CN106582820B - Catalyst used in ethylene process vinyl acetate synthesis - Google Patents
Catalyst used in ethylene process vinyl acetate synthesis Download PDFInfo
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Abstract
The present invention relates to catalyst used in ethylene process vinyl acetate synthesis, mainly solve the problems, such as that catalyst activity and selectivity is not high in the prior art.For the present invention using catalyst used in ethylene process vinyl acetate synthesis, the catalyst includes carrier, active component and co-catalyst；The carrier uses SiO2、Al2O3Or its mixture, the co-catalyst is alkali metal acetate, the active component includes metal Pd, metal Au and the technical solution selected from least one of platinum group metal and alkaline-earth 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 catalyst used in ethylene process vinyl acetate synthesis, the preparation method of catalyst and ethylene process vinegar
The synthetic method of sour ethylene.
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 dipping
Catalyst preparation method, this method comprises: 1. with the solution impregnating carrier containing palladium, gold compound；2. the carrier after dipping
It is contacted with the aqueous solution of the sodium metasilicate containing alkali compounds, water-soluble palladium, gold compound is precipitated as insoluble palladium, gold compound；
3. palladium, gold compound are changed into Metal Palladium, gold with reducing agent；4. being dried to obtain institute after contacting after washing with alkali metal acetate
State 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.Catalyst used in a kind of ethylene process vinyl acetate synthesis 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 ethylene method vinegar described in one of technical problem
The method of sour ethylene.
One of in order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: ethylene process vinyl acetate synthesis
Catalyst used, the catalyst include carrier, active component and co-catalyst；The carrier uses SiO2、Al2O3Or
Its mixture, the co-catalyst be alkali metal acetate, the active component include metal Pd, metal Au and selected from platinum family gold
Belong to the compound at least one of alkaline-earth metal metallic element.
At least one of the preferred platinum of platinum group described in above-mentioned technical proposal, osmium, iridium, ruthenium and rhodium；The alkali
At least one of the preferred beryllium of earth metal element, magnesium, calcium, strontium and barium；The alkali metal acetate is preferably potassium acetate.
In above-mentioned technical proposal, as most preferred technical solution, the catalyst includes simultaneously Pd, Au, potassium acetate, platinum
The compound of race's metallic element and the compound of alkali earth metal；Such as the catalyst includes Pd, Au, potassium acetate, platinum
The compound of compound (or compound of ruthenium) and barium, or including Pd, Au, potassium acetate, the compound of platinum, ruthenium compound
The compound of (or compound of rhodium) and barium, or the change including Pd, Au, potassium acetate, the compound of platinum, the compound of ruthenium, rhodium
Close the compound of object and barium.
In above-mentioned technical proposal, the content of activity component metal Pd is preferably 1.0~12.0g/L in the catalyst；Institute
The content for stating activity component metal Au in catalyst is preferably 0.1~10.0g/L；The active component is selected from platinum group metal and alkali
At least one metal element content of metal is preferably 0.5~7.0g/L in soil；The content of potassium acetate is preferred in the catalyst
For 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 and gold is mixed with carrier by the composition of catalyst, before obtaining catalyst
Body I；
(2) so that compound containing Pd and 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) composition for pressing catalyst loads metallic compound in platinum group metal compounds and/or alkaline earth using infusion process
Catalyst precarsor IV is obtained after catalyst precarsor III, dry, roasting；
(5) co-catalyst liquor kalii acetici and catalyst precarsor IV are sufficiently mixed, are dried to obtain the 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) and step (5) are dry
Temperature is preferably 80~120 DEG C, and drying time is preferably 1~5 hour；Step (4) roasting condition with by platinum group metal compounds,
Alkaline earth compound, which is converted into oxide, to be advisable, such as maturing temperature is preferably 300~500 DEG C, and calcining time is preferably 1~5 small
When.
In above-mentioned technical proposal, compound, the ruthenium of the compound of the preferred rhodium of step (4) platinum group metal compounds, palladium
Compound, the compound of platinum, the compound of osmium and iridium compound (such as, but not limited to rhodium acetate, radium chloride, sulfuric acid
Rhodium, rhodium nitrate, palladium chloride, four ammonia palladium of dichloro, palladium acetate, ruthenic chloride, ammonium chloroplatinite, four ammino platinum chlorides, chloroplatinic acid, chlorination
At least one of osmium, chlorine osmic acid ammonium and ammonium chloroiridate)；The preferred alkaline-earth metal oxide of step (4) alkaline earth metal compound
At least one of object, alkaline earth metal chloride, alkali earth metal sulfate, alkaline earth nitrate and Alkaline Earth Metal Acetate；
More preferable Alkaline Earth Metal Acetate.
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 be include metal Pd, metal Au, potassium acetate and selected from platinum in catalyst
At least one of race's metal and alkaline-earth metal metallic element are conducive to the activity and stability that improve catalyst, to improve
The yield and selectivity of vinyl acetate.
The catalyst of above method synthesis with comparative catalyst with evaluating apparatus to be evaluated 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 375.52g/Lh, Dichlorodiphenyl Acetate second when using catalyst of the present invention
The selectivity of alkene is 95.11%, achieve in preferable technical effect, especially catalyst include simultaneously metal Pd, metal Au,
At least one of potassium acetate, platinum group metal metallic element and when selected from least one of alkaline-earth metal metallic element, obtains
Technical effect more outstanding, can be used in the industrial production of vinyl acetate.The present invention is made into one below by embodiment
Step 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 3.85gPd'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 four ammino platinum chloride (Pt (NH containing 1.37gPt3)4Cl2·XH2O) aqueous solution 150ml is immersed in precursor
It on III, is dried in vacuo through 110 DEG C, 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Pt content is 1.37g/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 375.52g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.11%.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 3.85gPd'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 barium acetate (Ba (OA containing 1.37gBaC)2·H2O) aqueous solution 150ml is immersed on precursor II I, through 110
DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Ba content is 1.37g/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 375.48g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.20%.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 3.85gPd'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 I V, in 100 DEG C of dryings, obtains the catalysis
Agent.
The Pd content for measuring the catalyst through ICP is 3.85g/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 365.56g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 94.22%.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 metal Pd, metal
Au, potassium acetate and platinum element, or simultaneously the catalyst performance ratio containing metal Pd, metal Au, potassium acetate and barium element containing only metal
Pd, metal Au, the performance of potassium acetate catalyst are more excellent, and the space-time yield and selectivity 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 3.85gPd'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) by the radium chloride (RhCl containing 1.37gRh3·3H2O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C
Vacuum drying, 400 DEG C of roastings, obtains catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Rh content is 1.37g/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 375.49g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.15%.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 3.85gPd'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 osmium chloride (OsCl containing 1.37gOs3·3H2O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C
Vacuum drying, 400 DEG C of roastings, obtains catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Os content is 1.37g/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 375.38g/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 5]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 ruthenic chloride (RuCl containing 1.37gRu3·XH2O) aqueous solution 150ml is immersed on precursor II I, through 110 DEG C
Vacuum drying, 400 DEG C of roastings, obtains catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Ru content is 1.37g/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 375.34g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.16%.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 3.85gPd'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 chloro-iridic acid (H containing 1.37gIr2IrCl6·XH2O) aqueous solution 150ml is immersed on precursor II I, through 110
DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Ir content is 1.37g/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 375.48g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.12%.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 3.85gPd'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 beryllium acetate (Be (OAc) containing 1.37gBe2) be dissolved in the aqueous acetic acid that concentration is 60wt%, it obtains
Solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Be content is 1.37g/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 375.41g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.17%.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 3.85gPd'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 magnesium acetate (Mg (OAc) containing 1.37gMg2·4H2O) aqueous solution 150ml is immersed on precursor II I, through 110
DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Mg content is 1.37g/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 375.46g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.22%.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 9]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 calcium acetate (Ca (OAc) containing 1.37gCa2·H2O) aqueous solution 150ml is immersed on precursor II I, through 110
DEG C vacuum drying, 400 DEG C roasting, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Ca content is 1.37g/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 375.53g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.30%.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 3.85gPd'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 strontium acetate (Sr (OA containing 1.37gSrC)2·0.5H2O) aqueous solution 150ml is immersed on precursor II I, warp
110 DEG C of vacuum drying, 400 DEG C of roastings, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Sr content is 1.37g/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 375.37g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.26%.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 11]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 four ammino platinum chloride (Pt (NH of the Pt containing 0.80g3)4Cl2·XH2) and the barium acetate of the Ba containing 0.57g O
(Ba(OAC)2·H2O) aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst
Precursor I V；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Pt content is 0.80g/L, and Ba contains
Amount is 0.57g/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 379.06g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.81%.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 11 and embodiment 1 and embodiment 2, improve vinyl acetate catalyst space-time yield and
In terms of selectivity, in the catalyst that the present invention uses, metal Ba has preferably in the Pt metal and alkaline-earth metal in platinum group metal
Synergistic effect illustrates metal Pd, metal Au, potassium acetate, platinum element and barium element in the activity and selectivity for improving catalyst
Aspect has preferable synergistic effect.
[embodiment 12]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 ruthenic chloride (RuCl of the Ru containing 0.80g3·XH2) and the barium acetate (Ba (OA of the Ba containing 0.57g OC)2·H2O)
Aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Ru content is 0.80g/L, and Ba contains
Amount is 0.57g/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 378.97g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 95.90%.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 13]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 four ammino platinum chloride (Pt (NH of the Pt containing 0.52g3)4Cl2·XH2O), the ruthenic chloride of the Ru containing 0.28g
(RuCl3·XH2) and the barium acetate (Ba (OA of the Ba containing 0.57g OC)2·H2O) aqueous solution 150ml is immersed on precursor II I, warp
110 DEG C of vacuum drying, 400 DEG C of roastings, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Pt content is 0.52g/L, and Ru contains
Amount is 0.28g/L, and Ba content is 0.57g/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 379.72g/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 13 and embodiment 11 and embodiment 12, is improving vinyl acetate catalyst space-time yield
In the catalyst used with selective aspect, the present invention, metal Ba has in Pt metal, metal Ru and alkaline-earth metal in platinum group metal
Preferable synergistic effect illustrates that metal Pd, metal Au, potassium acetate, platinum element, ruthenium element and barium element are improving catalyst
There is preferable synergistic effect in terms of activity and selectivity.
[embodiment 14]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 four ammino platinum chloride (Pt (NH of the Pt containing 0.52g3)4Cl2·XH2O), the radium chloride of the Rh containing 0.28g
(RhCl3·3H2) and the barium acetate (Ba (OA of the Ba containing 0.57g OC)2·H2O) aqueous solution 150ml is immersed on precursor II I, warp
110 DEG C of vacuum drying, 400 DEG C of roastings, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Pt content is 0.52g/L, and Rh contains
Amount is 0.28g/L, and Ba content is 0.57g/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 379.81g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.23%.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 15]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 four ammino platinum chloride (Pt (NH of the Pt containing 0.52g3)4Cl2·XH2O), the ruthenic chloride of the Ru containing 0.13g
(RuCl3·XH2O), the radium chloride (RhCl of the Rh containing 0.15g3·3H2) and the barium acetate (Ba (OA of the Ba containing 0.57g OC)2·
H2O) aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Pt content is 0.52g/L, and Ru contains
Amount is 0.13g/L, and Rh content is 0.15g/L, and Ba content is 0.57g/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 380.35g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.54%.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 15 and embodiment 13 and embodiment 14, is improving vinyl acetate catalyst space-time yield
In the catalyst used with selective aspect, the present invention, in platinum group metal in Pt metal, metal Ru, metal Rh and alkaline-earth metal
Metal Ba has preferable synergistic effect, illustrates metal Pd, metal Au, potassium acetate, platinum element, ruthenium element, rhodium element and barium member
Element has preferable synergistic effect in terms of the activity and selectivity for improving catalyst.
[embodiment 16]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 four ammino platinum chloride (Pt (NH of the Pt containing 0.52g3)4Cl2·XH2O), the ruthenic chloride of the Ru containing 0.13g
(RuCl3·XH2O), the radium chloride (RhCl of the Rh containing 0.15g3·3H2) and the calcium acetate of the Ca containing 0.57g (Ca (OAc) O2·
H2O) aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C, and 400 DEG C of roastings obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Pt content is 0.52g/L, and Ru contains
Amount is 0.13g/L, and Rh content is 0.15g/L, and Ca content is 0.57g/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 380.41g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.51%.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 17]
The preparation of catalyst:
(1) using sodium bicarbonate pH adjusting agent and water to prepare pH as solvent is 1.09, containing 3.85gPd'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 four ammino platinum chloride (Pt (NH of the Pt containing 0.52g3)4Cl2·XH2O), the ruthenic chloride of the Ru containing 0.13g
(RuCl3·XH2O), the radium chloride (RhCl of the Rh containing 0.15g3·3H2O), the barium acetate (Ba (OA of the Ba containing 0.44gC)2·H2O)
With the calcium acetate (Ca (OAc) of the Ca containing 0.13g2·H2O) aqueous solution 150ml is immersed on precursor II I, is dried in vacuo through 110 DEG C,
400 DEG C of roastings, obtain catalyst precarsor IV；
(5) 33g potassium acetate will be contained to be dissolved in pure water, and will obtain maceration extract 300ml and is immersed on precursor I V, it is dry through 100 DEG C
It is dry, obtain the catalyst.
The Pd content for measuring the catalyst through ICP is 3.85g/L, and Au content 1.87g/L, Pt content is 0.52g/L, and Ru contains
Amount is 0.13g/L, and Rh content is 0.15g/L, and Ba content is 0.44g/L, and Ca content is 0.13g/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 382.86g/Lh, and the selectivity of Dichlorodiphenyl Acetate ethylene is 96.89%.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 17 and embodiment 15 and embodiment 16, is improving vinyl acetate catalyst space-time yield
In the catalyst used with selective aspect, the present invention, in platinum group metal in Pt metal, metal Ru, metal Rh and alkaline-earth metal
Metal Ba, metal Ca have preferable synergistic effect, illustrate metal Pd, metal Au, potassium acetate, platinum element, ruthenium element, rhodium member
Element, barium element and calcium constituent have preferable synergistic effect in terms of the activity and selectivity for improving catalyst.
Table 1
Table 2
Claims (6)
1. catalyst used in a kind of ethylene process vinyl acetate synthesis, which is characterized in that the catalyst includes carrier, active group
Point and co-catalyst；The carrier uses SiO2、Al2O3Or its mixture, the co-catalyst are alkali metal acetate, institute
State active component by metal Pd, metal Au, selected from least one of platinum group metal metallic element and in alkaline-earth metal
At least one metallic element composition；Wherein, the platinum group is selected from least one of platinum, osmium, iridium, ruthenium and rhodium；Institute
It states alkali earth metal and is selected from least one of beryllium, magnesium, calcium, strontium and barium；Platinum group metal and alkaline earth gold in the active component
The total content of category is 0.5 ~ 7.0g/L；The alkali metal acetate is potassium acetate.
2. catalyst used in ethylene process vinyl acetate synthesis according to claim 1, wherein active component in catalyst
The content of metal Pd is 1.0 ~ 12.0g/L, and the content of activity component metal Au is 0.1 ~ 10.0 g/L.
3. catalyst used in ethylene process vinyl acetate synthesis according to claim 1, wherein potassium acetate in catalyst
Content is 10 ~ 90 g/L.
4. the preparation method of catalyst described in any one of claim 1-3, which comprises the steps of:
(1) compound solution of the compound of palladium and gold is mixed by the composition of catalyst with carrier, obtains catalyst precarsor I；
(2) so that compound containing Pd and 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) platinum group metal compounds and alkaline earth metal compound are supported on catalyst using infusion process by the composition for pressing catalyst
Precursor II I obtains catalyst precarsor IV after dry, roasting；
(5) co-catalyst liquor kalii acetici and catalyst precarsor IV are sufficiently mixed, are dried to obtain the catalyst.
5. the synthetic method of ethylene process vinyl acetate, which is characterized in that using ethylene, acetic acid and oxygen as raw material, in claim 1
Reaction obtains vinyl acetate in the presence of any one of ~ 3 catalyst.
6. synthetic method according to claim 5, wherein the temperature of reaction is 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 be 1500~
2500h-1。
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| WO2007092188A8 (en) * | 2006-02-07 | 2008-04-17 | Celanese Int Corp | Integrated process for the production of acetic acid and vinyl acetate |
| CN101172230A (en) * | 2006-11-02 | 2008-05-07 | 中国石油化工股份有限公司 | Method for producing catalyzer for synthesizing vinyl acetate |
| 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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| CN1303320A (en) * | 1998-04-02 | 2001-07-11 | 英国石油化学品有限公司 | Catalyst and process for oxidation of ethane and/or ethylene |
| WO2007092188A8 (en) * | 2006-02-07 | 2008-04-17 | Celanese Int Corp | Integrated process for the production of acetic acid and vinyl acetate |
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