of zinc acetate, and c represents impregnation of zinc acetate first and then impregnation of cucurbituril.
Table 2 catalyst evaluation
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Claims (15)

1. A catalyst for acetylene-process vinyl acetate synthesis, the catalyst comprising: a carrier, and the following components supported on the carrier per liter of catalyst:
160-240 g/L of zinc acetate;
cucurbituril 1.0-10 g/L;
the carrier is activated carbon.
2. The catalyst of claim 1, wherein the cucurbituril comprises at least one of the group consisting of cucurbituril [6] urea, cucurbituril [7] urea, and cucurbituril [8] urea.
3. The catalyst according to claim 1, characterized in that the activated carbon support is cylindrical activated carbon.
4. The catalyst according to claim 3, wherein the diameter of the cylindrical activated carbon is 1.5-3.5 mm; the length is 3.0-5.0 mm.
5. The catalyst according to claim 1, wherein the specific surface area of the carrier is 1000 to 2000m 2 /g。
6. The catalyst according to claim 1, wherein the total pore volume of adsorption of the carrier is 0.2-0.8 cm 3 /g。
7. The catalyst preparation method of the catalyst according to any one of claims 1 to 6, comprising the steps of:
(1) Loading zinc acetate and cucurbituril on the activated carbon to obtain a catalyst precursor;
(2) And drying the catalyst precursor to obtain the catalyst.
8. The method according to claim 7, wherein the embodiment of step (1) is selected from any one of the following methods:
method a: mixing and impregnating the impregnating solution containing zinc acetate and cucurbituril with activated carbon;
method b: the cucurbituril is loaded by an impregnation method, and zinc acetate is loaded by the impregnation method;
method c: zinc acetate is loaded by the impregnation method, and cucurbituril is loaded by the impregnation method.
9. The preparation method according to claim 8, wherein the concentration of cucurbituril in the impregnating solution is 0.5-5.0 g/L.
10. The method according to claim 9, wherein the concentration of zinc acetate in the impregnating solution is 80.0 to 120.0 g/L.
11. Use of the catalyst according to any one of claims 1 to 6 or the catalyst obtained according to the preparation method of any one of claims 7 to 10 in the synthesis of acetylene-process vinyl acetate.
12. A method for synthesizing vinyl acetate, comprising the steps of reacting acetic acid and acetylene as raw materials in the presence of the catalyst according to any one of claims 1 to 6 or the catalyst obtained by the preparation method according to any one of claims 7 to 10 to obtain vinyl acetate.
13. The synthesis method according to claim 12, wherein the molar ratio of acetylene to acetic acid is 5-12.
14. The synthesis method according to claim 12, wherein the reaction pressure is 0.1 to 0.5atm.
15. The synthesis method according to claim 12, wherein the reaction temperature is 160-220 ℃.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103878023A (en) * 2012-12-19 2014-06-25 中国石油化工股份有限公司 Preparation method of catalyst for synthesizing vinyl acetate
CN104437623A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Catalyst for acetylene-method vinyl acetate and synthesis method of vinyl acetate
CN105498778A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 Acetylene process vinyl acetate catalyst
CN107313066A (en) * 2017-07-24 2017-11-03 中国科学院福建物质结构研究所 Supported catalyst and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103878023A (en) * 2012-12-19 2014-06-25 中国石油化工股份有限公司 Preparation method of catalyst for synthesizing vinyl acetate
CN104437623A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Catalyst for acetylene-method vinyl acetate and synthesis method of vinyl acetate
CN105498778A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 Acetylene process vinyl acetate catalyst
CN107313066A (en) * 2017-07-24 2017-11-03 中国科学院福建物质结构研究所 Supported catalyst and its preparation method and application

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