CN106268942B - It is used to prepare the catalyst of acetylene method vinyl acetate - Google Patents
It is used to prepare the catalyst of acetylene method vinyl acetate Download PDFInfo
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Abstract
The present invention relates to the catalyst for being used to prepare acetylene method vinyl acetate, mainly solve the problems, such as that acetylene in gas phase method catalyst activity is not high in the prior art.The present invention is used to prepare the catalyst 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 VA or IIB metal metallic element, it preferably solves the problems, such as this, can be used in the industrial production of acetylene in gas phase method synthesizing vinyl acetate.
Description
Technical field
The present invention relates to the catalyst for being used to prepare acetylene method vinyl acetate, the acetylene in gas phase method vinyl acetate catalyst
Preparation method and acetylene in gas phase method vinyl acetate synthetic method.
Background technique
Vinyl acetate (Vinyl acetate, abbreviation VAC) it is important Organic Chemicals, it is poly- to be widely used in manufacture
Vinyl acetate, polyvinyl alcohol are simultaneously further processed for binder, coating, vinylon fibre, fabric processing, lotion, resin and thin
Film etc..Currently, the method for industrial production vinyl acetate has acetylene in gas phase method and ethylene vapor phase method.
Producing vinyl acetate by acetylene method experienced two developing stage of liquid and gas technique.Before 1940, mainly
It based on liquid phase process, is reacted under 30~70 DEG C of normal pressures, catalyst is mercury oxide and sulfuric acid or phosphoric acid；40 years 20th century
After generation, start based on acetylene in gas phase method, catalyst is the active carbon for having loaded zinc acetate.
The zinc acetate of nineteen twenty-two Germany Wacker company Muqaen discovery dipping on the activated carbon can be with vapor- phase synthesis acetic acid
Ethylene then proposes the method using acetylene in gas phase synthesis VAc, improves investment industrial production by Hochst company.It is catalyzed
Agent is with Zn (OAc)2For active component, using active carbon as carrier, and use till today always.United States Patent (USP) (US166482,
Production of vinyl acetate) it reports using catalyst Z n (OAc)2/ C, has synthesized vinyl acetate.It is Chinese special
Sharp CN1903435 (a kind of title are as follows: catalyst and preparation method thereof for vinyl acetate synthesis) provides a kind of acetylene method
The preparation method of vinyl acetate catalyst, catalyst activity component uses zinc oxide and acetic acid, and a small amount of waltherite is added, by it
It is immersed in active carbon and is dried to obtain catalyst.But the catalyst activity that above-mentioned technology provides is not high, limits acetylene method acetic acid
The application of ethylene.
Summary of the invention
The first technical problem to be solved by the present invention is that acetylene method vinyl acetate catalyst activity is low in the prior art
Problem provides a kind of new catalyst for being used to prepare acetylene method vinyl acetate, the active high feature of the catalyst.
The second technical problem to be solved by the present invention is the producer using catalyst described in one of above-mentioned technical problem
Method.
The third technical problem to be solved by the present invention is the acetic acid second using catalyst described in one of above-mentioned technical problem
The synthetic method of alkene.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: being used to prepare acetylene method acetic acid second
The catalyst of alkene, the catalyst use active carbon for carrier, and active component includes zinc acetate, potassium acetate and selected from VA or IIB
At least one of metallic element compound.It is preferred that the active component includes simultaneously zinc acetate, potassium acetate, in VA
At least one metallic element and compound selected from least one of IIB metallic element.The chemical combination of the metallic element of VA at this time
Have in terms of the space-time yield for improving vinyl acetate catalyst between object and the compound of the metallic element in IIB and cooperates with work
With.
In above-mentioned technical proposal, the active carbon preferably is selected from coal quality column charcoal, cocoanut active charcoal, apricot shell active carbon and bamboo matter
At least one of active carbon.The specific surface area of the active carbon is preferably 1000~1500cm2/ g, adsorption hole hold preferably 0.60
~1.00cm3/g。
In above-mentioned technical proposal, the VA metal preferably is selected from least one of antimony and bismuth, more preferably simultaneously include antimony and
Bismuth.The IIB metal preferably is selected from least one of cadmium and mercury, more preferably simultaneously includes cadmium and mercury.
In above-mentioned technical proposal, as most preferred technical solution, the active component includes simultaneously zinc acetate, acetic acid
The compound of potassium, the compound of VA metallic element and IIB metallic element；Such as the active component is by zinc acetate, potassium acetate, lemon
Lemon acid bismuth ammonium (or antimony acetate) and cadmium acetate composition, or by zinc acetate, potassium acetate, bismuth and ammonium citrate, antimony acetate and cadmium acetate
(or mercuric acetate) composition, or be made of zinc acetate, potassium acetate, bismuth and ammonium citrate, antimony acetate, cadmium acetate and mercuric acetate.
In above-mentioned technical proposal, the content of zinc acetate is preferably 50~300g/L in the catalyst, more preferably 80~
200g/L；The content of potassium acetate is preferably 0.10~10.00g/L in the catalyst, more preferably 3.00~7.00g/L；Institute
State in catalyst that at least one content of metal is preferably 0.50~8.00g/L in VA and IIB, 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. the solution and carrier of metallic element compound in zinc acetate, potassium acetate, VA and IIB are mixed by the composition of catalyst
It closes；
2. drying.
In above-mentioned technical proposal, the preferred basic bismuth carbonate of compound, the bismuth subnitrate, citric acid of the step 1. VA metal
At least one of bismuth ammonium, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate, antimony acetate and antimony chloride；More preferably from lemon
At least one of lemon acid bismuth ammonium and antimony acetate；Step 1. in the IIB compound of metal preferably be selected from cadmium acetate, caddy,
At least one of cadmium nitrate, mercuric acetate, mercurous nitrate and mercuric sulfate；More preferably from least one in cadmium acetate and mercuric acetate
Kind.2. the drying temperature is 80~120 DEG C, more preferably 100~120 DEG C to step.
To solve above-mentioned technical problem three, technical scheme is as follows: vinyl acetate synthesis method, with acetic acid,
Acetylene is raw material, and reaction generates acetic acid in the presence of the catalyst described in any one of technical solution of one of above-mentioned technical problem
Ethylene.
Key of the invention is the selection of catalyst, and skilled person will know how suitable determine according to actual needs
Reaction temperature, the reaction time, reaction pressure and material proportion.But the temperature reacted in above-mentioned technical proposal is preferably
150~200 DEG C；The pressure of reaction is preferably 0.1~0.5MPa；Preferably acetylene: acetic acid=(5 is formed with molar ratio computing raw material
~12): 1；Raw material volume air speed is preferably 250~350h-1。
The content gas chromatography analysis of each component in reaction product of the present invention, and calculate the space-time yield of catalyst.
Compared with prior art, key of the invention is in the active component of catalyst including zinc acetate, potassium acetate and choosing
From the compound of at least one of VA and IIB metallic element, be conducive to the activity and stability that improve catalyst, to improve
The yield of vinyl acetate.
The experimental results showed that the space-time yield of catalyst reaches 163.42g/Lh when using catalyst of the present invention, obtain
Active component includes simultaneously zinc acetate, potassium acetate, at least one in VA in preferable technical effect, especially catalyst
When planting metallic element compound and being selected from least one of IIB metallic element compound, technology effect more outstanding is achieved
Fruit 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 6.70g (KOAc) and contain 3.10gBi
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain
Maceration extract 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g is cylindric
Absorbent charcoal carrier is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The catalysis is measured through ICP
The Zn content of agent is 102g/L, K content 6.70g/L, Bi content 3.10g/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 0.28MPa；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 163.42g/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 2]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.70g (KOAc) and contain 3.10gCd
Cadmium acetate (Cd (OAc)2·2H2O 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 6.70g/L, Cd content 3.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 163.35g/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.
[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 6.70g (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 6.70g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 123.76g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
The catalyst used by can be seen that the present invention compared with Examples 1 to 2, using simultaneously containing zinc acetate, acetic acid
Potassium and bismuth and ammonium citrate active component, simultaneously the catalyst performance ratio containing zinc acetate, potassium acetate and cadmium acetate active component containing only
Zinc acetate, the performance of potassium acetate active constituent catalyst are more excellent, and the space-time yield of vinyl acetate catalyst will be high.
[embodiment 3]
The preparation of catalyst: 80g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 3.00g (KOAc) and containing 1.00gBi's
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, soaked
Stain liquid 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.60cm3/ g, specific surface area 1000cm2The cylindrical type coconut husk of/g is living
Property high-area carbon be immersed in above-mentioned maceration extract, stand 3h in 80 DEG C of dryings, obtain the catalyst.The catalyst is measured through ICP
Zn content be 80g/L, K content 3.00g/L, Bi content 1.00g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 127.34g/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 5.00gBi
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain
Maceration extract 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 1.00cm3/ g, specific surface area 1500cm2The cylindrical type apricot shell of/g
Absorbent charcoal carrier 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
The Zn content of agent is 200g/L, K content 7.00g/L, Bi content 5.00g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 164.07/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 6.70g (KOAc) and contain 3.10gSb
Antimony acetate (Sb (OAc)3) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain maceration extract 350ml, will
1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The cylindrical type activated carbon from bamboo carrier impregnation of/g
In above-mentioned maceration extract, 3h is stood in 120 DEG C of dryings, obtains the catalyst.The Zn content for measuring the catalyst through ICP is
102g/L, K content 6.70g/L, Sb content 3.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 163.46g/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 6]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.70g (KOAc) and contain 3.10gHg
Mercuric acetate (Hg (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 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 6.70g/L, Hg content 3.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 163.29g/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 6.70g (KOAc) and contain 3.10gBi
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain
Maceration extract 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g is cylindric
Absorbent charcoal carrier is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The catalysis is measured through ICP
The Zn content of agent is 102g/L, K content 6.70g/L, Bi content 3.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 150 DEG C, instead
Answering pressure is 0.10MPa；Raw material volume air speed: 250h-1；Raw material composition: acetylene/acetic acid molar ratio=5:1, sustained response 50h
Afterwards, stop reaction.
Product analysis: the reaction mixture that above-mentioned reaction is obtained is cooling, decompression, separates, and liquid phase uses gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The space-time yield for being computed catalyst is 151.84g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 8]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.70g (KOAc) and contain 3.10gBi
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain
Maceration extract 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g is cylindric
Absorbent charcoal carrier is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The catalysis is measured through ICP
The Zn content of agent is 102g/L, K content 6.70g/L, Bi content 3.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 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 164.30g/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 6.70g (KOAc), containing 2.00gBi's
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2) and (Cd (OAc) of the cadmium acetate containing 1.10gCd O2·2H2O it) is sufficiently mixed and is dissolved in
Concentration is maceration extract 350ml to be obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm in the aqueous acetic acid of 60wt%3/g、
Specific surface area is 1200cm2It 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 102g/L, K content 6.70g/L, Bi content 2.00g/
L, Cd content 1.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 165.62g/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 Cd has preferable synergistic effect in VA metal Bi and IIB, illustrates zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable synergistic effect between sour potassium, bismuth and ammonium citrate and cadmium acetate.
[embodiment 10]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.70g (KOAc), containing 2.00gSb's
Antimony acetate (Sb (OAc)3) and cadmium acetate (Cd (OAc) containing 1.10gCd2·2H2O) being sufficiently mixed and being dissolved in concentration is 60wt%
Aqueous acetic acid in, 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 6.70g/L, Sb content 2.00g/L, Cd 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 175 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 165.47g/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 6.70g (KOAc), containing 1.30gBi's
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O), (Sb (OAc) of the antimony acetate containing 0.70gSb3) and cadmium acetate containing 1.10gCd
(Cd(OAc)2·2H2O 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, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The 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
102g/L, K content 6.70g/L, Bi content 1.30g/L, Sb content 0.70g/L, Cd content 1.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cuts acetylene, opens acetic acid pump, control reaction temperature is 175 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 168.04g/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.
Found out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, is improving vinyl acetate catalyst space-time yield
In terms of yield, in the catalyst that the present invention uses, there is synergistic effect in VA metal between Bi and Sb.Illustrate zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable synergistic effect between sour potassium, bismuth and ammonium citrate, antimony acetate and cadmium acetate.
[embodiment 12]
The preparation of catalyst: 102g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.70g (KOAc), containing 1.30gBi's
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O), (Sb (OAc) of the antimony acetate containing 0.70gSb3) and the Hg containing 1.10g mercuric acetate
(Hg(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 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g is above-mentioned
In 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 6.70g/L, Bi content 1.30g/L, Sb content 0.70g/L, Hg content 1.10g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 167.91g/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 6.70g (KOAc), containing 1.30gBi's
Bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O), (Sb (OAc) of the antimony acetate containing 0.70gSb3), the cadmium acetate containing 0.60gCd
(Cd(OAc)2·2H2) and the mercuric acetate of the Hg containing 0.40g (Hg (OAc) O2) 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 1200cm2/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 102g/L, and K content 6.70g/L, Bi content 1.30g/L, Sb content 0.70g/L, Cd contain
Measure 0.60g/L, Hg content 0.40g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, after N2 leak test, N is used2It is right
System sufficiently purges, and after system heating, closes N2, successively cut acetylene, open acetic acid pump, control reaction temperature is 175 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 169.87g/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 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 IIB metal between Cd and Hg.Illustrate zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable collaboration between sour potassium, bismuth and ammonium citrate, antimony acetate, cadmium acetate and mercuric acetate
Effect.
Table 1
Table 2
Claims (7)
1. being used to prepare the catalyst of acetylene method vinyl acetate, the catalyst uses active carbon for carrier, and active component includes
Zinc acetate, potassium acetate and the compound selected from least one of IIB metal metallic element, 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, in catalyst in IIB metallic element at least one
Kind content are as follows: 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 IIB metallic element in cadmium and mercury at least one
Kind.
5. the production method of catalyst described in claim 1, includes the following steps:
1. the solution of metallic element compound in zinc acetate, potassium acetate, VA and IIB is mixed with carrier by the composition of catalyst；
2. drying.
6. vinyl acetate synthesis method is closed under catalyst described in any one of Claims 1 to 4 using acetic acid, acetylene as raw material
At 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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1110663A (en) * | 1965-06-04 | 1968-04-24 | Asahi Chemical Ind | Process for producing vinyl acetate |
| CN104549498A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing vinyl acetate by virtue of acetylene method and synthetic method of vinyl acetate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1110663A (en) * | 1965-06-04 | 1968-04-24 | Asahi Chemical Ind | Process for producing vinyl acetate |
| CN104549498A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing vinyl acetate by virtue of acetylene method and synthetic method of vinyl acetate |
Non-Patent Citations (1)
| Title |
|---|
| 乙炔法气相合成醋酸乙烯催化剂的研究;于政锡;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20061215;B014-122页 |
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