CN106423267B - The catalyst of preparing vinyl acetate using acetylene method - Google Patents
The catalyst of preparing vinyl acetate using acetylene method Download PDFInfo
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Abstract
The present invention relates to the catalyst of preparing vinyl acetate using 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 preparing vinyl acetate using 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 platinum cluster metallic element or 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 of preparing vinyl acetate using 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 preparing vinyl acetate using 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: preparing vinyl acetate using acetylene method
Catalyst, the catalyst use active carbon for carrier, active component include zinc acetate, potassium acetate and selected from platinum group metal member or
The compound of at least one of alkaline-earth metal metallic element.It is preferred that the active component includes simultaneously zinc acetate, potassium acetate, choosing
From the compound of at least one of platinum group metallic element and selected from least one of alkaline-earth metal metallic element
Compound.At this time between the compound of the metallic element in the compound and alkaline-earth metal of the metallic element in platinum group metal
There is synergistic effect in terms of improving the space-time yield of vinyl acetate catalyst.
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 platinum group preferably is selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium,
It more preferably simultaneously include palladium and rhodium.
In above-mentioned technical proposal, the alkaline-earth metal metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium, more excellent
It selects while including beryllium and strontium.
In above-mentioned technical proposal, more more preferably the platinum group includes palladium and rhodium, the alkaline-earth metal gold simultaneously
Belong to while including beryllium and strontium.
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 platinum group and alkali earth metal；Such as the active component is by zinc acetate, acetic acid
Potassium, palladium acetate (or rhodium acetate) and beryllium acetate composition, or by zinc acetate, potassium acetate, palladium acetate, rhodium acetate and beryllium acetate (or
Strontium acetate) composition, or be made of zinc acetate, potassium acetate, palladium acetate, rhodium acetate, beryllium acetate and strontium 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 platinum group metal 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 the composition of catalyst by the solution and load of the compound of zinc acetate, potassium acetate, platinum group metal and alkaline-earth metal
Body mixing；
2. drying.
In above-mentioned technical proposal, the compound of the step 1. platinum group preferably is selected from radium chloride, rhodium acetate two is matched
Body, rhodium nitrate, palladium chloride, four ammonia palladium of dichloro, palladium acetate, ammonium chloropalladite, ruthenic chloride, is crossed in ruthenic acid four triphenylphosphine chlorine rhodium
Amine, acetic acid ruthenium, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, platinum acetate, osmium trichloride, acetic acid osmium, iridous chloride, acetic acid iridium and
At least one of chloro-iridic acid；The acetate of more excellent platinum group；Step 1. in the alkaline-earth metal metal compound
It preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkali earth metal sulfate, alkaline earth nitrate and alkaline-earth metal vinegar
At least one of hydrochlorate；More preferable Alkaline Earth 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 platinum group and alkaline-earth 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 162.49g/Lh when using catalyst of the present invention, obtain
Active component includes simultaneously zinc acetate, potassium acetate, in platinum family element in preferable technical effect, especially catalyst
At least one metallic element compound and when selected from least one of alkaline-earth metal metallic element compound, achieves more prominent
Technical effect out, 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: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc) and containing 3.20gPd's
Palladium acetate (Pd (OAc)2) 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 98g/L,
K content 6.30g/L, Pd content 3.20g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 162.49g/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: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc) and Be containing 3.20g
Beryllium acetate (Be (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 98g/
L, K content 6.30g/L, Be content 3.20g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 162.38g/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: 98g zinc acetate (Zn (OAc) will be contained2) and potassium acetate containing 6.30g (KOAc) be sufficiently mixed dissolution
In the aqueous acetic acid that concentration is 60wt%, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/
G, specific surface area is 1200m2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for the coal quality cylindrical activated carbon carrier impregnation of/g
It is dry, obtain the catalyst.The Zn content for measuring the catalyst through ICP is 98g/L, K content 6.30g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 121.75g/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 rhodium acetate active component, simultaneously the catalyst performance ratio containing zinc acetate, potassium acetate and beryllium 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 1.00gRh's
Rhodium acetate (Rh2(OAc)4) 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 0.60cm3/ g, specific surface area 1000m2The cylindrical type cocoanut active charcoal carrier impregnation of/g is upper
It states in maceration extract, stands 3h in 80 DEG C of dryings, obtain the catalyst.The Zn content for measuring the catalyst through ICP is 80g/L, K
Content 3.00g/L, Rh 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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 127.04g/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 Mg containing 5.00g
Magnesium acetate (Mg (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 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, Mg 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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 163.05Lh, 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: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc) and Ca containing 3.20g
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 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 98g/L, K content 6.30g/L, Ca content 3.20g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 6]
The preparation of catalyst: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc) and containing 3.20gSr'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 0.80cm3/ 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 98g/L, K content 6.30g/L, Sr content 3.20g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 162.46g/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: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc) and containing 3.20gIr's
Acetic acid iridium (Ir (OAc)3·XH2O 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 98g/L, K content 6.30g/L, Ir content 3.20g/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 153.24g/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.
[embodiment 8]
The preparation of catalyst: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc) and containing 3.20gBa's
Barium acetate (Ba (OAc)2) 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 98g/L,
K content 6.30g/L, Ba content 3.20g/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 163.13g/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: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc), containing 1.70gPd's
Palladium acetate (Pd (OAc)2) and the Be containing 1.50g beryllium acetate (Be (OAc)2) it is sufficiently mixed the acetic acid for being dissolved in that concentration is 60wt%
In aqueous solution, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2/g
Coal quality cylindrical activated carbon carrier impregnation in above-mentioned maceration extract, stand 3h in 100 DEG C of dryings, obtain the catalyst.Through
The Zn content that ICP measures the catalyst is 98g/L, K content 6.30g/L, Pd content 1.70g/L, Be content 1.50g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 164.87g/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, there is metal Pd with metal Be in alkaline-earth metal in the catalyst that the present invention uses, in platinum group preferably cooperates with work
With illustrating that there is in terms of the activity for improving catalyst preferable collaboration between zinc acetate, potassium acetate, palladium acetate and beryllium acetate
Effect.
[embodiment 10]
The preparation of catalyst: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc), containing 1.70gRh's
Rhodium acetate (Rh2(OAc)4) and the Be containing 1.50g beryllium acetate (Be (OAc)2) it is sufficiently mixed the vinegar for being dissolved in that concentration is 60wt%
In aqueous acid, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200m2/
The coal quality cylindrical activated carbon carrier impregnation of g stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through
The Zn content that ICP measures the catalyst is 98g/L, K content 6.30g/L, Rh content 1.70g/L, Be content 1.50g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 164.93g/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: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc), containing 1.00gPd's
Palladium acetate (Pd (OAc)2), the rhodium acetate (Rh containing 0.70gRh2(OAc)4) and beryllium acetate (Be (OAc) containing 1.50gBe2) 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 98g/L, K content 6.30g/L, Pd content
1.00g/L, Rh content 0.70g/L, Be content 1.50g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 167.28g/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 platinum group metal between Pd, Rh.It illustrates
There is in terms of the activity for improving catalyst preferable collaboration effect between zinc acetate, potassium acetate, palladium acetate, rhodium acetate and beryllium acetate
It answers.
[embodiment 12]
The preparation of catalyst: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc), containing 1.00gPd's
Palladium acetate (Pd (OAc)2), the rhodium acetate (Rh containing 0.70gRh2(OAc)4) and strontium acetate (Sr (OA containing 1.50gSrC)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 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 98g/L, K content
6.30g/L, Pd content 1.00g/L, Rh content 0.70g/L, Sr content 1.50g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 167.42g/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 13]
The preparation of catalyst: 98g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.30g (KOAc), containing 1.00gPd's
Palladium acetate (Pd (OAc)2), the rhodium acetate (Rh containing 0.70gRh2(OAc)4), the beryllium acetate (Be (OAc) containing 0.55gBe2) and contain
Strontium acetate (Sr (the OA of 0.95gSrC)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 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 98g/L, K content 6.30g/L, Pd content 1.00g/L, Rh content 0.70g/L, Be content 0.55g/L, Sr content
0.95g/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 173 DEG C, instead
Answering pressure is 0.28MPa；Raw material volume air speed: 300h-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 169.70g/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 Be and Sr.Illustrate zinc acetate,
There is in terms of the activity for improving catalyst preferable collaboration effect between potassium acetate, palladium acetate, rhodium acetate, beryllium acetate and strontium acetate
It answers.
Table 1
Table 2
Claims (8)
1. the catalyst of preparing vinyl acetate using acetylene method, the catalyst uses active carbon for carrier, active component by zinc acetate,
Potassium acetate and compound selected from least one of platinum group metal metallic element and golden selected from least one of alkaline-earth metal
Belong to the compound composition of element；
Wherein, the compound selected from least one of platinum group metal metallic element described in catalyst and in alkaline-earth metal
At least one metallic element compound content be 3.2~8.00g/L；
The content of zinc acetate is 98~300g/L in catalyst, and the content of potassium acetate is 6.3~10.00g/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 platinum group be selected from platinum, palladium, osmium, iridium, ruthenium and
At least one of rhodium.
5. catalyst according to claim 1, it is characterised in that the alkali earth metal is in beryllium, magnesium, calcium, strontium and barium
At least one.
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, platinum group metal and alkaline-earth metal and carrier are mixed by the composition of catalyst
It closes；
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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