CN106268764B - Prepare catalyst used in acetylene method vinyl acetate - Google Patents
Prepare catalyst used in acetylene method vinyl acetate Download PDFInfo
- Publication number
- CN106268764B CN106268764B CN201510235802.5A CN201510235802A CN106268764B CN 106268764 B CN106268764 B CN 106268764B CN 201510235802 A CN201510235802 A CN 201510235802A CN 106268764 B CN106268764 B CN 106268764B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetate
- acetic acid
- acetylene
- vinyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to catalyst used in acetylene method vinyl acetate is prepared, 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 and prepares catalyst used in 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 lanthanide series metal or vib 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 prepare catalyst used in 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, provide it is a kind of new prepare catalyst used in 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: preparing acetylene method vinyl acetate institute
Catalyst, the catalyst use active carbon for carrier, and active component includes zinc acetate, potassium acetate and selected from lanthanide series metal
Or the compound of at least one of VIB metallic element.It is preferred that the active component includes simultaneously zinc acetate, potassium acetate, is selected from
At least one of lanthanide series metal metallic element and compound selected from least one of VIB metallic element.Group of the lanthanides gold at this time
In the space-time for improving vinyl acetate catalyst between the compound of metallic element in the compound and VIB of metallic element in category
There is synergistic effect in terms of 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 lanthanide element preferably is selected from least one in lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium
Kind, it more preferably simultaneously include lanthanum and samarium.
In above-mentioned technical proposal, the vib metal preferably is selected from least one of chromium, molybdenum and tungsten, more preferably includes simultaneously
Chromium and molybdenum.
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 lanthanide element and vib metal element；Such as the active component by zinc acetate, potassium acetate,
Acetic acid samarium (or lanthanum acetate) and chromic acetate composition, or by zinc acetate, potassium acetate, acetic acid samarium, lanthanum acetate and chromic acetate (or acetic acid
Molybdenum) composition, or be made of zinc acetate, potassium acetate, acetic acid samarium, lanthanum acetate, chromic acetate and acetic acid molybdenum.
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 lanthanide series metal and VIB, 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 the solution of metallic element compound in zinc acetate, potassium acetate, lanthanide series metal and VIB with
Carrier mixing；
2. drying.
In above-mentioned technical proposal, the preferred lanthanum acetate of compound, the lanthanum chloride, nitric acid of the step 1. lanthanide element
At least one in lanthanum, cerous acetate, cerous nitrate, cerium chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, ytterbium chloride, Europium chloride and lutecium chloride
Kind；The acetate of more preferable lanthanide series metal；Step 1. the preferred chromic acetate of compound of the vib metal, chromic nitrate, chromium chloride,
At least one of ammonium molybdate, molybdenum pentachloride and ammonium tungstate；More preferably from least one of chromic acetate and acetic acid molybdenum.Step is 2.
The drying temperature is 80~120 DEG C, 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 lanthanide series metal and VIB metallic element, be conducive to the activity and stability that improve catalyst, from
And improve the yield of vinyl acetate.
The experimental results showed that the space-time yield of catalyst reaches 162.48g/Lh when using catalyst of the present invention, obtain
Active component includes simultaneously zinc acetate, potassium acetate, in lanthanide series metal in preferable technical effect, especially catalyst
At least one metallic element compound and when selected from least one of VIB metallic element compound, achieves more outstanding
Technical 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: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 3.40gSm
Acetic acid samarium (Sm (OAc)3·6H2O 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 104g/L, K content 6.50g/L, Sm content 3.40g/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 178 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 162.48g/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: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 3.40gCr
Chromic acetate (Cr (OAc)3·6H2O 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 104g/L, K content 6.50g/L, Cr content 3.40g/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 178 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 162.61g/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: 104g zinc acetate (Zn (OAc) will be contained2) and potassium acetate containing 6.50g (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 104g/L, K content 6.50g/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 178 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 123.44g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
The catalyst used by can be seen that the present invention compared with Examples 1 to 2, using simultaneously containing zinc acetate, acetic acid
Potassium and acetic acid samarium active component, simultaneously the catalyst performance ratio containing zinc acetate, potassium acetate and chromic 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 1.00gLa's
Lanthanum acetate (La (OAc)3·5H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.60cm3/ g, specific surface area 1000cm2The cylindrical type cocoanut active charcoal of/g
Carrier impregnation stands 3h in 80 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 80g/L, K content 3.00g/L, La 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 178 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 126.93g/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 4]
The preparation of catalyst: 200g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 7.00g (KOAc) and contain 5.00gCe
Cerous acetate (Ce (OAc)3·6H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 1.00cm3/ g, specific surface area 1500cm2The cylindrical type apricot shell active carbon of/g
Carrier impregnation stands 3h in 120 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn of the catalyst is measured through ICP
Content is 200g/L, K content 7.00g/L, Ce 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 178 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 163.52/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: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 3.40gMo
Acetic acid molybdenum (Mo2(OAc)4) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain maceration extract 350ml, will
1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 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
104g/L, K content 6.50g/L, Mo content 3.40g/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 178 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 162.36g/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: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 3.40gLu
Acetic acid lutetium (Lu (OAc)3·6H2O 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 104g/L, K content 6.50g/L, Lu content 3.40g/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 178 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 162.41g/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 7]
The preparation of catalyst: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 3.40gCr
Chromic acetate (Cr (OAc)3·6H2O 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 104g/L, K content 6.50g/L, Cr content 3.40g/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 152.09g/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: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 3.40gSm
Acetic acid samarium (Sm (OAc)3·6H2O 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 104g/L, K content 6.50g/L, Sm content 3.40g/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: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 1.60gSm's
Acetic acid samarium (Sm (OAc)3·6H2) and (Cr (OAc) of the chromic acetate containing 1.80gCr O3·6H2O it) is sufficiently mixed and is dissolved in concentration and is
In the aqueous acetic acid of 60wt%, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface
Product is 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g stands 3h in 100 DEG C of dryings, obtains in above-mentioned maceration extract
The catalyst.The Zn content for measuring the catalyst through ICP is 104g/L, and K content 6.50g/L, Sm content 1.60g/L, Cr contain
Measure 1.80g/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 178 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 165.64g/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 Cr has preferable synergistic effect in lanthanide series metal Sm and VIB, illustrate zinc acetate,
There is in terms of the activity for improving catalyst preferable synergistic effect between potassium acetate, acetic acid samarium and chromic acetate.
[embodiment 10]
The preparation of catalyst: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 1.60gLa's
Lanthanum acetate (La (OAc)3·5H2) and (Cr (OAc) of the chromic acetate containing 1.80gCr O3·6H2O it) is sufficiently mixed and is dissolved in concentration and is
In the aqueous acetic acid of 60wt%, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface
Product is 1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g stands 3h in 100 DEG C of dryings, obtains in above-mentioned maceration extract
The catalyst.The Zn content for measuring the catalyst through ICP is 104g/L, and K content 6.50g/L, La content 1.60g/L, Cr contain
Measure 1.80g/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 178 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 165.75g/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.
[embodiment 11]
The preparation of catalyst: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 0.90gSm's
Acetic acid samarium (Sm (OAc)3·6H2O), (La (OAc) of the lanthanum acetate containing 0.70gLa3·5H2O chromic acetate (the Cr) and containing 1.80gCr
(OAc)3·6H2O 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 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 104g/L, K
Content 6.50g/L, Sm content 0.90g/L, La content 0.70g/L, Cr content 1.80g/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 178 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 168.05g/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 lanthanide series metal between Sm and La.Illustrate zinc acetate,
There is in terms of the activity for improving catalyst preferable synergistic effect between potassium acetate, acetic acid samarium, lanthanum acetate and chromic acetate.
[embodiment 12]
The preparation of catalyst: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 0.90gSm's
Acetic acid samarium (Sm (OAc)3·6H2O), (La (OAc) of the lanthanum acetate containing 0.70gLa3·5H2O the acetic acid molybdenum (Mo) and containing 1.80gMo2
(OAc)4) 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 104g/L, K content
6.50g/L, Sm content 0.90g/L, La content 0.70g/L, Mo content 1.80g/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 178 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 167.90g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
[embodiment 13]
The preparation of catalyst: 104g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 0.90gSm's
Acetic acid samarium (Sm (OAc)3·6H2O), (La (OAc) of the lanthanum acetate containing 0.70gLa3·5H2O), the chromic acetate (Cr containing 0.95gCr
(OAc)3·6H2O the acetic acid molybdenum (Mo) and containing 0.85gMo2(OAc)4) it is sufficiently mixed the acetic acid water for being dissolved in that concentration is 60wt%
In solution, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 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 104g/L, K content 6.50g/L, Sm content 0.90g/L, La content 0.70g/L, Cr content
0.95g/L, Mo content 0.85g/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 178 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 169.82g/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 vib metal between Cr and Mo.Illustrate zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable collaboration effect between sour potassium, acetic acid samarium, lanthanum acetate, chromic acetate and acetic acid molybdenum
It answers.
Table 1
Table 2
Claims (10)
1. preparing catalyst used in acetylene method vinyl acetate, the catalyst uses active carbon for carrier, and active component includes
Zinc acetate, potassium acetate, the compound selected from least one of lanthanide series metal metallic element and in group vib metal at least
A kind of compound of metallic element.
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 lanthanide element is selected from lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium
At least one of with lutetium.
5. catalyst according to claim 1, it is characterised in that the group vib metallic element in chromium, molybdenum and tungsten extremely
Few one kind.
6. catalyst according to claim 1, it is characterised in that the content of zinc acetate in catalyst are as follows: 50~300g/L, vinegar
The content of sour potassium are as follows: 0.10~10.00g/L.
7. catalyst according to claim 1, it is characterised in that selected from lanthanide series metal and the metal in group vib in catalyst
The content of element is 0.50~8.00g/L.
8. 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 metallic element compound in zinc acetate, potassium acetate, lanthanide series metal and group vib
Body mixing；
2. drying.
9. vinyl acetate synthesis method is closed under catalyst described in any one of claim 1~7 using acetic acid, acetylene as raw material
At vinyl acetate.
10. synthetic method according to claim 9, it is characterized in that becoming acetylene: acetic acid=(5 with molar ratio computing raw material group
~12): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510235802.5A CN106268764B (en) | 2015-05-11 | 2015-05-11 | Prepare catalyst used in acetylene method vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510235802.5A CN106268764B (en) | 2015-05-11 | 2015-05-11 | Prepare catalyst used in acetylene method vinyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106268764A CN106268764A (en) | 2017-01-04 |
| CN106268764B true CN106268764B (en) | 2019-01-25 |
Family
ID=57630634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510235802.5A Active CN106268764B (en) | 2015-05-11 | 2015-05-11 | Prepare catalyst used in acetylene method vinyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106268764B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774320B (en) * | 2016-08-29 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by acetylene method |
| CN107778169B (en) * | 2016-08-29 | 2020-12-29 | 中国石油化工股份有限公司 | Catalyst for producing vinyl acetate by acetylene method |
| CN114768785A (en) * | 2022-03-29 | 2022-07-22 | 木林森活性炭江苏有限公司 | Production process of activated carbon-based carbon, catalyst using activated carbon-based carbon and production process of catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903435A (en) * | 2006-07-31 | 2007-01-31 | 中国石油化工集团公司 | Catalyst used for synthesis of vinyl acetate and its prepn. method |
| CN103934030A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis and a preparation method thereof |
| CN104437627A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Acetylene method vinyl acetate catalyst and preparation method thereof |
| CN104437623A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for acetylene-method vinyl acetate and synthesis method of 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 |
-
2015
- 2015-05-11 CN CN201510235802.5A patent/CN106268764B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1903435A (en) * | 2006-07-31 | 2007-01-31 | 中国石油化工集团公司 | Catalyst used for synthesis of vinyl acetate and its prepn. method |
| CN103934030A (en) * | 2013-01-23 | 2014-07-23 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis and a preparation method thereof |
| CN104437627A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Acetylene method vinyl acetate catalyst and preparation method thereof |
| CN104437623A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Catalyst for acetylene-method vinyl acetate and synthesis method of 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;第63-66页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106268764A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106268764B (en) | Prepare catalyst used in acetylene method vinyl acetate | |
| CN106552637B (en) | Cobalt molybdenum system low temperature sulfur tolerant shift catalyst and preparation method | |
| CN106423266B (en) | Acetylene method vinyl acetate preparation catalyst used | |
| CN106423157B (en) | The catalyst of Synthesizing Vinyl Acetate from Acetylene | |
| CN106423128B (en) | Catalyst used in acetylene method vinyl acetate production | |
| CN104368360B (en) | The catalyst of a kind of crotonic aldehyde gas phase selective hydrogenation synthesis crotonyl alcohol. and preparation method | |
| CN106268945B (en) | For synthesizing the catalyst of acetylene method vinyl acetate | |
| CN106423221B (en) | Produce catalyst used in acetylene method vinyl acetate | |
| CN105801383B (en) | A method of butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol | |
| CN106268943B (en) | Synthesize catalyst used in acetylene method vinyl acetate | |
| CN107774323B (en) | Natural gas produces catalyst used in acetylene method vinyl acetate | |
| CN106423268B (en) | The catalyst of producing vinyl acetate by acetylene method | |
| CN107774321B (en) | Produce the catalyst of vinyl acetate | |
| CN106423127B (en) | Catalyst used in acetylene method vinyl acetate synthesis | |
| CN105727954B (en) | A kind of preparation method of synthesis gas preparing natural gas catalyst | |
| CN106423267B (en) | The catalyst of preparing vinyl acetate using acetylene method | |
| CN106268942B (en) | It is used to prepare the catalyst of acetylene method vinyl acetate | |
| CN106268944B (en) | For producing the catalyst of acetylene method vinyl acetate | |
| CN107774324B (en) | Natural gas prepares catalyst used in acetylene method vinyl acetate | |
| CN105498847B (en) | The method that supported copper catalyst and its preparation method and application and propylene oxidation prepare propylene oxide | |
| CN107774322B (en) | It is used to prepare catalyst used in acetylene method vinyl acetate | |
| CN108499559A (en) | A kind of catalyst for preparing isobutene through dehydrogenation of iso-butane, preparation method and application | |
| CN104689853B (en) | A kind of preparation method and application for being used to prepare the catalyst of iso-amylene | |
| CN105413686B (en) | Synthesize the catalyst used in ethylidene diacetate | |
| CN105435784B (en) | For preparing the catalyst of 3 acetoxyl group propionic aldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |