CN106582824B - Catalyst for synthesizing ethylene method vinyl acetate - Google Patents
Catalyst for synthesizing ethylene method vinyl acetate Download PDFInfo
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- CN106582824B CN106582824B CN201510675455.8A CN201510675455A CN106582824B CN 106582824 B CN106582824 B CN 106582824B CN 201510675455 A CN201510675455 A CN 201510675455A CN 106582824 B CN106582824 B CN 106582824B
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- 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
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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
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- 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 present invention relates to the catalyst for synthesizing ethylene method vinyl acetate, mainly solve the problems, such as that catalyst activity and selectivity is not high in the prior art.The present invention uses the catalyst for synthesizing ethylene method vinyl acetate, and the catalyst includes carrier, active component and co-catalyst；The carrier uses SiO2、Al2O3Or its mixture, the active component include metal Pd and metal Au, the co-catalyst is selected from the technical solution of the compound of at least one of alkali metal and vib metal metallic element, preferably solves the problems, such as this, can be used in the industrial production of vinyl acetate.
Description
Technical field
The present invention relates to the preparation methods and vinyl acetate of catalyst, catalyst for synthesizing ethylene method vinyl acetate
Synthetic method.
Background technique
Vinyl acetate (VAc) is one of maximum 50 kinds of industrial chemicals of world wide production, is total to by autohemagglutination or with other monomers
It is poly-, polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) lotion, vinyl acetate-ethylene copolymerization emulsions (VAE) or total can be generated
The derivatives such as poly resin (EVA), vinyl acetate-chloride copolymer (EVC).These derivatives are widely used in adhesive, build
Cementing agent, coating, ink, leather processing, fiber process, emulsifier, water-solubility membrane and the soil for building coating, paper or fabric change
Good dose etc..In the world today produce ethylene process vinyl acetate main method be using ethylene, oxygen and acetic acid as raw material, with
Pd-Au-KOAc/SiO2System makees catalyst, is synthesized by gas phase catalytic reaction.
From after the technique of nineteen seventies discovery ethylene vapor phase method production vinylacetate, people are dedicated to higher
The catalyst research of reactivity and selectivity.Currently, people more concentrate on research precious metal palladium and gold or other elements exist
Dispersion and distribution on carrier, distribution of the active component on carrier also develop to eggshell type, the utilization of noble metal from protein type
Rate effectively improves, and increases the reactivity of units activity component agent, reduces the generation of side reaction, improves reaction choosing
Selecting property.
Chinese patent (CN1226188A is used to prepare the palladium-gold catalyst of vinyl acetate), which provides, a kind of prepares load
There is the preparation method of the catalyst of major catalyst noble metal, promoter metal and alkali or alkaline earth metal compound.It has
Body manufacturing process is as follows: 1. in the dipping tank of rotation, the mixed liquor of configured noble metal and co-catalyst being added, is passed through
Hot-air is dry；2., will be original in the catalyst after taking a certain amount of solution with alkaline matters such as sodium metasilicate to make an addition to drying
The palladium and gold of the chlorination state of water soluble are converted to the insoluble hydroxide state palladium of water and gold；3. restoring hydroxide in nitrogen atmosphere
The palladium and Au catalyst of state are reduced into the palladium and Au catalyst of metallic state；4. it is washed till no chloride ion, it is dry, potassium acetate is soaked,
Up to the catalyst after drying.
United States Patent (USP) (US 3743607, entitled Palladium-gold catalyst) describes urging for homogeneous impregnation
The preparation method of agent, this method comprises: 1. with palladium, the solution impregnating carrier of gold compound；2. drying；3. palladium, aurification are closed
Object is reduced to Metal Palladium, gold；4. washing, drying.
United States Patent (USP) (US 4048096, entitled Surface impregnated catalyst) describes shell leaching
The preparation method of the catalyst of stain, this method comprises: 1. with the solution impregnating carrier containing palladium, gold compound；2. the load after dipping
Body is contacted with the aqueous solution of the sodium metasilicate containing alkali compounds, water-soluble palladium, gold compound is precipitated as insoluble palladium, aurification is closed
Object；3. palladium, gold compound are changed into Metal Palladium, gold with reducing agent；4. dry after being contacted after washing with alkali metal acetate
To the catalyst.The space time yield and selectivity of catalyst obtained by the above method are lower.
Summary of the invention
The first technical problem to be solved by the present invention is the vinyl acetate catalyst activity and choosing synthesized in the prior art
The not high problem of selecting property.A kind of catalyst for synthesizing ethylene method vinyl acetate is provided, which has high activity high
The feature of selectivity.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of technical problem.
The third technical problem to be solved by the present invention is using catalyst synthesizing vinyl acetate described in one of technical problem
Method.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: being used for synthesizing ethylene method acetic acid
The catalyst of ethylene, the catalyst include carrier, active component and co-catalyst；The carrier uses SiO2、Al2O3Or
Its mixture, the active component include metal Pd and metal Au, the co-catalyst in alkali metal and vib metal extremely
A kind of compound of few metallic element.
In above-mentioned technical proposal, the alkali metal element preferably is selected from least one of Li, Na, K, Rb and Cs；More preferably
The alkali metal includes K and at least one of selected from Li, Na, Rb and Cs simultaneously.
At least one of vib metal element described in above-mentioned technical proposal preferred Cr, Mo and W；
In above-mentioned technical proposal, as most preferred technical solution, the catalyst includes simultaneously Pd, Au, potassium acetate, choosing
From the alkali metal compound of at least one of Li, Na, Rb and Cs and the compound of vib metal element；Such as the catalyst
Including Pd, Au, potassium acetate, Rb (or Cs) and Cr, perhaps including Pd, Au, potassium acetate, Rb, Cs and Cr (or Mo) or including
Pd, Au, potassium acetate, Rb, Cs, Cr and Mo composition.
In above-mentioned technical proposal, the content of Pd is preferably 1.0~12.0g/L in the catalyst.
In above-mentioned technical proposal, the content of Au is preferably 0.1~10.0g/L in the catalyst.
In above-mentioned technical proposal, at least one content of metal is preferably in alkali metal and VIB described in catalyst
0.5~7.0g/L, the alkali metal is selected from least one of Li, Na, Rb and Cs at this time.
In above-mentioned technical proposal, when alkali metal described in catalyst is selected from including K, K is in terms of potassium acetate, the catalyst
The content of middle potassium acetate is preferably 10~90g/L.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
Method for preparing catalyst described in case, includes the following steps:
(1) compound solution of the compound of palladium, gold is mixed by the composition of catalyst with carrier, arrives catalyst precarsor I；
(2) so that compound containing Pd, compound containing Au is converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(3) compound state Pd in catalyst precarsor II and compound state Au are reduced to metal Pd and before metal Au obtains catalyst
Body III；
(4) metallic compound in alkali metal compound and/or VIB is supported on by the composition of catalyst using infusion process and is urged
Agent precursor II I obtains catalyst.
In above-mentioned technical proposal, the reducing agent of the understanding step (3) based on those skilled in the art is not specially required, also
Former agent can be at least one of gas or liquid, the preferred hydrogen of reducing agent, hydrazine hydrate；Step (4) drying temperature is preferred
It is 80~120 DEG C, drying time is preferably 1~5 hour.
In above-mentioned technical proposal, step (4) described alkali metal compound preferably is selected from alkali carbonate, bicarbonate and vinegar
At least one of hydrochlorate.The preferred chromic acetate of the vib metal compound, chromic nitrate, chromium chloride, acetic acid molybdenum, ammonium molybdate, pentachloro-
Change at least one of molybdenum and ammonium tungstate；More preferably from least one of chromic acetate and acetic acid molybdenum.
To solve above-mentioned technical problem three, technical scheme is as follows: the synthetic method of ethylene process vinyl acetate,
Using ethylene, acetic acid and oxygen as raw material, reaction obtains vinyl acetate in the presence of above-mentioned catalyst.
Key of the invention is the selection of catalyst, and skilled person will know how suitable determine according to actual needs
Reaction temperature, the reaction time, reaction pressure and material proportion.But in above-mentioned technical proposal, the temperature of reaction is preferably
130~150 DEG C, reaction pressure be preferably 0.1~1.0MPa, with molar ratio computing ethylene: acetic acid: oxygen be preferably 1:(0.1~
0.3): (0.05~0.2), raw material volume air speed are preferably 1500~2500h-1。
Compared with prior art, key of the invention to be in catalyst include metal Pd, metal Au and selected from alkali metal and
The compound of at least one of vib metal metallic element is conducive to the activity and stability that improve catalyst, to improve
The yield of vinyl acetate.
The catalyst of above method synthesis and comparative catalyst are evaluated with evaluating apparatus respectively and calculate catalyst
Activity and and selectivity.Evaluation method be in the reactor loading 900ml catalyst, using nitrogen leak test, it is ensured that system without
After leak source, the flow of ethylene is adjusted to 64.4mol/h, is heated up simultaneously, when reaction bed temperature reaches 120 DEG C, investment
The acetic acid of 9.30mol/h, starts to throw oxygen after twenty minutes, sufficient oxygen is thrown after 120 minutes, the amount of oxygen is 3.88mol/h, and air speed is
2000h-1, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa in reaction process, controls raw material ratio are as follows: and ethylene/acetic acid/
Oxygen=83.0/12.0/5.0 (molar ratio).
The content of each component in gas chromatography analysis reaction product, and be calculated according to the following formula catalyst activity (when
Empty yield) and selectivity:
The experimental results showed that the activity of catalyst reaches 375.21g/Lh, Dichlorodiphenyl Acetate second when using catalyst of the present invention
The selectivity of alkene is 95.08%, achieve in preferable technical effect, especially catalyst include simultaneously metal Pd, metal Au,
At least one of alkali metal metallic element compound and when selected from least one of VIB metallic element compound, achieves
Technical effect more outstanding, can be used in the industrial production of vinyl acetate.The present invention is made below by embodiment further
It illustrates.
Specific embodiment
[embodiment 1]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) it weighs potassium acetate containing 33g and the acetic acid rubidium containing 1.06gRb is sufficiently mixed and is dissolved in pure water, obtain maceration extract
500ml is immersed on precursor II I, in 100 DEG C of dryings, obtains the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Rb content is 1.06g/L, acetic acid
Potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 375.21g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.08%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 2]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromic acetate (Cr (OAc) containing 1.06gCr3·6H2O) aqueous solution 200ml is immersed on precursor II I, through 110
DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；The solution 300ml for weighing the potassium acetate containing 33g, is immersed in precursor I V
On, in 100 DEG C of dryings, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Cr content is 1.06g/L, acetic acid
Potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 374.92g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.14%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) the solution 300ml for weighing the potassium acetate containing 33g, is immersed on precursor II I, in 100 DEG C of dryings, obtains described urge
Agent.
The Pd content for measuring the catalyst through ICP is 3.83g/L, Au content 1.87g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 365.49g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 94.27%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
The catalyst used by can be seen that the present invention compared with Examples 1 to 2, using simultaneously containing Pd, Au, acetic acid
Potassium and acetic acid rubidium, the simultaneously catalyst performance containing Pd, Au, potassium acetate and chromic acetate are than the property containing only Pd, Au, potassium acetate catalyst
Can be more excellent, the space-time yield of vinyl acetate catalyst will be high.
[embodiment 3]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape Al2O3Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) it weighs potassium acetate containing 33g and the cesium acetate containing 1.06gCs is sufficiently mixed and is dissolved in pure water, obtain maceration extract
500ml is immersed on precursor II I, in 100 DEG C of dryings, obtains the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Cs content is 1.06g/L, acetic acid
Potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 375.62g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.05%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 4]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) it weighs potassium acetate containing 33g and the sodium acetate containing 1.06gNa is sufficiently mixed and is dissolved in pure water, obtain maceration extract
500ml is immersed on precursor II I, in 100 DEG C of dryings, obtains the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Na content is 1.06g/L, acetic acid
Potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 375.15g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.03%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 5]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and it is 5.6mm's that carrier 1.0L diameter is immersed in turning pot
Spherical SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) it weighs potassium acetate containing 33g and the lithium acetate containing 1.06gLi is sufficiently mixed and is dissolved in pure water, obtain maceration extract
500ml is immersed on precursor II I, in 100 DEG C of dryings, obtains the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Li content is 1.06g/L, acetic acid
Potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 375.40g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.13%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 6]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid molybdenum (Mo containing 1.06gMo2(OAc)4) be dissolved in the aqueous acetic acid that concentration is 60wt%, it obtains
Maceration extract 200ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；It weighs and contains
The solution 300ml of 33g potassium acetate, is immersed on precursor I V, in 100 DEG C of dryings, obtains the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Mo content is 1.06g/L, acetic acid
Potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 375.32g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 94.98%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 7]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the ammonium tungstate ((NH containing 1.06gW4)10W12O41·4H2O) aqueous solution 200ml is immersed on precursor II I, warp
110 DEG C of vacuum drying, 400 DEG C of roastings, obtain catalyst precarsor IV；The solution 300ml for weighing the potassium acetate containing 33g, before being immersed in
On body IV, in 100 DEG C of dryings, the catalyst is obtained.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, W content is 1.06 g/L, acetic acid
Potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 374.95g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.02%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 8]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromic acetate (Cr (OAc) containing 0.40gCr3·6H2O it) is sufficiently mixed and is dissolved in pure water, obtain maceration extract
100ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；Weigh vinegar containing 33g
Sour potassium and acetic acid rubidium containing 0.66gRb, which are sufficiently mixed, to be dissolved in pure water, is obtained maceration extract 400ml, is immersed on precursor I V,
100 DEG C of dryings, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Rb content is 0.66g/L, and Cr contains
Amount is 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 378.82g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.84%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis by embodiment 8 and embodiment 1 and embodiment 2, improve vinyl acetate catalyst space-time yield and
In terms of selectivity, metal Rb has with Cr in vib metal in the catalyst that the present invention uses, in alkali metal element preferably cooperates with work
With, illustrate between metal Pd, metal Au, potassium acetate, acetic acid rubidium and chromic acetate improve catalyst activity and selectivity side
Face has preferable synergistic effect.
[embodiment 9]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromic acetate (Cr (OAc) containing 0.40gCr3·6H2O it) is sufficiently mixed and is dissolved in the water, obtain maceration extract
100ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；Weigh vinegar containing 33g
Sour potassium and cesium acetate containing 0.66gCs, which are sufficiently mixed, to be dissolved in pure water, is obtained maceration extract 400ml, is immersed on precursor I V,
100 DEG C of dryings, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Cs content is 0.66g/L, and Cr contains
Amount is 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 378.73g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.96%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 10]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromic acetate (Cr (OAc) containing 0.40gCr3·6H2O it) is sufficiently mixed and is dissolved in the water, obtain maceration extract
100ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；Weigh vinegar containing 33g
Sour potassium, the acetic acid rubidium containing 0.30gRb and the cesium acetate containing 0.36gCs, which are sufficiently mixed, to be dissolved in pure water, and maceration extract is obtained
400ml is immersed on precursor I V, in 100 DEG C of dryings, obtains the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Rb content is 0.30g/L, and Cs contains
Amount is 0.36g/L, and Cr content is 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-
Mass spectrometer (GC-MASS) analysis.
The activity for being computed the catalyst is 379.64g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.35%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis by embodiment 10 and embodiment 8 and embodiment 9, improve vinyl acetate catalyst space-time yield and
In terms of selectivity, in the catalyst that the present invention uses, Cr has preferably in metal Rb, metal Cs and vib metal in alkali metal element
Synergistic effect, illustrate improving catalyst between metal Pd, metal Au, potassium acetate, acetic acid rubidium, cesium acetate and chromic acetate
There is preferable synergistic effect in terms of activity and selectivity.
[embodiment 11]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid molybdenum (Mo containing 0.40gMo2(OAc)4) be dissolved in the aqueous acetic acid that concentration is 60wt%, it obtains
Maceration extract 100ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；It weighs and contains
33g potassium acetate, the acetic acid rubidium containing 0.30gRb and the cesium acetate containing 0.36gCs, which are sufficiently mixed, to be dissolved in pure water, and maceration extract is obtained
400ml is immersed on precursor I V, in 100 DEG C of dryings, obtains the catalyst.
The Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Rb content is 0.30g/L, and Cs contains
Amount is 0.36g/L, and Mo content is 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The activity for being computed the catalyst is 380.36g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.21%.In order to just
In comparing, the main preparation condition of catalyst is listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
[embodiment 12]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.83gPd's and 1.87gAu
Chlorine palladium acid, aqueous solution of chloraurate, obtain maceration extract 500ml, and the ball that carrier 1.0L diameter is 5.6mm is immersed in turning pot
Shape SiO2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, contain 20.5g Na with 98ml2SiO3·9H2The solution of O is sufficiently mixed, and ageing obtains for 24 hours
Catalyst precarsor II；
It (3) is 12% (with N with solubility2H4·H2O weight ratio meter) it is that 500ml hydrazine hydrate is restored, it is washed to no chlorine
Ion, 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromic acetate (Cr (OAc) containing 0.15gCr3·6H2O the acetic acid molybdenum (Mo) and containing 0.25gMo2(OAc)4) molten
Solution obtains maceration extract 100ml, is immersed on precursor II I in the aqueous acetic acid that concentration is 60wt%, dry through 110 DEG C of vacuum
Dry, 400 DEG C of roastings obtain catalyst precarsor IV；Weigh potassium acetate containing 33g, the acetic acid rubidium containing 0.30gRb and containing 0.36gCs's
Cesium acetate, which is sufficiently mixed, to be dissolved in pure water, and maceration extract 400ml is obtained, and is immersed on precursor I V, in 100 DEG C of dryings, obtains institute
State catalyst.
The synthesis of ethylene process vinyl acetate: by 900ml Catalyst packing in fixed bed reactors, N is used2After leak test, N is used2
System is sufficiently purged, after system heating, closes N2, cut ethylene, and be warming up to reaction bed temperature up to after 120 DEG C, open
Acetic acid pump is opened, control reaction temperature is 142 DEG C, reaction pressure 0.78MPa；Raw material volume air speed: 2000h-1；Raw material composition:
Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0 after sustained response 120h, stops reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
Being computed the Pd content for measuring the catalyst through ICP is 3.83g/L, and Au content 1.87g/L, Rb content is 0.30g/
L, Cs content are 0.36g/L, and Cr content is 0.15g/L, and Mo content is 0.25g/L, acetic acid potassium content 33g/L.
The activity of the catalyst is 383.11g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.80%.For the ease of than
Compared with the main preparation condition of catalyst being listed in table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis by embodiment 12 and embodiment 10 and embodiment 11, is improving vinyl acetate catalyst space-time yield
In the catalyst used with selective aspect, the present invention, Cr, metal in metal Rb, metal Cs and vib metal in alkali metal element
Mo has preferable synergistic effect, illustrate metal Pd, metal Au, potassium acetate, acetic acid rubidium, cesium acetate, chromic acetate and acetic acid molybdenum it
Between improve catalyst activity and selectivity in terms of have preferable synergistic effect.
Table 1
Table 2
Claims (8)
1. being used for the catalyst of synthesizing ethylene method vinyl acetate, the catalyst includes carrier, active component and co-catalyst；Institute
Carrier is stated using SiO2、Al2O3Or its mixture, the active component include metal Pd and metal Au, the co-catalyst choosing
From the compound of at least one of alkali metal and vib metal metallic element, and the catalyst includes simultaneously Pd, Au, acetic acid
The compound of potassium, the alkali metal compound selected from least one of Li, Na, Rb and Cs and vib metal element,
Wherein, the total content selected from Li, Na, Rb and Cs and vib metal element described in catalyst is 0.5~7.0g/L.
2. the catalyst according to claim 1 for synthesizing ethylene method vinyl acetate, it is characterised in that the vib metal
Element is selected from least one of Cr, Mo and W.
3. the catalyst according to claim 1 for synthesizing ethylene method vinyl acetate, it is characterised in that Pd in catalyst
Content be 1.0~12.0g/L.
4. the catalyst according to claim 1 for synthesizing ethylene method vinyl acetate, it is characterised in that Au in catalyst
Content be 0.1~10.0g/L.
5. the catalyst according to claim 1 for synthesizing ethylene method vinyl acetate, which is characterized in that vinegar in catalyst
The content of sour potassium is 10~90g/L.
6. being included the following steps: by the synthetic method of catalyst described in claim 1
(1) compound solution of the compound of palladium, gold is mixed by the composition of catalyst with carrier, arrives catalyst precarsor I；
(2) so that compound containing Pd, compound containing Au is converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(3) compound state Pd in catalyst precarsor II and compound state Au are reduced to metal Pd and metal Au obtains catalyst precarsor
III；
(4) before metallic compound in alkali metal compound and VIB being supported on catalyst using infusion process by the composition of catalyst
Body III obtains catalyst.
7. the synthetic method of ethylene process vinyl acetate, using ethylene, acetic acid and oxygen as raw material, in any one of Claims 1 to 5
Reaction obtains vinyl acetate in the presence of the catalyst.
8. synthetic method according to claim 7, it is characterized in that the temperature of reaction is 130~150 DEG C, the pressure of reaction is
0.1~1.0MPa, with molar ratio computing ethylene: acetic acid: oxygen=1:(0.1~0.3): (0.05~0.2), raw material volume air speed are
1500~2500h-1。
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|---|---|---|---|---|
| BE738302A (en) * | 1968-09-04 | 1970-03-02 | ||
| CA852761A (en) * | 1970-09-29 | Erpenbach Heinz | Process for the manufacture of vinyl acetate | |
| CN101884916A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing catalyst carrier used for preparing vinyl acetate by fluidized bed process |
| CN103121952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate preparation method |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA852761A (en) * | 1970-09-29 | Erpenbach Heinz | Process for the manufacture of vinyl acetate | |
| BE738302A (en) * | 1968-09-04 | 1970-03-02 | ||
| CN101884916A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing catalyst carrier used for preparing vinyl acetate by fluidized bed process |
| CN103121952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate preparation method |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
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