CN106423268A - Catalyst used for acetylene method production of vinyl acetate - Google Patents
Catalyst used for acetylene method production of vinyl acetate Download PDFInfo
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Abstract
The invention relates to a catalyst used for acetylene method production of vinyl acetate in order to mainly solve the problem of low activity of acetylene method catalysts in the prior art. The catalyst used for acetylene method production of vinyl acetate adopts active carbon as a carrier, and active components comprise zinc acetate, potassium acetate and a compound of at least one metal element selected from group VIII metals and alkali earth metals. The catalyst provided by the invention well solves the problem and can be used in the industrial production of acetylene vapor phase method synthesis of vinyl acetate.
Description
Technical field
The present invention relates to the catalyst of producing vinyl acetate by acetylene method, the preparation of described acetylene in gas phase method vinyl acetate catalyst
Method and the synthetic method of acetylene in gas phase method vinyl acetate.
Background technology
Vinyl acetate (Vinyl acetate, abbreviation VAC) it is important Organic Chemicals, it is widely used in manufacturing and gather
Vinyl acetate, polyvinyl alcohol are simultaneously processed further for binding agent, coating, vinylon fibre, fabric processing, emulsion, tree
The aspect such as fat and thin film.At present, the method for commercial production vinyl acetate has acetylene in gas phase method and ethylene vapor phase method.
Producing vinyl acetate by acetylene method experienced two developmental stage of liquid and gas technique.Before 1940, mainly with
Based on liquid phase process, reacted under 30～70 DEG C of normal pressures, catalyst is mercury oxide and sulphuric acid or phosphoric acid；20th century
After the forties, start based on acetylene in gas phase method, catalyst is the activated carbon having loaded zinc acetate.
Nineteen twenty-two Germany Wacker company Muqaen finds that dipping zinc acetate on the activated carbon can be with vapor- phase synthesis acetic acid second
Alkene, the method subsequently proposing to synthesize VAc using acetylene in gas phase, improve by Hochst company and put into commercial production.Its
Catalyst is with Zn (OAc)2For active component, with activated carbon as carrier, and use till today always.United States Patent (USP) (US166482,
Production of vinyl acetate) report using catalyst Z n (OAc)2/ C, has synthesized vinyl acetate.In
State's patent CN1903435 is (entitled：A kind of catalyst for vinyl acetate synthesis and preparation method thereof) provide one
Plant the preparation method of acetylene method vinyl acetate catalyst, catalyst activity component adopts zinc oxide and acetic acid, and add a small amount of
Waltherite, is immersed in activated carbon and is dried to obtain catalyst.But the catalyst activity that above-mentioned technology provides is not high, limit
Make the application of acetylene method vinyl acetate.
Content of the invention
One of the technical problem to be solved is low the asking of acetylene method vinyl acetate catalyst activity in prior art
Topic, provides a kind of catalyst of new producing vinyl acetate by acetylene method, the active high feature of this catalyst.
The two of the technical problem to be solved are the production methods using the described catalyst of one of above-mentioned technical problem.
The three of the technical problem to be solved are the vinyl acetates using the described catalyst of one of above-mentioned technical problem
Synthetic method.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows：The urging of producing vinyl acetate by acetylene method
Agent, it is carrier that described catalyst adopts activated carbon, and active component includes zinc acetate, potassium acetate and is selected from VIII metal
Or the compound of at least one metallic element in alkali metal.Preferably described active component include simultaneously zinc acetate, potassium acetate,
At least one metal unit selected from the compound of at least one metallic element in VIII metallic element and in alkali metal
The compound of element.Now the compound of the metallic element in the compound of metallic element in VIII metal and alkali metal it
Between improve vinyl acetate catalyst space-time yield in terms of there is synergism.
In technique scheme, described activated carbon preferably is selected from ature of coal column charcoal, cocoanut active charcoal, Fructus Pruni shell activated carbon and bamboo matter
At least one of activated carbon.The specific surface area of described activated carbon is preferably 1000～1500cm2/ g, absorption pore volume is preferably
0.60～1.00cm3/g.
In technique scheme, described VIII metallic element preferably be selected from cobalt, nickel, ferrum, platinum, palladium, osmium, iridium, ruthenium and
At least one in rhodium, more preferably includes cobalt and rhodium simultaneously.
In technique scheme, described alkali metal metal preferably is selected from least one in lithium, sodium, rubidium and caesium, more preferably same
When include lithium and rubidium.
In technique scheme, more more preferably described VIII metallic element includes cobalt and rhodium, described alkali metal metal simultaneously
Include lithium and rubidium simultaneously.
In technique scheme, as most preferred technical scheme, described active component include simultaneously zinc acetate, potassium acetate,
The compound of VIII metallic element and the compound of alkali metal；For example described active component by zinc acetate, potassium acetate,
Acetic acid rubidium (or lithium acetate) and rhodium acetate composition, or by zinc acetate, potassium acetate, acetic acid rubidium, lithium acetate and rhodium acetate
(or cobaltous acetate) forms, or is made up of zinc acetate, potassium acetate, acetic acid rubidium, lithium acetate, rhodium acetate and cobaltous acetate.
In technique scheme, in described catalyst, the content of zinc acetate is preferably 50～300g/L, more preferably
80～200g/L；In described catalyst, the content of potassium acetate is preferably 0.10～10.00g/L, more preferably 3.00～7.00g/L；
At least one content being selected from metallic element in VIII metal and alkali metal in described catalyst is preferably
0.50～8.00g/L, more preferably 1.00～5.00g/L.
For solving the two of above-mentioned technical problem, technical scheme is as follows：The technical scheme of one of above-mentioned technical problem
Described in catalyst production method, comprise the steps：
1. by the composition of catalyst, zinc acetate, the solution of potassium acetate, VIII metal and alkali-metal compound and carrier are mixed
Close；
2. it is dried.
In technique scheme, the compound of step 1. described VIII metallic element preferably be selected from Ferrous acetate, ferrocene,
Iron chloride, iron sulfate, carbonyl cobalt, cobaltous acetate, cobaltous chloride, cobalt nitrate, Nickel tetracarbonyl., nickel acetate, nickel nitrate, sulphuric acid
Nickel, Nickel dichloride., radium chloride, rhodium acetate two part, triphenylphosphine chlorine rhodium, rhodium nitrate, Palladous chloride., dichloro four ammonia palladium,
Amine, acetic acid ruthenium, platinous chloride, ammonium chloroplatinite, chlorine platinum in palladium, ammonium chloropalladite, ruthenic chloride, mistake ruthenic acid four
At least one in acid, platinum acetate, osmium trichloride, acetic acid osmium, iridous chloride, acetic acid iridium and chloro-iridic acid；More excellent VIII
The acetate of metallic element；Step 1. in described alkali metal the compound of metal preferably be selected from alkali metal oxide, alkali metal chlorine
At least one in compound, alkali metal sulfates, alkali nitrates and alkali metal acetate；More preferably alkali metal acetic acid
Salt.2. described baking temperature is 80～120 DEG C to step, more preferably 100～120 DEG C.
For solving the three of above-mentioned technical problem, technical scheme is as follows：Vinyl acetate synthesis method, with acetic acid,
Acetylene is raw material, and reaction in the presence of catalyst described in any one of the technical scheme of one of above-mentioned technical problem generates vinegar
Sour ethylene.
The key of the present invention is the selection of catalyst, skilled person will know how determining according to actual needs suitably
The proportioning of reaction temperature, response time, reaction pressure and material.But, in technique scheme, the temperature of reaction is preferred
For 150～200 DEG C；The pressure of reaction is preferably 0.1～0.5MPa；Acetylene is preferably with molar ratio computing raw material composition:Acetic acid
=(5～12):1；Raw material volume air speed is preferably 250～350h-1.
The content gas chromatography analysis of each component in product of the present invention, and calculate the space-time yield of catalyst.
Compared with prior art, the key of the present invention is that the active component of catalyst includes zinc acetate, potassium acetate and is selected from
The compound of at least one metallic element in the compound and alkali metal of VIII metallic element, is conducive to improving catalyst
Activity and stability, thus improve the yield of vinyl acetate.
Test result indicate that, during using catalyst of the present invention, the space-time yield of catalyst reaches 162.31g/L h, obtains
Preferable technique effect, active component includes zinc acetate, potassium acetate simultaneously, is selected from VIII metal especially in catalyst
When at least one metallic element compound in element and at least one metallic element compound in alkali metal, obtain
More prominent technique effect, can be used in the commercial production of vinyl acetate.Below by embodiment the present invention is made into
One step illustrates.
Specific embodiment
【Embodiment 1】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gRb
Acetic acid rubidium (RbOAc) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain impregnation liquid 350ml,
1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The cylindric work of ature of coal of/g
Property high-area carbon be immersed in above-mentioned impregnation liquid, standing 3h in 100 DEG C of dryings, obtain described catalyst.Measuring through ICP should
The Zn content of catalyst is 100g/L, K content 6.10g/L, Rb content 3.50g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 162.31g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 2】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gRh
Rhodium acetate (Rh2(OAc)4) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain impregnation liquid 350ml,
1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The ature of coal cylindrical activated carbon of/g
, in above-mentioned impregnation liquid, 3h is in 100 DEG C of dryings for standing, obtains described catalyst for carrier impregnation.Measure this catalyst through ICP
Zn content be 100g/L, K content 6.10g/L, Rh content 3.50g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 162.40g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2) and potassium acetate containing 6.10g (KOAc) be sufficiently mixed
It is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid 350ml, by 1L diameter 3mm, long 2cm, hole
Hold for 0.80cm3/ g, specific surface area are 1200cm2The ature of coal cylindrical activated carbon carrier impregnation of/g in above-mentioned impregnation liquid,
3h is in 100 DEG C of dryings for standing, obtains described catalyst.It is 100g/L, K through the Zn content that ICP measures this catalyst
Content 6.10g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 121.44g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
By can be seen that the catalyst that the present invention adopts compared with embodiment 1～2, using simultaneously containing zinc acetate, acetic acid
Potassium and acetic acid rubidium active component, contain the catalyst performance of zinc acetate, potassium acetate and rhodium acetate active component than containing only vinegar simultaneously
Sour zinc, potassium acetate active constituent catalyst performance more excellent, 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 contain 1.00gCo
Cobaltous acetate (Co (OAc)2·4H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid
350ml, 1L diameter 3mm, long 2cm, pore volume are 0.60cm3/ g, specific surface area are 1000cm2The column type of/g
, in above-mentioned impregnation liquid, 3h is in 80 DEG C of dryings for standing, obtains described catalyst for cocoanut active charcoal carrier impregnation.Through ICP
The Zn content measuring this catalyst is 80g/L, K content 3.00g/L, Co content 1.00g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 127.53g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are 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 5.00g
Magnesium acetate (the NaOAc 3H of Na2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid
350ml, 1L diameter 3mm, long 2cm, pore volume are 1.00cm3/ g, specific surface area are 1500cm2The column type of/g
Fructus Pruni shell absorbent charcoal carrier is immersed in above-mentioned impregnation liquid, and 3h is in 120 DEG C of dryings for standing, obtains described catalyst.Through ICP
The Zn content measuring this catalyst is 200g/L, K content 7.00g/L, Na content 5.00g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 162.94L h, for convenience of description and compare, the preparation condition of catalyst,
Reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 5】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50g
Lithium acetate (the LiOAc 2H of Li2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid
350ml, 1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The column type of/g
, in above-mentioned impregnation liquid, 3h is in 120 DEG C of dryings for standing, obtains described catalyst for activated carbon from bamboo carrier impregnation.Through ICP
The Zn content measuring this catalyst with ICP-MS is 100g/L, K content 6.10g/L, Li content 3.50g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 162.34g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 6】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gCs
Cesium acetate (CsOAC) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain impregnation liquid 350ml,
1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The cylindric work of ature of coal of/g
Property high-area carbon be immersed in above-mentioned impregnation liquid, standing 3h in 100 DEG C of dryings, obtain described catalyst.Measuring through ICP should
The Zn content of catalyst is 100g/L, K content 6.10g/L, Cs content 3.50g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 162.35g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 7】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gNi
Nickel acetate (Ni (OAc)2) be sufficiently mixed be dissolved in concentration be 60wt% aqueous acetic acid in, obtain impregnation liquid 350ml,
1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The cylindric work of ature of coal of/g
Property high-area carbon be immersed in above-mentioned impregnation liquid, standing 3h in 100 DEG C of dryings, obtain described catalyst.Measuring through ICP should
The Zn content of catalyst is 100g/L, K content 6.10g/L, Ni content 3.50g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
150 DEG C, reaction pressure is 0.10MPa；Raw material volume air speed：250h-1；Raw material forms：Acetylene/acetic acid mol ratio=
5:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 153.15g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 8】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc) and contain 3.50gRu
Acetic acid ruthenium (Ru (OAc)3·3H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid
350ml, 1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The ature of coal circle of/g
, in above-mentioned impregnation liquid, 3h is in 100 DEG C of dryings for standing, obtains described catalyst for column-shaped active carbon carrier impregnation.Through ICP
The Zn content measuring this catalyst is 100g/L, K content 6.10g/L, Ru content 3.50g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
200 DEG C, reaction pressure is 0.50MPa；Raw material volume air speed：350h-1；Raw material forms：Acetylene/acetic acid mol ratio=
12:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 163.01g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), contain 1.60gRb
Acetic acid rubidium (RbOAc) and containing 1.90gRh rhodium acetate (Rh2(OAc)4) be sufficiently mixed be dissolved in concentration be 60wt%
Aqueous acetic acid in, obtain impregnation liquid 350ml, by 1L diameter 3mm, long 2cm, pore volume be 0.80cm3/ g, ratio
Surface area is 1200cm2, in above-mentioned impregnation liquid, 3h is in 100 DEG C for standing for the ature of coal cylindrical activated carbon carrier impregnation of/g
It is dried, obtain described catalyst.It is 100g/L through the Zn content that ICP measures this catalyst, K content 6.10g/L,
Rb content 1.60g/L, Rh content 1.90g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 164.59g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
Found out on year-on-year basis with embodiment 1 and embodiment 2 by embodiment 9, improving vinyl acetate catalyst space-time yield side
Face, in the catalyst that the present invention uses, in alkali metal, metal Rb and metal Rh in VIII metal has preferably collaborative work
With illustrating have preferably at the active aspect improving catalyst between zinc acetate, potassium acetate, acetic acid rubidium and rhodium acetate
Cooperative effect.
【Embodiment 10】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), contain 1.60gLi
Lithium acetate (LiOAc 2H2O rhodium acetate (the Rh) with containing 1.90gRh2(OAc)4) be sufficiently mixed be dissolved in concentration be 60wt%
Aqueous acetic acid in, obtain impregnation liquid 350ml, by 1L diameter 3mm, long 2cm, pore volume be 0.80cm3/ g, ratio
Surface area is 1200cm2, in above-mentioned impregnation liquid, 3h is in 100 DEG C for standing for the ature of coal cylindrical activated carbon carrier impregnation of/g
It is dried, obtain described catalyst.It is 100g/L through the Zn content that ICP measures this catalyst, K content 6.10g/L, Li
Content 1.60g/L, Rh content 1.90g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 164.68g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 11】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), contain 0.90gRb
Acetic acid rubidium (RbOAc), containing 0.70gLi lithium acetate (LiOAc 2H2O rhodium acetate (the Rh) with containing 1.90gRh2(OAc)4)
It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid 350ml, by 1L diameter 3mm, length
2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The ature of coal cylindrical activated carbon carrier impregnation of/g is above-mentioned
In impregnation liquid, 3h is in 100 DEG C of dryings for standing, obtains described catalyst.Through the Zn content that ICP measures this catalyst it is
100g/L, K content 6.10g/L, Rb content 0.90g/L, Li content 0.70g/L, Rh content 1.90g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 167.26g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
Found out on year-on-year basis with embodiment 9 and embodiment 10 by embodiment 11, improving vinyl acetate catalyst space-time yield
Yield aspect, in the catalyst that the present invention uses, has synergism between Rb, Li in alkali metal.Illustrate acetic acid
At the active aspect improving catalyst, there is preferably collaborative effect between zinc, potassium acetate, acetic acid rubidium, lithium acetate and rhodium acetate
Should.
【Embodiment 12】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), contain 0.90gRb
Acetic acid rubidium (RbOAc), containing 0.70gLi lithium acetate (LiOAc 2H2O cobaltous acetate (the Co (OAc)) with containing 1.90g Co2
·4H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid 350ml, by 1L diameter 3
Mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The ature of coal cylindrical activated carbon carrier impregnation of/g
In above-mentioned impregnation liquid, 3h is in 100 DEG C of dryings for standing, obtains described catalyst.Measure the Zn of this catalyst through ICP
Content is 100g/L, K content 6.10g/L, Rb content 0.90g/L, Li content 0.70g/L, Co content 1.90g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 167.18g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
【Embodiment 13】
The preparation of catalyst：100g zinc acetate (Zn (OAc) will be contained2), potassium acetate containing 6.10g (KOAc), contain 0.90gRb
Acetic acid rubidium (RbOAc), containing 0.70gLi lithium acetate (LiOAc 2H2O), contain the rhodium acetate (Rh of 1.00gRh2(OAc)4)
With the cobaltous acetate (Co (OAc) containing 0.90g Co2·4H2O) it is sufficiently mixed and be dissolved in the aqueous acetic acid that concentration is 60wt%,
Obtain impregnation liquid 350ml, 1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2/g
Ature of coal cylindrical activated carbon carrier impregnation in above-mentioned impregnation liquid, standing 3h in 100 DEG C of dryings, obtain described catalyst.
It is 100g/L through the Zn content that ICP measures this catalyst, K content 6.10g/L, Rb content 0.90g/L, Li content
0.70g/L, Rh content 1.00g/L, Co content 0.90g/L.
The synthesis of vinyl acetate：By 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use N2
System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, controlling reaction temperature is
175 DEG C, reaction pressure is 0.25MPa；Raw material volume air speed：280h-1；Raw material forms：Acetylene/acetic acid mol ratio=
6:1, after sustained response 50h, stopped reaction.
Product analysis：The reactant mixture that above-mentioned reaction is obtained cools down, decompression, separate, liquid phase adopt gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 169.65g/L h, for convenience of description and compare, catalyst prepare bar
Part, reaction condition, material inlet amount, the space-time yield of catalyst are listed in Tables 1 and 2 respectively.
Found out on year-on-year basis with embodiment 11 and embodiment 12 by embodiment 13, receive improving vinyl acetate catalyst space-time
Rate yield aspect, in the catalyst that the present invention uses, has synergism between Rh and Co in VIII metal.Illustrate
Have at the active aspect improving catalyst between zinc acetate, potassium acetate, acetic acid rubidium, lithium acetate, rhodium acetate and cobaltous acetate
Preferably cooperative effect.
Table 1
Table 2
Claims (10)
1. the catalyst of producing vinyl acetate by acetylene method, it is carrier that described catalyst adopts activated carbon, and active component includes acetic acid
The compound of zinc, potassium acetate and at least one metallic element in VIII metal or alkali metal.
2. catalyst according to claim 1 it is characterised in that described activated carbon be ature of coal column charcoal, cocoanut active charcoal,
Fructus Pruni shell activated carbon and at least one of activated carbon from bamboo.
3. catalyst according to claim 1 is it is characterised in that the specific surface area of described activated carbon is 1000～1500
cm2/ g, absorption pore volume is 0.60～1.00cm3/g.
4. according to claim 1 catalyst it is characterised in that described VIII metallic element be selected from cobalt, nickel, ferrum, platinum,
At least one in palladium, osmium, iridium, ruthenium and rhodium.
5. according to claim 1 catalyst it is characterised in that described alkali metal be selected from lithium, sodium, in rubidium and caesium
At least one.
6. according to claim 1 catalyst it is characterised in that in catalyst the content of zinc acetate be：50～300g/L,
The content of potassium acetate is：0.10～10.00g/L.
7. according to claim 1 catalyst it is characterised in that described in catalyst be selected from VIII metallic element and alkali metal
At least one content of middle metallic element is 0.50～8.00g/L.
8., by the production method of the catalyst described in claim 1, comprise the steps：
1. by the composition of catalyst, zinc acetate, the solution of potassium acetate, VIII metal and alkali-metal compound and carrier are mixed
Close；
2. it is dried.
9. vinyl acetate synthesis method, with acetic acid, acetylene as raw material, under catalyst any one of claim 1～7
Synthesizing vinyl acetate.
10. synthetic method according to claim 9, is characterized in that consisting of acetylene with molar ratio computing raw material:Acetic acid
=(5～12):1.
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