CN106268945A - For synthesizing the catalyst of acetylene method vinyl acetate - Google Patents
For synthesizing the catalyst of acetylene method vinyl acetate Download PDFInfo
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Abstract
The present invention relates to the catalyst for synthesizing acetylene method vinyl acetate, mainly solve the problem that in prior art, acetylene in gas phase method catalyst activity is the highest.The present invention uses the catalyst for synthesizing acetylene method vinyl acetate, described catalyst uses activated carbon to be carrier, active component includes the technical scheme of the compound of zinc acetate, potassium acetate and at least one metallic element in IVA or IB metal, preferably solve this problem, can be used in the commercial 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, described acetylene in gas phase method vinyl acetate catalyst
Preparation method and the synthetic method of acetylene in gas phase method vinyl acetate.
Background technology
(Vinyl acetate is called for short VA to vinyl acetateC) it is important Organic Chemicals, it is widely used in manufacturing poly-vinegar
Acid ethylene, polyvinyl alcohol are also processed further for binding agent, coating, vinylon fibre, fabric processing, emulsion, resin
With aspects such as 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 by two developmental stage of liquid and gas technique.Before 1940, mainly with
Liquid phase process is main, reacts under 30～70 DEG C of normal pressures, and catalyst is mercury oxide and sulphuric acid or phosphoric acid；20th century
After the forties, starting 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
Ethylene, the method proposing subsequently to use acetylene in gas phase synthesis VAc, 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) reports use catalyst Z n (OAc)2/ C, has synthesized acetic acid second
Alkene.Chinese patent CN1903435 (entitled: a kind of catalyst for vinyl acetate synthesis and preparation method thereof) carries
Having supplied the preparation method of a kind of acetylene method vinyl acetate catalyst, catalyst activity component uses zinc oxide and acetic acid, and adds
Enter a small amount of waltherite, be immersed in activated carbon and be dried to obtain catalyst.But the catalyst activity that above-mentioned technology provides is the most not
Height, limits the application of acetylene method vinyl acetate.
Summary 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, it is provided that a kind of new catalyst for synthesizing acetylene method vinyl acetate, the active high feature of this catalyst.
The two of the technical problem to be solved are the production methods using one of above-mentioned technical problem described catalyst.
The three of the technical problem to be solved are the vinyl acetates using one of above-mentioned technical problem described catalyst
Synthetic method.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: be used for synthesizing acetylene method vinyl acetate
Catalyst, described catalyst uses activated carbon to be carrier, active component include zinc acetate, potassium acetate and selected from IVA or
The compound of at least one metallic element in IB.The most described active component includes zinc acetate, potassium acetate simultaneously, is selected from
At least one metallic element in IVA and the compound of at least one metallic element in IB.The now gold of IVA
In the space-time yield side improving vinyl acetate catalyst between the compound of the metallic element in the compound of genus element and IB
Mask has 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 IVA metal preferably is selected from least one in germanium, stannum and lead, includes the most simultaneously
Stannum and lead.Described IB metal preferably is selected from least one in copper, silver and gold, includes copper and gold the most simultaneously.
In technique scheme, as most preferred technical scheme, described active component include simultaneously zinc acetate, potassium acetate,
The compound of IVA metallic element and the compound of IB metallic element；The most described active component by zinc acetate, potassium acetate,
Stannous chloride and tetra chlorauric acid ammonium (or Schweinfurt green) composition, or by zinc acetate, potassium acetate, stannous chloride (or acetic acid
Lead), tetra chlorauric acid ammonium and Schweinfurt green composition, or by zinc acetate, potassium acetate, stannous chloride, lead acetate, tetrachloro gold
Acid ammonium and Schweinfurt green composition.
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；
In described catalyst, in IVA and IB, at least one content of metal 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 the production method of catalyst, comprise the steps:
1. the composition of catalyst is pressed by the solution of metallic element compound in zinc acetate, potassium acetate, IVA and IB and carrier
Mixing；
2. it is dried.
In technique scheme, the preferred stannous oxalate of compound of step the most described IVA metal, germanium tetrachloride, protochloride
In stannum, nitric acid stannous, Tin monoxide, lead acetate and plumbi nitras at least one；More preferably in lead acetate and stannous chloride
At least one；In the most described IB of step, the compound of metal preferably is selected from copper citrate, Schweinfurt green, copper nitrate, acetic acid
At least one in silver, silver tetrafluoroborate and tetra chlorauric acid ammonium；More preferably at least in Schweinfurt green and tetra chlorauric acid ammonium
Kind.The most described baking temperature of step is 80～120 DEG C, more preferably 100～120 DEG C.
For solve above-mentioned technical problem three, technical scheme is as follows: vinyl acetate synthesis method, with acetic acid,
Acetylene is raw material, and in the presence of catalyst, reaction generates vinegar described in any one of the technical scheme of one of above-mentioned technical problem
Acid ethylene.
The present invention's, it is crucial that the selection of catalyst, skilled person will know how to determine 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
It it is 150～200 DEG C；The pressure of reaction is preferably 0.1～0.5MPa；With molar ratio computing raw material composition preferably acetylene: 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 present invention's it is crucial that the active component of catalyst includes zinc acetate, potassium acetate and is selected from
The compound of at least one metallic element in IVA and IB, is conducive to improving activity and the stability of catalyst, thus carries
The high yield of vinyl acetate.
Test result indicate that, when using catalyst of the present invention, the space-time yield of catalyst reaches 163.39g/L h, achieves
Preferably in technique effect, especially catalyst active component include simultaneously zinc acetate, potassium acetate, in IVA extremely
When few a kind of metallic element compound and at least one the metallic element compound in IB, achieve more prominent skill
Art effect, can be used in the commercial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc) with containing 2.80gSn
Stannous chloride (SnCl2·2H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid
350ml, is 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1200cm2The ature of coal of/g
Cylindrical activated carbon carrier impregnation, in above-mentioned impregnation liquid, stands 3h and is dried in 100 DEG C, obtain described catalyst.Warp
It is 105g/L, K content 6.50g/L that ICP measures the Zn content of this catalyst, Sn content 2.80g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 163.39g/L 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 2]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc) with containing 2.80gAu
Tetra chlorauric acid ammonium (NH4AuCl4·2H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain
Impregnation liquid 350ml, is 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1200cm2/g
Ature of coal cylindrical activated carbon carrier impregnation in above-mentioned impregnation liquid, stand 3h in 100 DEG C be dried, obtain described catalyst.
The Zn content measuring this catalyst through ICP 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, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 163.56g/L 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.
[comparative example 1]
For [embodiment 1] and the comparative example of [embodiment 2].
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2) and (KOAc) Han 6.50g potassium acetate the most mixed
Close be dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid 350ml, by 1L diameter 3mm, long 2cm,
Pore volume is 0.80cm3/ g, specific surface area are 1200cm2The ature of coal cylindrical activated carbon carrier impregnation of/g is at above-mentioned impregnation liquid
In, stand 3h and be dried in 100 DEG C, obtain described catalyst.The Zn content measuring this 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, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 124.83g/L 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.
By compared with embodiment 1～2 it can be seen that the catalyst that uses of the present invention, use simultaneously containing zinc acetate, acetic acid
Potassium and stannous chloride active component, simultaneously containing zinc acetate, potassium acetate and the catalyst performance ratio of tetra chlorauric acid ammonium active component
Performance containing only 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), containing 3.00g potassium acetate (KOAc) with containing 1.00gPb
Lead acetate (Pb (OAc)2·3H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, impregnated
Liquid 350ml, is 0.60cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1000cm2The circle of/g
Column type cocoanut active charcoal carrier impregnation, in above-mentioned impregnation liquid, stands 3h and is dried in 80 DEG C, obtain described catalyst.Warp
It is 80g/L, K content 3.00g/L that ICP measures the Zn content of this catalyst, Pb content 1.00g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 127.60g/L 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 4]
The preparation of catalyst: 200g zinc acetate (Zn (OAc) will be contained2), containing 7.00g potassium acetate (KOAc) with containing 5.00gPb
Lead acetate (Pb (OAc)2·3H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, impregnated
Liquid 350ml, is 1.00cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1500cm2The circle of/g
Column type Fructus Pruni shell absorbent charcoal carrier is immersed in above-mentioned impregnation liquid, stands 3h and is dried in 120 DEG C, obtains described catalyst.Warp
It is 200g/L, K content 7.00g/L that ICP measures the Zn content of this catalyst, Pb content 5.00g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 164.12g/L 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: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc) with containing 2.80gPb
Lead acetate (Pb (OAc)2·3H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, impregnated
Liquid 350ml, is 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1200cm2The circle of/g
Column type activated carbon from bamboo carrier impregnation, in above-mentioned impregnation liquid, stands 3h and is dried in 120 DEG C, obtain described catalyst.Warp
It is 105g/L, K content 6.50g/L that ICP measures the Zn content of this catalyst, Pb content 2.80g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 163.52g/L 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 6]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc) with containing 2.80gCu
Schweinfurt green Cu (OAc)2·H2O is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtains impregnation liquid
350ml, is 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1200cm2The ature of coal of/g
Cylindrical activated carbon carrier impregnation, in above-mentioned impregnation liquid, stands 3h and is dried in 100 DEG C, obtain described catalyst.Warp
It is 105g/L, K content 6.50g/L that ICP measures the Zn content of this catalyst, Cu content 2.80g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 163.64g/L 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 7]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc) with containing 2.80gCu
Schweinfurt green Cu (OAc)2·H2O is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtains impregnation liquid
350ml, is 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1200cm2The ature of coal of/g
Cylindrical activated carbon carrier impregnation, in above-mentioned impregnation liquid, stands 3h and is dried in 100 DEG C, obtain described catalyst.Warp
It is 105g/L, K content 6.50g/L that ICP measures the Zn content of this catalyst, Cu content 2.80g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 150 DEG C, and reaction pressure is 0.10MPa；Raw material volume air speed: 250h-1；Raw material forms: acetylene/acetic acid mole
Ratio=5:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 152.79g/L 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 8]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc) with containing 2.80gCu
Schweinfurt green (Cu (OAc)2·H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid
350ml, is 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1200cm2The ature of coal of/g
Cylindrical activated carbon carrier impregnation, in above-mentioned impregnation liquid, stands 3h and is dried in 100 DEG C, obtain described catalyst.Warp
It is 105g/L, K content 6.50g/L that ICP measures the Zn content of this catalyst, Cu content 2.80g/L.
The synthesis of vinyl acetate: by 30ml Catalyst packing in micro fixed-bed reactor, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 200 DEG C, and reaction pressure is 0.50MPa；Raw material volume air speed: 350h-1；Raw material forms: acetylene/acetic acid mole
Ratio=12:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 164.26g/L 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 9]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc), containing 1.05gSn
SnCl2·2H2O and the tetra chlorauric acid ammonium (NH containing 1.75gAu4AuCl4·2H2O) it is sufficiently mixed and is dissolved in concentration and is
In the aqueous acetic acid of 60wt%, obtain impregnation liquid 350ml, be 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/g、
Specific surface area is 1200cm2The ature of coal cylindrical activated carbon carrier impregnation of/g, in above-mentioned impregnation liquid, stands 3h in 100 DEG C
It is dried, obtains described catalyst.The Zn content measuring this 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, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 165.47g/L 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.
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 IB metal Au Yu IVA, metal Sn has preferable synergism, illustrates
Zinc acetate, potassium acetate, have at the active aspect improving catalyst between tetra chlorauric acid ammonium and stannous chloride preferably collaborative
Effect.
[embodiment 10]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc), containing 1.05gSn
SnCl2·2H2O and the Schweinfurt green (Cu (OAc) containing 1.75gCu2·H2O) it is sufficiently mixed that to be dissolved in concentration be 60wt%'s
In aqueous acetic acid, obtain impregnation liquid 350ml, be 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, ratio
Surface area is 1200cm2The ature of coal cylindrical activated carbon carrier impregnation of/g, in above-mentioned impregnation liquid, stands 3h in 100 DEG C
It is dried, obtains described catalyst.The Zn content measuring this catalyst through ICP 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, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 165.61g/L 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 11]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc), containing 1.05gSn
SnCl2·2H2O, tetra chlorauric acid ammonium (NH containing 1.05gAu4AuCl4·2H2O) Schweinfurt green with containing 0.70gCu
(Cu(OAc)2·H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid 350ml, will
1L diameter 3mm, long 2cm, pore volume are 0.80cm3/ g, specific surface area are 1200cm2The ature of coal of/g is cylindrical activated
High-area carbon is immersed in above-mentioned impregnation liquid, stands 3h and is dried in 100 DEG C, obtains described catalyst.Measuring through ICP should
The Zn content of catalyst 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, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 167.96g/L 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.
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 Au and Cu in IB metal.Illustrate vinegar
Acid zinc, potassium acetate, stannous chloride, between tetra chlorauric acid ammonium and Schweinfurt green improve catalyst active aspect have preferably
Cooperative effect.
[embodiment 12]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc), containing 1.05gPb
Lead acetate (Pb (OAc)2·3H2O), the tetra chlorauric acid ammonium (NH containing 1.05gAu4AuCl4·2H2O) with containing 0.70gCu
Schweinfurt green (Cu (OAc)2·H2O) it is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 60wt%, obtain impregnation liquid
350ml, is 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/ g, specific surface area are 1200cm2The ature of coal of/g
Cylindrical activated carbon carrier impregnation, in above-mentioned impregnation liquid, stands 3h and is dried in 100 DEG C, obtain described catalyst.Warp
It is 105g/L, K content 6.50g/L that ICP measures the Zn content of this catalyst, 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, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 167.71g/L 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 13]
The preparation of catalyst: 105g zinc acetate (Zn (OAc) will be contained2), containing 6.50g potassium acetate (KOAc), containing 0.40gSn
SnCl2·2H2O, lead acetate (Pb (OAc) containing 0.65gPb2·3H2O), the tetra chlorauric acid ammonium containing 1.05gAu
(NH4AuCl4·2H2O) Schweinfurt green (Cu (OAc) with containing 0.70gCu2·H2O) it is sufficiently mixed and is dissolved in concentration and is
In the aqueous acetic acid of 60wt%, obtain impregnation liquid 350ml, be 0.80cm by 1L diameter 3mm, long 2cm, pore volume3/g、
Specific surface area is 1200cm2The ature of coal cylindrical activated carbon carrier impregnation of/g, in above-mentioned impregnation liquid, stands 3h in 100 DEG C
It is dried, obtains described catalyst.The Zn content measuring this catalyst through ICP 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, use N2After leak test, use
N2System is fully purged, after system heats up, closes N2, cut acetylene successively, open acetic acid pump, control reaction temperature
Degree is 178 DEG C, and reaction pressure is 0.25MPa；Raw material volume air speed: 300h-1；Raw material forms: acetylene/acetic acid mole
Ratio=6:1, after sustained response 50h, stopped reaction.
Product analysis: the reactant mixture above-mentioned reaction obtained cools down, reduces pressure, separates, liquid phase employing gas chromatogram-
GC-MS (GC-MASS) is analyzed.
The space-time yield being computed catalyst is 169.95g/L 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.
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 Au and Cu in IVA metal.Explanation
Zinc acetate, potassium acetate, stannous chloride, have at the active aspect improving catalyst between tetra chlorauric acid ammonium and Schweinfurt green
Preferably cooperative effect.
Table 1
Table 2
Claims (10)
1., for synthesizing the catalyst of acetylene method vinyl acetate, described catalyst uses activated carbon to be carrier, and active component includes
Zinc acetate, potassium acetate and the compound of at least one metallic element in IVA or IB metal.
Catalyst the most according to claim 1, it is characterised in that described activated carbon be ature of coal column charcoal, cocoanut active charcoal,
At least one of Fructus Pruni shell activated carbon and activated carbon from bamboo.
Catalyst the most according to claim 1, 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。
Catalyst the most according to claim 1, it is characterised in that described IVA metallic element is selected from germanium, stannum and lead extremely
Few one.
Catalyst the most according to claim 1, it is characterised in that described IB metallic element is selected from copper, silver and gold at least
A kind of.
Catalyst the most according to claim 1, it is characterised in that in catalyst, the content of zinc acetate is: 50～300g/L,
The content of potassium acetate is: 0.10～10.00g/L.
Catalyst the most according to claim 1, it is characterised in that be selected from metallic element in IVA and IB described in catalyst
At least one content is 0.50～8.00g/L.
8., by the production method of the catalyst described in claim 1, comprise the steps:
1. the composition of catalyst is pressed by the solution of metallic element compound in zinc acetate, potassium acetate, IVA and IB and carrier
Mixing；
2. it is dried.
9. vinyl acetate synthesis method, with acetic acid, acetylene as raw material, under catalyst according to any one of claim 1～7
Synthesizing vinyl acetate.
Synthetic method the most 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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