CN106268945B - For synthesizing the catalyst of acetylene method vinyl acetate - Google Patents
For synthesizing the catalyst of acetylene method vinyl acetate Download PDFInfo
- Publication number
- CN106268945B CN106268945B CN201510235795.9A CN201510235795A CN106268945B CN 106268945 B CN106268945 B CN 106268945B CN 201510235795 A CN201510235795 A CN 201510235795A CN 106268945 B CN106268945 B CN 106268945B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- acetate
- acetylene
- vinyl acetate
- content
- 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
Abstract
The present invention relates to the catalyst for synthesizing 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 using the catalyst for synthesizing 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 IVA or IB 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 synthesizing 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 is (entitled：A kind of catalyst and preparation method thereof for vinyl acetate synthesis) provide 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 synthesize 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 present invention is as follows：For synthesizing 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 IVA or IB
At least one of metallic element compound.It is preferred that the active component includes simultaneously zinc acetate, potassium acetate, in IVA
At least one metallic element and compound selected from least one of IB metallic element.The change of the metallic element of IVA at this time
It closes to have in terms of the space-time yield for improving vinyl acetate catalyst between object and the compound of the metallic element in IB 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 IVA metal preferably is selected from least one of germanium, tin and lead, more preferably includes simultaneously
Tin and lead.The IB metal preferably is selected from least one of copper, silver and gold, more preferably simultaneously includes copper and gold.
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 IVA metallic element and IB metallic element；Such as the active component is by zinc acetate, potassium acetate, chlorine
Change stannous and tetra chlorauric acid ammonium (or copper acetate) composition, or by zinc acetate, potassium acetate, stannous chloride (or lead acetate), tetrachloro
Auric acid ammonium and copper acetate composition, or by zinc acetate, potassium acetate, stannous chloride, lead acetate, tetra chlorauric acid ammonium and copper acetate group
At.
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 IVA and IB, 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, IVA and IB are mixed by the composition of catalyst
It closes；
2. drying.
In above-mentioned technical proposal, the preferred stannous oxalate of compound, the germanium tetrachloride, protochloride of the step 1. IVA metal
At least one of tin, nitric acid stannous, stannous oxide, lead acetate and plumbi nitras；More preferably extremely from lead acetate and stannous chloride
Few one kind；1. the compound of metal preferably is selected from copper citrate, copper acetate, copper nitrate, silver acetate, tetrafluoro boric acid to step in the IB
At least one of silver and tetra chlorauric acid ammonium；More preferably from least one of copper acetate and tetra chlorauric acid ammonium.Step is 2. described
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 is formed with molar ratio computing raw material:Acetic acid=(5
~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 IVA and IB 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 163.39g/Lh when using catalyst of the present invention, obtain
In preferable technical effect, especially catalyst active component include simultaneously zinc acetate, potassium acetate, in IVA at least
A kind of metallic element compound and when selected from least one of IB metallic element compound, achieves technology effect more outstanding
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：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 2.80gSn
Stannous chloride (SnCl2·2H2O 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 105g/L, K content 6.50g/L, Sn content 2.80g/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 0.25MPa；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 163.39g/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：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 2.80gAu
Tetra chlorauric acid ammonium (NH4AuCl4·2H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, impregnated
Liquid 350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g is cylindrical activated
High-area carbon is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The catalyst is measured through ICP
Zn content is 105g/L, K content 6.50g/L, Au content 2.80g/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 0.25MPa；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 163.56g/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【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：105g 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 105g/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 0.25MPa；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 124.83g/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 stannous chloride active component, the catalyst performance containing zinc acetate, potassium acetate and tetra chlorauric acid ammonium active component compares only simultaneously
Performance containing zinc acetate, potassium acetate active constituent catalyst is 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 1.00gPb's
Lead acetate (Pb (OAc)2·3H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.60cm3/ 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, Pb 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 0.25MPa；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 127.60g/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 5.00gPb
Lead acetate (Pb (OAc)2·3H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 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, Pb 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 0.25MPa；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 164.12g/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 5】
The preparation of catalyst：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 2.80gPb
Lead acetate (Pb (OAc)2·3H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract
350ml, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The cylindrical type activated carbon from bamboo 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 105g/L, K content 6.50g/L, Pb content 2.80g/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 0.25MPa；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 163.52g/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：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 2.80gCu
Copper acetate Cu (OAc)2·H2O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 60wt%, and maceration extract 350ml is obtained,
By 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The cylindrical activated high-area carbon leaching of the coal quality of/g
Stain stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn content for measuring the catalyst through ICP is
105g/L, K content 6.50g/L, Cu content 2.80g/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 0.25MPa；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 163.64g/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.
【Embodiment 7】
The preparation of catalyst：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 2.80gCu
Copper acetate Cu (OAc)2·H2O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 60wt%, and maceration extract 350ml is obtained,
By 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The cylindrical activated high-area carbon leaching of the coal quality of/g
Stain stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Zn content for measuring the catalyst through ICP is
105g/L, K content 6.50g/L, Cu content 2.80g/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 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 152.79g/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：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc) and contain 2.80gCu
Copper acetate (Cu (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 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 105g/L, K content 6.50g/L, Cu content 2.80g/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 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 164.26g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of catalyst：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 1.05gSn's
SnCl2·2H2O and tetra chlorauric acid ammonium (NH containing 1.75gAu4AuCl4·2H2O) being sufficiently mixed and being dissolved in concentration is 60wt%'s
In aqueous acetic acid, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area are
1200cm2The coal quality cylindrical activated carbon carrier impregnation of/g stands 3h in 100 DEG C of dryings in above-mentioned maceration extract, obtains described
Catalyst.The Zn content for measuring the catalyst through ICP is 105g/L, K content 6.50g/L, Sn content 1.05g/L, Au content
1.75g/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 0.25MPa；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.
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 Sn has preferable synergistic effect in IB metal Au and IVA, illustrates zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable synergistic effect between sour potassium, tetra chlorauric acid ammonium and stannous chloride.
【Embodiment 10】
The preparation of catalyst：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 1.05gSn's
SnCl2·2H2O and copper acetate (Cu (OAc) containing 1.75gCu2·H2O) 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 105g/L, K content 6.50g/L, Sn content 1.05g/L, Cu content 1.75g/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 0.25MPa；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 165.61g/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.
【Embodiment 11】
The preparation of catalyst：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 1.05gSn's
SnCl2·2H2O, the tetra chlorauric acid ammonium (NH containing 1.05gAu4AuCl4·2H2) and (Cu (OAc) of the copper acetate containing 0.70gCu O2·
H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, maceration extract 350ml is obtained, by 1L diameter 3mm, length
2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The 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 105g/L, K content
6.50g/L, Sn content 1.05g/L, Au content 1.05g/L, Cu content 0.70g/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 0.25MPa；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 167.96g/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 IB metal between Au and Cu.Illustrate zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable synergistic effect between sour potassium, stannous chloride, tetra chlorauric acid ammonium and copper acetate.
【Embodiment 12】
The preparation of catalyst：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 1.05gPb's
Lead acetate (Pb (OAc)2·3H2O), the tetra chlorauric acid ammonium (NH containing 1.05gAu4AuCl4·2H2) and the copper acetate containing 0.70gCu O
(Cu(OAc)2·H2O it) is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain maceration extract 350ml, 1L is straight
Diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The 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 105g/
L, K content 6.50g/L, Pb content 1.05g/L, Au content 1.05g/L, Cu content 0.70g/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 0.25MPa；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 167.71g/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：105g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.50g (KOAc), containing 0.40gSn's
SnCl2·2H2O, (the Pb (OAc) of the lead acetate containing 0.65gPb2·3H2O), the tetra chlorauric acid ammonium (NH containing 1.05gAu4AuCl4·
2H2) and (Cu (OAc) of the copper acetate containing 0.70gCu O2·H2O) it is sufficiently mixed the aqueous acetic acid for being dissolved in that concentration is 60wt%
In, maceration extract 350ml is obtained, by 1L diameter 3mm, long 2cm, Kong Rongwei 0.80cm3/ g, specific surface area 1200cm2The coal quality of/g
Cylindrical activated carbon carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.It is measured through ICP
The Zn content of the catalyst is 105g/L, K content 6.50g/L, Sn content 0.40g/L, Pb content 0.65g/L, Au content
1.05g/L, Cu content 0.70g/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 0.25MPa；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 169.95g/Lh, for ease of description and is compared, the preparation of catalyst
Condition, reaction condition, material inlet amount, catalyst space-time yield be listed in Tables 1 and 2 respectively.
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 IVA metal between Au and Cu.Illustrate zinc acetate, vinegar
There is in terms of the activity for improving catalyst preferable synergistic effect between sour potassium, stannous chloride, tetra chlorauric acid ammonium and copper acetate.
Table 1
Table 2
Claims (10)
1. the catalyst for synthesizing acetylene method vinyl acetate, the catalyst use active carbon for carrier, active component includes
Zinc acetate, potassium acetate and the compound selected from least one of IVA metal metallic element and at least one in IB metal
The compound of kind 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 IVA metallic element in germanium, tin and lead at least
It is a kind of.
5. catalyst according to claim 1, it is characterised in that the IB metallic element in copper, silver and gold at least one
Kind.
6. catalyst according to claim 1, it is characterised in that the content of zinc acetate is in catalyst：50~300g/L, vinegar
The content of sour potassium is：0.10~10.00g/L.
7. catalyst according to claim 1, it is characterised in that selected from least one of IVA metal gold described in catalyst
The content of total metallic element is in the compound of category element and the compound selected from least one of IB metal metallic element
0.50~8.00g/L.
8. being included the following steps by the production method of catalyst described in claim 1：
1. the solution of metallic element compound in zinc acetate, potassium acetate, IVA and IB is mixed with carrier by the composition of catalyst；
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 with molar ratio computing raw material group:Acetic acid=(5
~12):1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510235795.9A CN106268945B (en) | 2015-05-11 | 2015-05-11 | For synthesizing the catalyst of acetylene method vinyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510235795.9A CN106268945B (en) | 2015-05-11 | 2015-05-11 | For synthesizing the catalyst of acetylene method vinyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106268945A CN106268945A (en) | 2017-01-04 |
| CN106268945B true CN106268945B (en) | 2018-11-20 |
Family
ID=57630582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510235795.9A Active CN106268945B (en) | 2015-05-11 | 2015-05-11 | For synthesizing the catalyst of acetylene method vinyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106268945B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774314B (en) * | 2016-08-29 | 2020-05-01 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by acetylene method |
| CN107790181B (en) * | 2016-08-29 | 2019-11-08 | 中国石油化工股份有限公司 | For synthesizing the catalyst of acetylene method vinyl acetate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391229A (en) * | 2008-11-06 | 2009-03-25 | 中国科学院化学研究所 | Catalyst containing rare-earth metal for preparing vinyl acetate using acetylene method and preparation method and use thereof |
| CN103962178A (en) * | 2013-02-05 | 2014-08-06 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and its preparation method |
| CN104549497A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof |
| 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 |
| CN104549517A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
-
2015
- 2015-05-11 CN CN201510235795.9A patent/CN106268945B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391229A (en) * | 2008-11-06 | 2009-03-25 | 中国科学院化学研究所 | Catalyst containing rare-earth metal for preparing vinyl acetate using acetylene method and preparation method and use thereof |
| CN103962178A (en) * | 2013-02-05 | 2014-08-06 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and its preparation method |
| CN104549497A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for vinyl acetate synthesis by acetylene method and preparation method thereof |
| 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 |
| CN104549517A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106268945A (en) | 2017-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103691451B (en) | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst | |
| CN106423269B (en) | Unsaturated acetic acid ester catalyst and preparation method thereof | |
| CN106268945B (en) | For synthesizing the catalyst of acetylene method vinyl acetate | |
| CN106423157B (en) | The catalyst of Synthesizing Vinyl Acetate from Acetylene | |
| CN106423266B (en) | Acetylene method vinyl acetate preparation catalyst used | |
| CN106423128B (en) | Catalyst used in acetylene method vinyl acetate production | |
| CN106423221B (en) | Produce catalyst used in acetylene method vinyl acetate | |
| CN106268764A (en) | Prepare the catalyst used by acetylene method vinyl acetate | |
| CN106268943B (en) | Synthesize catalyst used in acetylene method vinyl acetate | |
| CN106268942B (en) | It is used to prepare the catalyst of acetylene method vinyl acetate | |
| CN106423127B (en) | Catalyst used in acetylene method vinyl acetate synthesis | |
| CN106423268B (en) | The catalyst of producing vinyl acetate by acetylene method | |
| CN106423267B (en) | The catalyst of preparing vinyl acetate using acetylene method | |
| CN106268944B (en) | For producing the catalyst of acetylene method vinyl acetate | |
| CN107790181B (en) | For synthesizing the catalyst of acetylene method vinyl acetate | |
| CN107774324B (en) | Natural gas prepares catalyst used in acetylene method vinyl acetate | |
| CN106582825B (en) | It is used to prepare the catalyst of allyl acetate | |
| CN107774314A (en) | Synthesize the catalyst of acetylene method vinyl acetate | |
| CN107774308A (en) | Vinyl acetate catalyst | |
| CN107774304B (en) | The catalyst of vinyl acetate production | |
| CN107774332B (en) | Vinyl acetate synthesis catalyst and preparation method thereof | |
| CN107790190B (en) | Produce the catalyst of acetylene method vinylacetate | |
| CN107774323A (en) | Catalyst used in natural gas production acetylene method vinyl acetate | |
| CN107774310B (en) | Catalyst of vinyl acetate production and preparation method thereof | |
| CN107774322B (en) | It is used to prepare catalyst used in acetylene method vinyl acetate |
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 |