CN106268944B - For producing the catalyst of acetylene method vinyl acetate - Google Patents
For producing the catalyst of acetylene method vinyl acetate Download PDFInfo
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Abstract
The present invention relates to the catalyst for producing acetylene method vinyl acetate, mainly solve the problems, such as that acetylene in gas phase method catalyst activity is not high in the prior art.The present invention is using the catalyst for producing acetylene method vinyl acetate, the catalyst uses active carbon for carrier, active component includes the technical solution of zinc acetate, potassium acetate and the compound selected from least one of VA and alkaline-earth metal metallic element, it preferably solves the problems, such as this, can be used in the industrial production of acetylene in gas phase method synthesizing vinyl acetate.
Description
Technical field
The present invention relates to the catalyst for producing acetylene method vinyl acetate, the acetylene in gas phase method vinyl acetate catalyst
Preparation method and acetylene in gas phase method vinyl acetate synthetic method.
Background technique
Vinyl acetate (Vinyl acetate, abbreviation VAC) it is important Organic Chemicals, it is poly- to be widely used in manufacture
Vinyl acetate, polyvinyl alcohol are simultaneously further processed for binder, coating, vinylon fibre, fabric processing, lotion, resin and thin
Film etc..Currently, the method for industrial production vinyl acetate has acetylene in gas phase method and ethylene vapor phase method.
Producing vinyl acetate by acetylene method experienced two developing stage of liquid and gas technique.Before 1940, mainly
It based on liquid phase process, is reacted under 30~70 DEG C of normal pressures, catalyst is mercury oxide and sulfuric acid or phosphoric acid；40 years 20th century
After generation, start based on acetylene in gas phase method, catalyst is the active carbon for having loaded zinc acetate.
The zinc acetate of nineteen twenty-two Germany Wacker company Muqaen discovery dipping on the activated carbon can be with vapor- phase synthesis acetic acid
Ethylene then proposes the method using acetylene in gas phase synthesis VAc, improves investment industrial production by Hochst company.It is catalyzed
Agent is with Zn (OAc)2For active component, using active carbon as carrier, and use till today always.United States Patent (USP) (US166482,
Production of vinyl acetate) it reports using catalyst Z n (OAc)2/ C, has synthesized vinyl acetate.It is Chinese special
Sharp CN1903435 (a kind of title are as follows: catalyst and preparation method thereof for vinyl acetate synthesis) provides a kind of acetylene method
The preparation method of vinyl acetate catalyst, catalyst activity component uses zinc oxide and acetic acid, and a small amount of waltherite is added, by it
It is immersed in active carbon and is dried to obtain catalyst.But the catalyst activity that above-mentioned technology provides is not high, limits acetylene method acetic acid
The application of ethylene.
Summary of the invention
The first technical problem to be solved by the present invention is that acetylene method vinyl acetate catalyst activity is low in the prior art
Problem provides a kind of new catalyst for being used to produce acetylene method vinyl acetate, the active high feature of the catalyst.
The second technical problem to be solved by the present invention is the producer using catalyst described in one of above-mentioned technical problem
Method.
The third technical problem to be solved by the present invention is the acetic acid second using catalyst described in one of above-mentioned technical problem
The synthetic method of alkene.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: for producing acetylene method acetic acid second
The catalyst of alkene, the catalyst use active carbon for carrier, and active component includes zinc acetate, potassium acetate and selected from VA and alkaline earth
The compound of at least one of metal metallic element.It is preferred that the active component includes zinc acetate, potassium acetate, selected from VA simultaneously
At least one of metallic element and the compound selected from least one of alkaline-earth metal metallic element.The metal member of VA at this time
Have in terms of the activity for improving vinyl acetate between the compound and the compound of the metallic element in alkaline-earth metal of element and cooperates with
Effect.
In above-mentioned technical proposal, the active carbon preferably is selected from coal quality column charcoal, cocoanut active charcoal, apricot shell active carbon and bamboo matter
At least one of active carbon.The specific surface area of the active carbon is preferably 1000~1500cm2/ g, adsorption hole hold preferably 0.60
~1.00cm3/g。
In above-mentioned technical proposal, the VA metal preferably is selected from least one of bismuth and antimony, more preferably simultaneously include bismuth and
Antimony.The alkaline-earth metal metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium, more preferably simultaneously includes strontium and barium.
In above-mentioned technical proposal, as most preferred technical solution, the active component includes simultaneously zinc acetate, acetic acid
The compound of potassium, the compound of VA metallic element and alkali earth metal；Such as the active component by zinc acetate, potassium acetate,
Bismuth subsalicylate (or antimony acetate) and strontium acetate composition, or by zinc acetate, potassium acetate, bismuth subsalicylate, antimony acetate and acetic acid
Strontium (or barium acetate) composition, or be made of zinc acetate, potassium acetate, bismuth subsalicylate, antimony acetate, strontium acetate and barium acetate.
In above-mentioned technical proposal, the content of zinc acetate is preferably 50~300g/L in the catalyst, more preferably 80~
200g/L；The content of potassium acetate is preferably 0.10~10.00g/L in the catalyst, more preferably 3.00~7.00g/L；Institute
State in catalyst that at least one content of metal is preferably 0.50~8.00g/L in VA and alkaline-earth metal, more preferably
1.00~5.00g/L.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem
The production method of catalyst described in case, includes the following steps:
1. by catalyst composition by the solution of metallic element compound in zinc acetate, potassium acetate, VA and alkaline-earth metal with
Carrier mixing；
2. drying.
In above-mentioned technical proposal, the preferred basic bismuth carbonate of compound, the bismuth subnitrate, citric acid of the step 1. VA metal
At least one of bismuth ammonium, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate, antimony acetate and antimony chloride；More preferably time water
At least one of poplar acid bismuth and antimony acetate；1. the compound of metal preferably is selected from alkaline-earth metal oxide to step in the alkaline-earth metal
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.2. the drying temperature is 80~120 DEG C, more preferably 100~120 DEG C to step.
To solve above-mentioned technical problem three, technical scheme is as follows: vinyl acetate synthesis method, with acetic acid,
Acetylene is raw material, and reaction generates acetic acid in the presence of the catalyst described in any one of technical solution of one of above-mentioned technical problem
Ethylene.
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 the temperature reacted in above-mentioned technical proposal is preferably
150~200 DEG C；The pressure of reaction is preferably 0.1~0.5MPa；Preferably acetylene: acetic acid=(5 is formed with molar ratio computing raw material
~12): 1；Raw material volume air speed is preferably 250~350h-1。
The content gas chromatography analysis of each component in reaction product of the present invention, and calculate the space-time yield of catalyst.
Compared with prior art, key of the invention is in the active component of catalyst including zinc acetate, potassium acetate and choosing
From the compound of at least one of VA and alkaline-earth metal metallic element, be conducive to the activity and stability that improve catalyst, from
And improve the yield of vinyl acetate.
The experimental results showed that the space-time yield of catalyst reaches 162.12g/Lh when using catalyst of the present invention, obtain
Active component includes simultaneously zinc acetate, potassium acetate, at least one in VA in preferable technical effect, especially catalyst
When planting metallic element compound and being selected from least one of alkaline-earth metal metallic element compound, skill more outstanding is achieved
Art effect, can be used in the industrial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.90gBi
Bismuth subsalicylate (C7H5BiO4) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon of/g
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 103g/L, K content 6.60g/L, Bi content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 162.12g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 2]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.90gSr
Strontium acetate (Sr (OAC)2·0.5H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon of/g
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 103g/L, K content 6.60g/L, Sr content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cuts acetylene, opens acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 162.37g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2) and potassium acetate containing 6.60g (KOAc) be sufficiently mixed it is molten
Solution obtains maceration extract 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei in the aqueous acetic acid that concentration is 60wt%
0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Zn content for measuring the catalyst through ICP is 103g/L, K content 6.60g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 121.55g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
The catalyst used by can be seen that the present invention compared with Examples 1 to 2, using simultaneously containing zinc acetate, acetic acid
Potassium and bismuth subsalicylate active component, simultaneously the catalyst performance ratio containing zinc acetate, potassium acetate and strontium acetate active component containing only
Zinc acetate, the performance of potassium acetate active constituent catalyst are more excellent, and the space-time yield of vinyl acetate catalyst will be high.
[embodiment 3]
The preparation of catalyst: 80g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 3.00g (KOAc) and containing 1.00gSr's
Strontium acetate (Sr (OAC)2·0.5H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.60cm3/ g, specific surface area 1000cm2The cylindrical type cocoanut active charcoal of/g
Carrier impregnation stands 3h in 80 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 80g/L, K content 3.00g/L, Sr content 1.00g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cuts acetylene, opens acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 126.84g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 4]
The preparation of catalyst: 200g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 7.00g (KOAc) and contain 5.00gBa
Barium acetate (Ba (OAc)2·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 1.00cm3/ g, specific surface area 1500cm2The cylindrical type apricot shell active carbon of/g
Carrier impregnation stands 3h in 120 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 200g/L, K content 7.00g/L, Ba content 5.00g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 163.03g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 5]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.90gSb
Antimony acetate (Sb (OAc)3) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain maceration extract 350ml, will
1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The cylindrical type activated carbon from bamboo carrier impregnation of/g
In above-mentioned maceration extract, 3h is stood in 120 DEG C of dryings, obtains the catalyst.The Zn content for measuring the catalyst through ICP is
103g/L, K content 6.60g/L, Sb content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 162.51g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 6]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.90gCa
Calcium acetate (Ca (OAc)2·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon of/g
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 103g/L, K content 6.60g/L, Ca content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 162.42g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 7]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.90gSr
Strontium acetate (Sr (OAC)2·0.5H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon of/g
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 103g/L, K content 6.60g/L, Sr content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 150 DEG C, instead
Answering pressure is 0.10MPa；Raw material volume air speed: 250h-1；Raw material composition: acetylene/acetic acid molar ratio=5:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 151.39g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 8]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 2.90gSr
Strontium acetate (Sr (OAC)2·0.5H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon of/g
Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 103g/L, K content 6.60g/L, Sr content 2.90g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 200 DEG C, instead
Answering pressure is 0.50MPa；Raw material volume air speed: 350h-1；Raw material composition: acetylene/acetic acid molar ratio=12:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 163.06g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 9]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 1.60gBi's
Bismuth subsalicylate (C7H5BiO4) and strontium acetate (Sr (OA containing 1.30gSrC)2·0.5H2O it) is sufficiently mixed and is dissolved in concentration and is
In the aqueous acetic acid of 60wt%, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface
Product is 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g stands 3h in 100 DEG C of dryings, obtains in above-mentioned maceration extract
The catalyst.The Zn content for measuring the catalyst through ICP is 103g/L, and K content 6.60g/L, Bi content 1.60g/L, Sr contain
Measure 1.30g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 164.81g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 9 and embodiment 1 and embodiment 2, is improving vinyl acetate catalyst space-time yield side
Face, in the catalyst that the present invention uses, metal Sr has preferable synergistic effect in VA metal Bi and alkaline-earth metal, illustrates acetic acid
There is in terms of the activity for improving catalyst preferable synergistic effect between zinc, potassium acetate, bismuth subsalicylate and strontium acetate.
[embodiment 10]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 1.60gSb's
Antimony acetate (Sb (OAc)3) and strontium acetate (Sr (OA containing 1.30gSrC)2·0.5H2O it) is sufficiently mixed and is dissolved in concentration and is
In the aqueous acetic acid of 60wt%, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface
Product is 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g stands 3h in 100 DEG C of dryings, obtains in above-mentioned maceration extract
The catalyst.The Zn content for measuring the catalyst through ICP is 103g/L, and K content 6.60g/L, Sb content 1.60g/L, Sr contain
Measure 1.30g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 164.79g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 11]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 1.00gBi's
Bismuth subsalicylate (C7H5BiO4), the antimony acetate (Sb (OAc) containing 0.60gSb3) and strontium acetate (Sr (OA containing 1.30gSrC)2·
0.5H2O) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain maceration extract 350ml, by 1L diameter 3mm,
Long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g is in above-mentioned dipping
In liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Zn content for measuring the catalyst through ICP is 103g/L, K content
6.60g/L, Bi content 1.00g/L, Sb content 0.60g/L, Sr content 1.30g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 166.90g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, is improving vinyl acetate catalyst space-time yield
In terms of yield, in the catalyst that the present invention uses, there is synergistic effect in VA metal between Bi and Sb.Illustrate zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable synergistic effect between sour potassium, bismuth subsalicylate, antimony acetate and strontium acetate.
[embodiment 12]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 1.00gBi's
Bismuth subsalicylate (C7H5BiO4), the antimony acetate (Sb (OAc) containing 0.60gSb3) and barium acetate (Ba (OAc) containing 1.30gBa2·
H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, maceration extract 350ml is obtained, by 1L diameter 3mm, length
2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g is in above-mentioned maceration extract
In, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Zn content for measuring the catalyst through ICP is 103g/L, K content
6.60g/L, Bi content 1.00g/L, Sb content 0.60g/L, Ba content 1.30g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 167.08g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 13]
The preparation of catalyst: 103g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 1.00gBi's
Bismuth subsalicylate (C7H5BiO4), the antimony acetate (Sb (OAc) containing 0.60gSb3), the strontium acetate (Sr (OA containing 0.85gSrC)2·
0.5H2) and (Ba (OAc) of the barium acetate containing 0.45gBa O2·H2O) be sufficiently mixed be dissolved in concentration be 60wt% acetic acid it is water-soluble
In liquid, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal of/g
Matter cylindrical activated carbon carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.It is surveyed through ICP
The Zn content of the fixed catalyst is 103g/L, K content 6.60g/L, Bi content 1.00g/L, Sb content 0.60g/L, Sr content
0.85g/L, Ba content 0.45g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, N is used2After leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 177 DEG C, instead
Answering pressure is 0.25MPa；Raw material volume air speed: 280h-1；Raw material composition: acetylene/acetic acid molar ratio=6:1, sustained response 50h
Afterwards, stop 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 space-time yield for being computed catalyst is 169.14g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
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 terms of yield, in the catalyst that the present invention uses, there is synergistic effect in alkaline-earth metal between Sr and Ba.Illustrate zinc acetate,
There is in terms of the activity for improving catalyst preferable association between potassium acetate, bismuth subsalicylate, antimony acetate, strontium acetate and barium acetate
Same effect.
Table 1
Table 2
Claims (6)
1. the catalyst for producing acetylene method vinyl acetate, the catalyst use active carbon for carrier, active component includes
Zinc acetate, potassium acetate, the compound of VA race metallic element and alkali earth metal compound, wherein the alkali earth metal
For strontium, VA race metallic element is bismuth and/or antimony；Alternatively, the alkali earth metal is selected from combination or the barium of strontium and barium, institute
State the combination that VA race metallic element is bismuth and antimony；
Wherein, in the catalyst, the content of zinc acetate is 50~300g/L, and the content of potassium acetate is 0.10~10.00g/
The content of L, VA race metallic element and alkali earth metal is 0.50~8.00g/L.
2. catalyst according to claim 1, it is characterised in that the active carbon be coal quality column charcoal, cocoanut active charcoal,
At least one of apricot shell active carbon and activated carbon from bamboo.
3. catalyst according to claim 1, it is characterised in that the specific surface area of the active carbon is 1000~1500cm2/
G, it is 0.60~1.00cm that adsorption hole, which holds,3/g。
4. being included the following steps: by the production method of catalyst described in claim 1
1. by the composition of catalyst by zinc acetate, potassium acetate, VA race metallic element compound and alkaline-earth metal component
Solution is mixed with carrier；
2. drying.
5. vinyl acetate synthesis method is closed under catalyst described in any one of claims 1 to 3 using acetic acid, acetylene as raw material
At vinyl acetate.
6. synthetic method according to claim 5, it is characterized in that with molar ratio computing raw material group as acetylene: acetic acid=(5~
12):1。
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