CN106582824A - Catalyst used for synthesizing vinyl acetate by ethylene process - Google Patents

Catalyst used for synthesizing vinyl acetate by ethylene process Download PDF

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CN106582824A
CN106582824A CN201510675455.8A CN201510675455A CN106582824A CN 106582824 A CN106582824 A CN 106582824A CN 201510675455 A CN201510675455 A CN 201510675455A CN 106582824 A CN106582824 A CN 106582824A
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catalyst
vinyl acetate
metal
ethylene
compound
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CN106582824B (en
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查晓钟
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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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 catalyst used for synthesizing vinyl acetate by an ethylene process. The catalyst used for synthesizing vinyl acetate by the ethylene process mainly solves the problems that in the prior art, the activity and selectivity of a catalyst are not high. According to the technical scheme, the catalyst used for synthesizing vinyl acetate by the ethylene process comprises a carrier, active components and auxiliary catalysts, wherein SiO2, Al2O3 or a mixture of SiO2 and Al2O3 is adopted as the carrier, the active components comprise metal P and metal Au, and the auxiliary catalysts are selected from compounds of at least one metal element in alkali metal and VIB metal, the problems are favorably solved, and the catalyst used for synthesizing vinyl acetate by the ethylene process can be used in industrial production of vinyl acetate.

Description

For the catalyst of synthesizing ethylene method vinyl acetate
Technical field
The present invention relates to be used for the synthetic method of the catalyst of synthesizing ethylene method vinyl acetate, the preparation method of catalyst and vinyl acetate.
Background technology
Vinyl acetate (VAc) is one of 50 kinds of maximum industrial chemicals of world wide production, by autohemagglutination or with other monomer copolymerizations, the derivants such as polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) emulsion, vinyl acetate-ethylene copolymerization emulsions (VAE) or copolymer resinses (EVA), vinyl acetate-chloride copolymer (EVC) can be generated.These derivants are widely used in the aspects such as cementing agent, coating, ink, leather processing, fiber process, emulsifying agent, water-solubility membrane and the soil conditioner of adhesive, building coating, paper or fabric.The main method that ethylene process vinyl acetate is produced in the world today is with ethylene, oxygen and acetic acid as raw material, with Pd-Au-KOAc/SiO2System makees catalyst, is synthesized by gas phase catalytic reaction.
After the technique for finding ethylene vapor phase method production vinylacetate from nineteen seventies, people are devoted to more high reaction activity with selective catalyst research.At present, people are more to concentrate on the dispersion of research precious metal palladium and gold or other elements on carrier and distribution, distribution of the active component on carrier also develops into eggshell type from protein type, the utilization rate of noble metal effectively improves, increased the reactivity of units activity component agent, the generation of side reaction is reduced, reaction selectivity is improve.
Chinese patent (CN1226188A, for preparing the palladium-gold catalyst of vinyl acetate) provide a kind of preparation method for preparing the catalyst for being loaded with major catalyst noble metal, promoter metal and alkali metal or alkaline earth metal compound.Its concrete manufacture process is as follows：1. in the maceration tank of rotation, the mixed liquor of the noble metal for having configured and promoter is added, is passed through hot-air drying；2. the solution for taking the alkaline matters such as a certain amount of sodium silicate is made an addition in dried catalyst, and the palladium and gold of the chlorination state of original water soluble are changed into into the insoluble hydroxide state palladium of water and gold；3. the palladium and Au catalyst of hydroxide state are reduced in nitrogen atmosphere, that is, is reduced into the palladium and Au catalyst of metallic state；4. it is washed till without chloride ion, is dried, soak potassium acetate, after being dried the catalyst is obtained final product.
United States Patent (USP) (US 3743607, entitled Palladium-gold catalyst) describes the preparation method of the catalyst of homogeneous impregnation, and the method includes：1. palladium, the solution impregnating carrier of gold compound are used；2. it is dried；3. palladium, gold compound are reduced to into Metal Palladium, gold；4. wash, be dried.
United States Patent (USP) (US 4048096, entitled Surface impregnated catalyst) describes the preparation method of the catalyst of shell dipping, and the method includes：1. with containing palladium, the solution impregnating carrier of gold compound；2. the carrier after impregnating is contacted with the aqueous solution containing alkali compoundss sodium silicate, and water-soluble palladium, gold compound are precipitated as into insoluble palladium, gold compound；3. palladium, gold compound are changed into into Metal Palladium, gold with reducing agent；4. it is dried to obtain the catalyst after contacting with alkali metal acetate after washing.The space time yield and selectivity of the catalyst that said method is obtained is relatively low.
The content of the invention
One of the technical problem to be solved is the not high problem of the vinyl acetate catalyst activity and selectivity synthesized in prior art.There is provided a kind of catalyst for synthesizing ethylene method vinyl acetate, the characteristics of the catalyst has high-activity high-selectivity.
The two of the technical problem to be solved are the preparation methoies of one of technical problem catalyst.
The three of the technical problem to be solved are the methods using one of the technical problem catalyst synthesizing vinyl acetate.
In order to solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：For the catalyst of synthesizing ethylene method vinyl acetate, the catalyst includes carrier, active component and promoter；The carrier adopts SiO2、Al2O3Or its mixture, the active component includes metal Pd and metal Au, the compound of at least one metallic element of the promoter in alkali metal and vib metal.
In above-mentioned technical proposal, the alkali metal preferably is selected from least one in Li, Na, K, Rb and Cs；More preferably described alkali metal includes K and at least one in Li, Na, Rb and Cs simultaneously.
At least one in vib metal element described in above-mentioned technical proposal preferred Cr, Mo and W；
In above-mentioned technical proposal, used as most preferred technical scheme, the catalyst includes the compound of Pd, Au, potassium acetate, at least one alkali metal compound in Li, Na, Rb and Cs and vib metal element simultaneously；Such as described catalyst includes Pd, Au, potassium acetate, Rb (or Cs) and Cr, or 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 0.5～7.0g/L in alkali metal and VIB described in catalyst, now at least one of the alkali metal in Li, Na, Rb and Cs.
In above-mentioned technical proposal, selected from when including K, in terms of potassium acetate, the content of potassium acetate is preferably 10～90g/L to K to alkali metal described in catalyst in the catalyst.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Method for preparing catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the steps：
(1) compound solution of the compound of palladium, gold is mixed with carrier by the composition of catalyst, to catalyst precarsor I；
(2) make compound containing Pd, compound containing Au be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(3) compound state Pd and compound state Au in catalyst precarsor II are reduced to into metal Pd and metal Au obtains catalyst precarsor III；
(4) metallic compound in alkali metal compound and/or VIB is supported on into catalyst precarsor III using infusion process by the composition of catalyst and obtains catalyst.
In above-mentioned technical proposal, do not specially required based on the reducing agent of the understanding step (3) of those skilled in the art, reducing agent can be gas or liquid, at least one in the preferred hydrogen of reducing agent, hydrazine hydrate；Step (4) baking temperature is preferably 80～120 DEG C, is preferably 1～5 hour drying time.
In above-mentioned technical proposal, step (4) alkali metal compound preferably is selected from least one in alkali carbonate, bicarbonate and acetate.At least one in the preferred chromium acetate of the vib metal compound, chromic nitrate, Chlorizate chromium, acetic acid molybdenum, ammonium molybdate, molybdenum pentachloride and ammonium tungstate；At least one more preferably from chromium acetate and acetic acid molybdenum.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of ethylene process vinyl acetate, with ethylene, acetic acid and oxygen as raw material, the reaction in the presence of above-mentioned catalyst obtains vinyl acetate.
The key of the present invention is the selection of catalyst, skilled person will know how determining the proportioning of suitable reaction temperature, response time, reaction pressure and material according to actual needs.But, in above-mentioned technical proposal, the temperature of reaction be preferably 130～150 DEG C, the pressure of reaction be preferably 0.1～1.0MPa, with molar ratio computing ethylene:Acetic acid:Oxygen is preferably 1:(0.1～0.3):(0.05～0.2), raw material volume air speed is preferably 1500～2500h-1。
Compared with prior art, the key of the present invention is the compound that catalyst includes metal Pd, metal Au and at least one metallic element in alkali metal and vib metal, be conducive to improving the activity of catalyst and stability, so as to improve the yield of vinyl acetate.
The catalyst of said method synthesis and comparative catalyst are evaluated respectively and are calculated the activity and and selectivity of catalyst with evaluating apparatus.Evaluation methodology is to load 900ml catalyst in the reactor, using nitrogen leak test, after guaranteeing system without leak source, the flow of ethylene is adjusted to into 64.4mol/h, while heating up, when reaction bed temperature reaches 120 DEG C, the acetic acid of input 9.30mol/h, starts to throw oxygen after 20 minutes, and sufficient oxygen is thrown after 120 minutes, the amount of oxygen is 3.88mol/h, and air speed is 2000h-1, controlling reaction temperature is 142 DEG C in course of reaction, reaction pressure 0.78MPa, and controlling raw material ratio is：Ethylene/acetic acid/oxygen=83.0/12.0/5.0 (mol ratio).
The content of each component in gas chromatography analysis product, and calculate the activity (space-time yield) and selectivity of catalyst by following equation：
Test result indicate that, during using catalyst of the present invention, the activity of catalyst reaches 375.21g/Lh, the selectivity of Dichlorodiphenyl Acetate ethylene is 95.08%, achieve preferable technique effect, when especially including at least one metallic element compound in metal Pd, metal Au, alkali metal and at least one metallic element compound in VIB in catalyst simultaneously, more prominent technique effect is achieved, in can be used for the commercial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) weigh potassium acetate containing 33g and the acetic acid rubidium containing 1.06gRb is sufficiently mixed and is dissolved in pure water, obtain impregnation liquid 500ml, be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Rb contents are 1.06g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.21g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.08%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 2】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromium acetate (Cr (OAc) containing 1.06gCr3·6H2O) aqueous solution 200ml is immersed in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；The solution 300ml containing 33g potassium acetates is weighed, is immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Cr contents are 1.06g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 374.92g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.14%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) the solution 300ml containing 33g potassium acetates is weighed, is immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
Jing ICP determine the catalyst Pd contents be 3.83g/L, Au contents 1.87g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 365.49g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 94.27%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
By can be seen that compared with embodiment 1～2, the catalyst that the present invention is adopted, using simultaneously containing Pd, Au, potassium acetate and acetic acid rubidium, while the ratio of the catalyst performance containing Pd, Au, potassium acetate and chromium acetate is more excellent containing only the performance of Pd, Au, potassium acetate catalyst, the space-time yield of vinyl acetate catalyst will be high.
【Embodiment 3】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical Al of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2O3Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) weigh potassium acetate containing 33g and the cesium acetate containing 1.06gCs is sufficiently mixed and is dissolved in pure water, obtain impregnation liquid 500ml, be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Cs contents are 1.06g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.62g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.05%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 4】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) weigh potassium acetate containing 33g and the sodium acetate containing 1.06gNa is sufficiently mixed and is dissolved in pure water, obtain impregnation liquid 500ml, be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Na contents are 1.06g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.15g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.03%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 5】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) weigh potassium acetate containing 33g and the lithium acetate containing 1.06gLi is sufficiently mixed and is dissolved in pure water, obtain impregnation liquid 500ml, be immersed in precursor II I, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Li contents are 1.06g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.40g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.13%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 6】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid molybdenum (Mo containing 1.06gMo2(OAc)4) aqueous acetic acid that concentration is 60wt% is dissolved in, obtain impregnation liquid 200ml and be immersed in precursor II I, 110 DEG C of Jing vacuum drying, 400 DEG C of roastings obtain catalyst precarsor IV；The solution 300ml containing 33g potassium acetates is weighed, is immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Mo contents are 1.06g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 375.32g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 94.98%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 7】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 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 in precursor II I, and 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtain catalyst precarsor IV；The solution 300ml containing 33g potassium acetates is weighed, is immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 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 packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 374.95g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.02%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 8】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromium acetate (Cr (OAc) containing 0.40gCr3·6H2O) it is sufficiently mixed and is dissolved in pure water, obtain impregnation liquid 100ml, be immersed in precursor II I, 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtains catalyst precarsor IV；Weigh potassium acetate containing 33g and the acetic acid rubidium containing 0.66gRb is sufficiently mixed and is dissolved in pure water, obtain impregnation liquid 400ml, be immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Rb contents are 0.66g/L, and Cr contents are 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 378.82g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.84%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 1 and embodiment 2 by embodiment 8, in terms of vinyl acetate catalyst space-time yield and selectivity is improved, in the catalyst that the present invention is used, Cr has preferable synergism in metal Rb and vib metal in alkali metal, illustrates between metal Pd, metal Au, potassium acetate, acetic acid rubidium and chromium acetate to there is preferable cooperative effect in terms of the activity and selectivity of catalyst is improved.
【Embodiment 9】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromium acetate (Cr (OAc) containing 0.40gCr3·6H2O) it is sufficiently mixed and is dissolved in the water, obtain impregnation liquid 100ml, be immersed in precursor II I, 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtains catalyst precarsor IV；Weigh potassium acetate containing 33g and the cesium acetate containing 0.66gCs is sufficiently mixed and is dissolved in pure water, obtain impregnation liquid 400ml, be immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Cs contents are 0.66g/L, and Cr contents are 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 378.73g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.96%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 10】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromium acetate (Cr (OAc) containing 0.40gCr3·6H2O) it is sufficiently mixed and is dissolved in the water, obtain impregnation liquid 100ml, be immersed in precursor II I, 110 DEG C of vacuum drying of Jing, 400 DEG C of roastings obtains catalyst precarsor IV；Weigh potassium acetate containing 33g, the acetic acid rubidium containing 0.30gRb and the cesium acetate containing 0.36gCs and be sufficiently mixed and be dissolved in pure water, obtain impregnation liquid 400ml, be immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Rb contents are 0.30g/L, and Cs contents are 0.36g/L, and Cr contents are 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 379.64g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.35%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 8 and embodiment 9 by embodiment 10, in terms of vinyl acetate catalyst space-time yield and selectivity is improved, in the catalyst that the present invention is used, Cr has preferable synergism in metal Rb, metal Cs and vib metal in alkali metal, illustrate metal Pd, metal Au, potassium acetate, acetic acid rubidium, between cesium acetate and chromium acetate improve catalyst activity and selectivity in terms of have preferable cooperative effect.
【Embodiment 11】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the acetic acid molybdenum (Mo containing 0.40gMo2(OAc)4) aqueous acetic acid that concentration is 60wt% is dissolved in, impregnation liquid 100ml is obtained, it is immersed in precursor II I, 110 DEG C of Jing vacuum drying, 400 DEG C of roastings obtain catalyst precarsor IV；Weigh potassium acetate containing 33g, the acetic acid rubidium containing 0.30gRb and the cesium acetate containing 0.36gCs and be sufficiently mixed and be dissolved in pure water, obtain impregnation liquid 400ml, be immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
It is 3.83g/L that Jing ICP determine the Pd contents of the catalyst, and Au contents 1.87g/L, Rb contents are 0.30g/L, and Cs contents are 0.36g/L, and Mo contents are 0.40g/L, acetic acid potassium content 33g/L.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
The activity for being computed the catalyst is 380.36g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.21%.For the ease of comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
【Embodiment 12】
The preparation of catalyst：
(1) it is 1.09 to prepare pH as solvent with sodium bicarbonate pH value regulator and water, and the acid of the chlorine palladium containing 3.83gPd and 1.87gAu, aqueous solution of chloraurate obtain impregnation liquid 500ml, and the spherical SiO of a diameter of 5.6mm of carrier 1.0L is immersed in pot is turned2Catalyst precarsor I is obtained on carrier；
After (2) 80 DEG C of dryings, with 98ml 20.5g Na are contained2SiO3·9H2The solution of O is sufficiently mixed, and ageing 24h obtains catalyst precarsor II；
(3) it is 12% (with N with solubility2H4·H2O weight ratio meters) reduced for 500ml hydrazine hydrates, Jing is washed to without chloride ion, and 90 DEG C are dried to obtain catalyst precarsor III；
(4) by the chromium acetate (Cr (OAc) containing 0.15gCr3·6H2O the acetic acid molybdenum (Mo) and containing 0.25gMo2(OAc)4) aqueous acetic acid that concentration is 60wt% is dissolved in, impregnation liquid 100ml is obtained, it is immersed in precursor II I, 110 DEG C of Jing vacuum drying, 400 DEG C of roastings obtain catalyst precarsor IV；Weigh potassium acetate containing 33g, the acetic acid rubidium containing 0.30gRb and the cesium acetate containing 0.36gCs and be sufficiently mixed and be dissolved in pure water, obtain impregnation liquid 400ml, be immersed in precursor I V, in 100 DEG C of dryings, obtain the catalyst.
The synthesis of ethylene process vinyl acetate：By 900ml Catalyst packings in fixed bed reactors, N is used2After leak test, N is used2System is fully purged, after system heats up, N is closed2, ethylene is cut, and reaction bed temperature is warming up to up to after 120 DEG C, unlatching acetic acid pump, controlling reaction temperature is 142 DEG C, and reaction pressure is 0.78MPa；Raw material volume air speed：2000h-1；Raw material is constituted：Ethylene/acetic acid/oxygen molar ratio=83.0/12.0/5.0, after sustained response 120h, stopped reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase is analyzed using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS).
Be computed Jing ICP determine the catalyst Pd contents be 3.83g/L, Au contents 1.87g/L, Rb contents be 0.30g/L, Cs contents be 0.36g/L, Cr contents be 0.15g/L, Mo contents be 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 comparing, the main preparation condition of catalyst is listed in into table 1, the physical property and catalytic performance of catalyst are listed in table 2.
Found out on year-on-year basis with embodiment 10 and embodiment 11 by embodiment 12, in terms of vinyl acetate catalyst space-time yield and selectivity is improved, in the catalyst that the present invention is used, Cr, metal Mo have preferable synergism in metal Rb, metal Cs and vib metal in alkali metal, illustrate between metal Pd, metal Au, potassium acetate, acetic acid rubidium, cesium acetate, chromium acetate and acetic acid molybdenum improve catalyst activity and selectivity in terms of have preferable cooperative effect.
Table 1
Table 2

Claims (10)

1. the catalyst of synthesizing ethylene method vinyl acetate is used for, and the catalyst includes carrier, active component and promoter； The carrier adopts SiO2、Al2O3Or its mixture, the active component includes metal Pd and metal Au, described to help The compound of at least one metallic element of the catalyst in alkali metal and vib metal.
2. the catalyst for synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that the alkali metal unit At least one of the element in Li, Na, K, Rb and Cs.
3. the catalyst for synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that the vib metal At least one of the element in Cr, Mo and W.
4. the catalyst for synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that Pd in catalyst Content be 1.0～12.0g/L.
5. the catalyst for synthesizing ethylene method vinyl acetate according to claim 1, it is characterised in that Au in catalyst Content be 0.1～10.0g/L.
6. the catalyst for synthesizing ethylene method vinyl acetate according to claim 2, it is characterised in that institute in catalyst State the metal in alkali metal and VIB at least one content be 0.5～7.0g/L, now the alkali metal selected from Li, Na, At least one in Rb and Cs.
7. the catalyst for synthesizing ethylene method vinyl acetate according to claim 2, it is characterised in that institute in catalyst Alkali metal is stated selected from when including K, in terms of potassium acetate, the content of potassium acetate is 10～90g/L to K in catalyst.
8., by the synthetic method of the catalyst described in claim 1, comprise the steps：
(1) compound solution of the compound of palladium, gold is mixed with carrier by the composition of catalyst, to catalyst precarsor I；
(2) make compound containing Pd, compound containing Au be converted into sedimentation type with alkaline solution and obtain catalyst precarsor II；
(3) compound state Pd and compound state Au in catalyst precarsor II are reduced to into metal Pd and metal Au obtains catalyst precarsor III；
(4) metallic compound in alkali metal compound and/or VIB is supported on into catalyst using infusion process by the composition of catalyst Precursor II I obtains catalyst.
9. the synthetic method of ethylene process vinyl acetate, with ethylene, acetic acid and oxygen as raw material, in any one of claim 1～7 Reaction in the presence of the catalyst obtains vinyl acetate.
10. synthetic method according to claim 9, it is characterized in that the temperature reacted be 130～150 DEG C, the pressure of reaction be 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 is 1500～2500h-1。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN103121952A (en) * 2011-11-18 2013-05-29 中国石油化工股份有限公司 Vinyl acetate preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
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
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
CN103121952A (en) * 2011-11-18 2013-05-29 中国石油化工股份有限公司 Vinyl acetate preparation method

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