CN106423268B - The catalyst of producing vinyl acetate by acetylene method - Google Patents
The catalyst of producing vinyl acetate by acetylene method Download PDFInfo
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Abstract
The present invention relates to the catalyst of producing vinyl acetate by acetylene method, mainly solve the problems, such as that acetylene in gas phase method catalyst activity is not high in the prior art.The present invention uses the catalyst of producing vinyl acetate by acetylene method, 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 VIII metal or alkali 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 of producing vinyl acetate by acetylene method, the system of the acetylene in gas phase method vinyl acetate catalyst
The synthetic method of Preparation Method and acetylene in gas phase method vinyl acetate.
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 catalyst of new producing vinyl acetate by acetylene method, 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: producing vinyl acetate by acetylene method
Catalyst, the catalyst use active carbon for carrier, and active component includes zinc acetate, potassium acetate and selected from VIII metal or alkali
The compound of at least one of metal metallic element.It is preferred that the active component includes simultaneously zinc acetate, potassium acetate, is selected from
The compound of at least one of VIII metallic element metallic element and change selected from least one of alkali metal metallic element
Close object.Vinegar is being improved between the compound of the metallic element in the compound and alkali metal of the metallic element in VIII metal at this time
There is synergistic effect in terms of the space-time yield of sour catalyst for ethylene.
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 1000~1500m2/ g, adsorption hole hold preferably 0.60
~1.00cm3/g。
In above-mentioned technical proposal, the VIII metallic element preferably is selected from cobalt, nickel, iron, platinum, palladium, osmium, iridium, ruthenium and rhodium
At least one more preferably includes cobalt and rhodium simultaneously.
In above-mentioned technical proposal, the alkali metal metal preferably is selected from least one of lithium, sodium, rubidium and caesium, more preferably same
When include lithium and rubidium.
In above-mentioned technical proposal, more more preferably the VIII metallic element includes simultaneously cobalt and rhodium, the alkali metal metal
It simultaneously include lithium and rubidium.
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 VIII metallic element and alkali metal element；Such as the active component by zinc acetate, potassium acetate,
Acetic acid rubidium (or lithium acetate) and rhodium acetate composition, or by zinc acetate, potassium acetate, acetic acid rubidium, lithium acetate and rhodium acetate (or acetic acid
Cobalt) composition, or be made of zinc acetate, potassium acetate, acetic acid rubidium, lithium acetate, rhodium acetate and cobalt 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 metallic element is preferably 0.50~8.00g/L in VIII metal and alkali 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 the composition of catalyst by the solution and carrier of the compound of zinc acetate, potassium acetate, VIII metal and alkali metal
Mixing；
2. drying.
In above-mentioned technical proposal, the compound of the step 1. VIII metallic element preferably is selected from ferrous acetate, ferrocene, chlorine
Change iron, ferric sulfate, carbonyl cobalt, cobalt acetate, cobalt chloride, cobalt nitrate, carbonyl nickel, nickel acetate, nickel nitrate, nickel sulfate, nickel chloride, chlorine
Change rhodium, two ligand of rhodium acetate, triphenylphosphine chlorine rhodium, rhodium nitrate, palladium chloride, four ammonia palladium of dichloro, palladium acetate, ammonium chloropalladite, chlorine
Change ruthenium, cross amine, acetic acid ruthenium, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, platinum acetate, osmium trichloride, acetic acid osmium, three in ruthenic acid four
At least one of iridium chloride, acetic acid iridium and chloro-iridic acid；The acetate of more excellent VIII metallic element；Step is 1. in the alkali metal
The compound of metal preferably is selected from alkali metal oxide, alkali metal chloride, alkali metal sulfates, alkali nitrates and alkali metal
At least one of acetate；More preferable alkali metal acetate.2. the drying temperature is 80~120 DEG C to step, more preferably
100~120 DEG C.
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 the compound of VIII metallic element and alkali metal metallic element, be conducive to improve catalyst
Activity and stability, to improve the yield of vinyl acetate.
The experimental results showed that the space-time yield of catalyst reaches 162.31g/Lh when using catalyst of the present invention, obtain
Active component includes zinc acetate, potassium acetate, selected from VIII metallic element simultaneously in preferable technical effect, especially catalyst
At least one of metallic element compound and when selected from least one of alkali metal metallic element compound, achieve more
Technical effect outstanding, 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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gRb
Acetic acid rubidium (RbOAc) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, maceration extract 350ml is obtained, by 1L
Diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The coal quality cylindrical activated carbon carrier impregnation of/g is upper
It states in maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Zn content for measuring the catalyst through ICP is 100g/
L, K content 6.10g/L, Rb content 3.50g/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 175 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 162.31g/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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gRh
Rhodium acetate (Rh2(OAc)4) 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 1200m2The coal quality cylindrical activated carbon carrier impregnation of/g exists
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Zn content for measuring the catalyst through ICP is
100g/L, K content 6.10g/L, Rh content 3.50g/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 175 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 162.40g/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: 100g zinc acetate (Zn (OAc) will be contained2) and potassium acetate containing 6.10g (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 1200m2The 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 100g/L, K content 6.10g/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 175 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 121.44g/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 acetic acid rubidium active component, simultaneously the catalyst performance ratio containing zinc acetate, potassium acetate and rhodium acetate active component are containing only acetic acid
Zinc, 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 1.00gCo's
Cobalt acetate (Co (OAc)2·4H2O 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 1000m2The cylindrical type cocoanut active charcoal of/g carries
Body is immersed in above-mentioned maceration extract, is stood 3h in 80 DEG C of dryings, is obtained the catalyst.The Zn for measuring the catalyst through ICP contains
Amount is 80g/L, K content 3.00g/L, Co content 1.00g/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 175 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 127.53g/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 Na containing 5.00g
Magnesium acetate (NaOAc3H2O 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 1500m2The cylindrical type apricot shell carried by active carbon of/g
Body is immersed in above-mentioned maceration extract, is stood 3h in 120 DEG C of dryings, is obtained the catalyst.The Zn for measuring the catalyst through ICP contains
Amount is 200g/L, K content 7.00g/L, Na 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 175 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 162.94Lh, for ease of description and is compared, catalyst prepares item
Part, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 5]
The preparation of catalyst: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and Li containing 3.50g
Lithium acetate (LiOAc2H2O 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 1200m2The cylindrical type activated carbon from bamboo of/g carries
Body is immersed in above-mentioned maceration extract, is stood 3h in 120 DEG C of dryings, is obtained the catalyst.The catalysis is measured through ICP and ICP-MS
The Zn content of agent is 100g/L, K content 6.10g/L, Li content 3.50g/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 175 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 162.34g/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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gCs
Cesium acetate (CsOAC) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, maceration extract 350ml is obtained, by 1L
Diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2The coal quality cylindrical activated carbon carrier impregnation of/g is upper
It states in maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Zn content for measuring the catalyst through ICP is 100g/
L, K content 6.10g/L, Cs content 3.50g/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 175 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 162.35g/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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gNi
Nickel acetate (Ni (OAc)2) 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 1200m2The coal quality cylindrical activated carbon carrier impregnation of/g exists
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Zn content for measuring the catalyst through ICP is
100g/L, K content 6.10g/L, Ni content 3.50g/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 153.15g/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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gRu
Acetic acid ruthenium (Ru (OAc)3·3H2O 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 1200m2The coal quality cylindrical activated carbon of/g carries
Body is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The Zn for measuring the catalyst through ICP contains
Amount is 100g/L, K content 6.10g/L, Ru content 3.50g/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 163.01g/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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), containing 1.60gRb's
Acetic acid rubidium (RbOAc) and rhodium acetate (Rh containing 1.90gRh2(OAc)4) it is sufficiently mixed the acetic acid water for being dissolved in that concentration is 60wt%
In solution, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2/ g's
Coal quality cylindrical activated carbon carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP
The Zn content for measuring the catalyst is 100g/L, K content 6.10g/L, Rb content 1.60g/L, Rh content 1.90g/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 175 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 164.59g/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 Rh has preferable synergistic effect, explanation in metal Rb and VIII metal in alkali metal
There is between zinc acetate, potassium acetate, acetic acid rubidium and rhodium acetate preferable synergistic effect in terms of the activity for improving catalyst.
[embodiment 10]
The preparation of catalyst: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), containing 1.60gLi's
Lithium acetate (LiOAc2H2O rhodium acetate (the Rh) and containing 1.90gRh2(OAc)4) it is sufficiently mixed that be dissolved in concentration be 60wt%
In aqueous acetic acid, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area are
1200m2The coal quality cylindrical activated carbon carrier impregnation of/g stands 3h in 100 DEG C of dryings in above-mentioned maceration extract, obtains described urge
Agent.The Zn content for measuring the catalyst through ICP is 100g/L, K content 6.10g/L, Li content 1.60g/L, Rh content
1.90g/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 175 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 164.68g/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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), containing 0.90gRb's
Acetic acid rubidium (RbOAc), the lithium acetate (LiOAc2H containing 0.70gLi2O rhodium acetate (the Rh) and containing 1.90gRh2(OAc)4) sufficiently
Mixed dissolution 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 1200m2The 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 100g/L, and K content 6.10g/L, Rb contain
Measure 0.90g/L, Li content 0.70g/L, Rh content 1.90g/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 175 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 167.26g/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 alkali metal between Rb, Li.Illustrate zinc acetate, acetic acid
There is in terms of the activity for improving catalyst preferable synergistic effect between potassium, acetic acid rubidium, lithium acetate and rhodium acetate.
[embodiment 12]
The preparation of catalyst: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), containing 0.90gRb's
Acetic acid rubidium (RbOAc), the lithium acetate (LiOAc2H containing 0.70gLi2) and the cobalt acetate of the Co containing 1.90g (Co (OAc) O2·
4H2O 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 1200m2The 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 100g/L, K content
6.10g/L, Rb content 0.90g/L, Li content 0.70g/L, Co content 1.90g/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 175 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 167.18g/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: 100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), containing 0.90gRb's
Acetic acid rubidium (RbOAc), the lithium acetate (LiOAc2H containing 0.70gLi2O), the rhodium acetate (Rh containing 1.00gRh2(OAc)4) and contain
Cobalt acetate (the Co (OAc) of 0.90g Co2·4H2O 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 1200m2The cylindric work of the coal quality of/g
Property high-area carbon be immersed in above-mentioned maceration extract, stand 3h in 100 DEG C of dryings, obtain the catalyst.The catalyst is measured through ICP
Zn content be 100g/L, K content 6.10g/L, Rb content 0.90g/L, Li content 0.70g/L, Rh content 1.00g/L, Co contain
Measure 0.90g/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 175 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 169.65g/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 VIII metal between Rh and Co.Illustrate zinc acetate,
There is in terms of the activity for improving catalyst preferable collaboration effect between potassium acetate, acetic acid rubidium, lithium acetate, rhodium acetate and cobalt acetate
It answers.
Table 1
Table 2
Claims (8)
1. the catalyst of producing vinyl acetate by acetylene method, the catalyst uses active carbon for carrier, and active component includes acetic acid
Zinc, potassium acetate, the compound selected from least one of VIII metal metallic element and golden selected from least one of alkali metal
Belong to the compound of element；The content of zinc acetate in catalyst are as follows: 100~300g/L, the content of potassium acetate are as follows: 6.10~
10.00g/L；Described in catalyst in VIII metallic element and alkali metal metallic element at least one content be 3.50~
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 1000~1500m2/
G, it is 0.60~1.00cm that adsorption hole, which holds,3/g。
4. catalyst according to claim 1, it is characterised in that the VIII metallic element be selected from cobalt, nickel, iron, platinum, palladium,
At least one of osmium, iridium, ruthenium and rhodium.
5. catalyst according to claim 1, it is characterised in that the alkali metal element in lithium, sodium, rubidium and caesium extremely
Few one kind.
6. being included the following steps: by the production method of catalyst described in claim 1
1. the solution of the compound of zinc acetate, potassium acetate, VIII metal and alkali metal is mixed with carrier by the composition of catalyst；
2. drying.
7. vinyl acetate synthesis method is closed under catalyst described in any one of Claims 1 to 5 using acetic acid, acetylene as raw material
At vinyl acetate.
8. synthetic method according to claim 7, it is characterized in that with molar ratio computing raw material group as acetylene: acetic acid=(5~
12):1。
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