CN106423266B - Acetylene method vinyl acetate preparation catalyst used - Google Patents
Acetylene method vinyl acetate preparation catalyst used Download PDFInfo
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Abstract
The present invention relates to acetylene method vinyl acetate preparation catalyst used, mainly solve the problems, such as that acetylene in gas phase method catalyst activity is not high in the prior art.The present invention catalyst used using the preparation of 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 Ferrious material or VB metal 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 acetylene method vinyl acetate preparation catalyst used, the acetylene in gas phase method vinyl acetate catalysts
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 catalyst that new acetylene method vinyl acetate preparation is used, 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: acetylene method vinyl acetate prepares institute
Catalyst, the catalyst use active carbon for carrier, and active component includes zinc acetate, potassium acetate and selected from Ferrious material
Or the compound of at least one of VB metal element.It is preferred that the active component includes zinc acetate, potassium acetate, selected from iron simultaneously
It is the compound of at least one of metallic element element and the compound selected from least one of VB metal element.Iron at this time
It is to improve vinyl acetate catalyst between the compound of the metallic element in the compound and VB of the metallic element in metal
There is synergistic effect in terms of space-time yield.
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 iron series element preferably is selected from least one of iron, cobalt and nickel, more preferably includes simultaneously
Cobalt and nickel.
In above-mentioned technical proposal, the VB metal preferably is selected from least one of vanadium, niobium and tantalum, more preferably simultaneously includes vanadium
And niobium.
In above-mentioned technical proposal, more more preferably the iron series element includes simultaneously cobalt and nickel, and the VB metal includes simultaneously
Vanadium and niobium.
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 Ferrious material element and VB metallic element；Such as the active component by zinc acetate, potassium acetate,
Cobalt acetate (or nickel acetate) and acetic acid vanadium composition, or by zinc acetate, potassium acetate, cobalt acetate, nickel acetate and acetic acid vanadium (or acetic acid
Niobium) composition, or be made of zinc acetate, potassium acetate, cobalt acetate, nickel acetate, acetic acid vanadium and acetic acid niobium.
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 Ferrious material and VB, more preferably
For 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 zinc acetate, potassium acetate, Ferrious material element and VB metallic element compound it is molten
Liquid is mixed with carrier；
2. drying.
In above-mentioned technical proposal, the compound of the step 1. iron series element preferably is selected from ferrous acetate, ferrocene, chlorination
In iron, ferric sulfate, carbonyl cobalt, cobalt acetate, cobalt chloride, cobalt nitrate, carbonyl nickel, nickel acetate, nickel nitrate, nickel sulfate and nickel chloride
It is at least one；The acetate of more excellent Ferrious material element；1. metallic compound preferably is selected from vanadium trichloride, inclined vanadium to step in the VB
At least one of sour ammonium, acetic acid vanadium, vanadic anhydride, columbium pentachloride, niobium oxalate, acetic acid niobium, acetic acid tantalum and tantalic chloride；More
It is preferred that at least one of acetic acid niobium and acetic acid vanadium.Step 2. the drying temperature be 80~120 DEG C, more preferably 100~120
℃。
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 Ferrious material element and VB metallic element, be conducive to the activity for improving catalyst
And stability, to improve the yield of vinyl acetate.
The experimental results showed that the space-time yield of catalyst reaches 162.41g/Lh when using catalyst of the present invention, obtain
Active component includes simultaneously zinc acetate, potassium acetate, in iron series element in preferable technical effect, especially catalyst
At least one metallic element compound and when selected from least one of VB metallic element compound, achieves skill more outstanding
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: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.60gCo
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 0.80cm3/ 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 102g/L, K content 6.60g/L, Co content 2.60g/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 0.28MPa；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 162.41g/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: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and V containing 2.60g
Acetic acid vanadium (V (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 coal quality cylindrical activated carbon carrier impregnation of/g
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
102g/L, K content 6.60g/L, V content 2.60g/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 0.28MPa；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 162.24g/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: 102g 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 102g/L, K content 6.60g/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 0.28MPa；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 123.95g/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 cobalt acetate active component, simultaneously the catalyst performance ratio containing zinc acetate, potassium acetate and acetic acid vanadium 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 1.00gFe's
Ferrous acetate (Fe (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 0.60cm3/ g, specific surface area 1000cm2The cylindrical type cocoanut active charcoal carrier impregnation of/g
In above-mentioned maceration extract, 3h is stood in 80 DEG C of dryings, obtains the catalyst.The Zn content for measuring the catalyst through ICP is
80g/L, K content 3.00g/L, Fe 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 177 DEG C, instead
Answering pressure is 0.28MPa；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 126.34g/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 4]
The preparation of catalyst: 200g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 7.00g (KOAc) and contain 5.00gNi
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 1.00cm3/ g, specific surface area 1500cm2The cylindrical type apricot shell absorbent charcoal carrier of/g impregnates
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
200g/L, K content 7.00g/L, Ni 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 0.28MPa；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 163.15/Lh, 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: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.60gNi
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 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 of the catalyst is measured through ICP and ICP-MS
Content is 102g/L, K content 6.60g/L, Ni content 2.60g/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 0.28MPa；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 162.45g/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: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.60gNb
Acetic acid niobium (Nb (OAc)5) 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 coal quality cylindrical activated carbon carrier impregnation of/g
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
102g/L, K content 6.60g/L, Nb content 2.60g/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 0.28MPa；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 162.22g/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: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.60gCo
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 0.80cm3/ 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 102g/L, K content 6.60g/L, Co content 2.60g/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 152.65g/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.
[embodiment 8]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc) and contain 2.60gCo
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 0.80cm3/ 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 102g/L, K content 6.60g/L, Co content 2.60g/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 163.31g/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 9]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 1.50gCo's
Cobalt acetate (Co (OAc)2·4H2) and the acetic acid vanadium (V (OAc) of the V containing 1.10g O3) 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
1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g stands 3h in 100 DEG C of dryings in above-mentioned maceration extract, obtains described
Catalyst.The Zn content for measuring the catalyst through ICP is 102g/L, K content 6.60g/L, Co content 1.50g/L, V content
1.10g/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 177 DEG C, instead
Answering pressure is 0.28MPa；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 164.92g/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, V has preferable synergistic effect in metal Co and VB metal in iron series element, illustrates vinegar
There is in terms of the activity for improving catalyst preferable synergistic effect between sour zinc, potassium acetate, cobalt acetate and acetic acid vanadium.
[embodiment 10]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 1.50gNi's
Nickel acetate (Ni (OAc)2) and the V containing 1.10g acetic acid vanadium (V (OAc)3) 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 1200cm2/ 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 102g/L, K content 6.60g/L, Ni content 1.50g/L, V content 1.10g/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 177 DEG C, instead
Answering pressure is 0.28MPa；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 164.78g/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: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 0.85gCo's
Cobalt acetate (Co (OAc)2·4H2O), the nickel acetate (Ni (OAc) of the Ni containing 0.65g2) and the V containing 1.10g acetic acid vanadium (V
(OAc)3) 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 102g/L, K content
6.60g/L, Co content 0.85g/L, Ni content 0.65g/L, V content 1.10g/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 177 DEG C, instead
Answering pressure is 0.28MPa；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 166.85g/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 iron series element metal between Co and Ni.Illustrate acetic acid
There is in terms of the activity for improving catalyst preferable synergistic effect between zinc, potassium acetate, cobalt acetate, nickel acetate and acetic acid vanadium.
[embodiment 12]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 0.85gCo's
Cobalt acetate (Co (OAc)2·4H2O), the nickel acetate (Ni (OAc) of the Ni containing 0.65g2) and the Nb containing 1.10g acetic acid niobium (Nb
(OAc)5) 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 102g/L, K content
6.60g/L, Co content 0.85g/L, Ni content 0.65g/L, Nb content 1.10g/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 177 DEG C, instead
Answering pressure is 0.28MPa；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 167.02g/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: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.60g (KOAc), containing 0.85gCo's
Cobalt acetate (Co (OAc)2·4H2O), the nickel acetate (Ni (OAc) of the Ni containing 0.65g2), the acetic acid vanadium (V (OAc) of the V containing 0.50g3)
With the acetic acid niobium (Nb (OAc) of the Nb containing 0.60g5) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, soaked
Stain liquid 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The 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 102g/L, K content 6.60g/L, Co content 0.85g/L, Ni content 0.65g/L, V content 0.50g/L, Nb content
0.60g/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 0.28MPa；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 169.17g/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 VB metal between V and Nb.Illustrate zinc acetate, acetic acid
There is in terms of the activity for improving catalyst preferable synergistic effect between potassium, cobalt acetate, nickel acetate, acetic acid vanadium and acetic acid niobium.
Table 1
Table 2
Claims (7)
1. acetylene method vinyl acetate preparation catalyst used, the catalyst use active carbon for carrier, active component includes
Zinc acetate, potassium acetate, the compound of Ferrious material element and the compound selected from least one of VB metallic element element；Institute
It states Ferrious material element while including cobalt and nickel；The content of zinc acetate in catalyst are as follows: 50~300g/L, the content of potassium acetate
Are as follows: 0.10~10.00g/L；Ferrious material element described in catalyst and the content selected from least one of VB metallic element
For 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. catalyst according to claim 1, it is characterised in that the VB metallic element in vanadium, niobium and tantalum at least one
Kind.
5. being included the following steps: by the production method of catalyst described in claim 1
1. by the composition of catalyst by the solution and load of the element compound in zinc acetate, potassium acetate, Ferrious material and VB metal
Body mixing；
2. drying.
6. vinyl acetate synthesis method, using acetic acid, acetylene as raw material, the catalyst described in any one of Claims 1 to 4 or power
Benefit require 5 described in method production catalyst under synthesizing vinyl acetate.
7. synthetic method according to claim 6, it is characterized in that with molar ratio computing raw material group as acetylene: acetic acid=(5~
12):1。
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