CN105585491B - Method used in vinyl acetate synthesis - Google Patents
Method used in vinyl acetate synthesis Download PDFInfo
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Abstract
The present invention relates to the method used in vinyl acetate synthesis, mainly solves the problems, such as that methyl acetate is successively low through being carbonylated, cracking the yield of vinyl acetate and selectivity when route prepares vinyl acetate.By using the method used in vinyl acetate synthesis, comprise the following steps：Methyl acetate carbonylation obtains ethylidene diacetate；Ethylidene diacetate obtains vinyl acetate through cracking；The carbonylating catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkali metal and the technical scheme selected from least one of IVA and VA metallic element, the technical problem is preferably resolved, available in the industrial production of vinyl acetate.
Description
Technical field
The present invention relates to the method used in vinyl acetate synthesis.
Background technology
Vinyl acetate, i.e. vinyl acetate (vinyl acetate, abbreviation VAC or VAM), are water white transparency at room temperature
Inflammable liquid, the ether fragrance with sweet tea.It is one of Organic Chemicals that yield is larger in the world, and it is poly- to be widely used in production
Vinyl acetate (PVAc), polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resin, acetal resin etc.
A series of chemical industry and fiber product, are widely used in all trades and professions.
Ethene vapor phase method and acetylene in gas phase method technique are used inside and outside the producing country of vinyl acetate, belongs to petrochemical process
Route, from after rising C1 chemistry, in the 1980s, U.S. Ha Erkang (Halcon) companies and BP (BP) company are successively
It is proposed is prepared new technology-carbonyl process synthesizing vinyl acetate of vinyl acetate by methanol and synthesis gas.The technique is independent of oil
Work raw material, but by methyl acetate and the carbonylation of synthesis gas, synthetic intermediate ethylidene diacetate (EDDA), then pass through
Cross thermal cracking production vinyl acetate and acetic acid.The novel part of whole technique is the hydroformylation reaction of methyl acetate, is catalyzed
Agent radium chloride is simultaneously modified with beta-picoline and iodomethane, and carbon monoxide intercalation reaction is the key point of whole technology.
United States Patent (USP) US5354886 is (entitled：Catalysts on inorganic carriers for
Producing ethylidene diacetate) mention RhCl3Or rhodium compound is supported on diatomite, titanium oxide, oxygen
Change and loaded catalyst is made on magnesium, aluminum oxide and zinc oxide.Using methyl acetate, carbon monoxide and hydrogen as raw material, in polarity
Under solvent condition, the reaction synthesis ethylidene diacetate under above-mentioned catalyst.US4843170 is (entitled：Process for
Produing vinyl acetate) in mention utilize halogen acids, sulfuric acid, nitric acid, polyphosphoric acid, benzene sulfonic acid, alkyl sulfonic acid etc. make
The catalyst of vinyl acetate is prepared for ethylidene diacetate cracking.Acetic acid second during synthesizing vinyl acetate be present in the above method
The problem of alkene yield is low and selective not high.
The content of the invention
The problem of technical problems to be solved by the invention are that vinyl acetate yield is low and selectivity is not high, there is provided Yi Zhongxin
Vinyl acetate synthesis used in method, this method have vinyl acetate high income and selectivity it is high the characteristics of.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Method used in vinyl acetate synthesis,
Comprise the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, carbonyl is carried out in the presence of carbonylating catalyst
Change reaction and obtain ethylidene diacetate；(2) in the presence of catalyst for cracking, ethylidene diacetate cracking is made to obtain vinyl acetate；
Wherein, the carbonylating catalyst uses SiO2、Al2O3Or its mixture is carrier, active component include rhodium, alkali metal and
Selected from least one of IVA and VA metallic element.It is preferred that the active component is simultaneously including rhodium, alkali metal, in IVA
At least one metallic element and selected from least one of VA metallic elements.Now IVA metallic element and VA metallic element
Between improve vinyl acetate selectivity and yield in terms of have synergy.
In above-mentioned technical proposal, the alkali metal preferably is selected from least one of lithium, sodium, potassium, rubidium and caesium.
In above-mentioned technical proposal, the IVA metals preferably are selected from least one of germanium, tin and lead.
In above-mentioned technical proposal, VA metals preferably are selected from least one of antimony and bismuth described in root.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including rhodium, alkali metal, tin
Element and antimony element；Such as the active component rhodium, lithium, rubidium, tin and antimony element when being made up of.
In above-mentioned technical proposal, the content of rhodium is preferably 3.00~15.00g/L in the carbonylating catalyst, more preferably
For 5.00~10.00g/L；The content of alkali metal is preferably 0.10~3.00g/L in the carbonylating catalyst, more preferably
0.50~2.00g/L；In the carbonylating catalyst selected from IVA and VA at least one content of metal be preferably 0.50
~8.00g/L, more preferably 1.00~5.00g/L.Load surface area per unit volume used in the carbonylating catalyst is preferably 50~
300m2/ g, more preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.Above-mentioned technology
Iodide described in scheme are preferably iodomethane.
In above-mentioned skill technical scheme, the optional preparation method of the carbonylating catalyst, comprise the following steps：
1. by the composition of catalyst by the solution and load of metallic compound in rhodium compound, alkali metal compound, IVA and VA
Body mixes；
2. dry.
In above-mentioned technical proposal, 1. the rhodium compound preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate step
At least one；1. the alkali metal compound preferably is selected from alkali metal oxide, alkali metal chloride, alkali metal nitric acid to step
At least one of salt, alkali metal sulfates and alkali metal acetate；The step 1. preferred titanium dioxide of IVA metallic compounds
At least one of germanium, stannous chloride, nitric acid stannous, stannous oxide, lead acetate and plumbi nitras；Step 1. metal compound in the VA
Thing preferably is selected from least one of basic bismuth carbonate, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate and antimony chloride；Step
Rapid 2. described drying temperature is 80~120 DEG C, more preferably 100~120 DEG C.
In above-mentioned technical proposal, gold in rhodium compound, alkali metal compound, IVA and VA will be included by the composition of catalyst
Category compound is not particularly limited with carrier hybrid mode, and the opportunity that their aqueous solution contacts with carrier does not also limit especially
System.Such as can in the present invention will be included to rhodium compound, alkali metal compound, IVA and VA by the composition of catalyst metal
Compound is first mixed to be dissolved in water or sequentially form to be mixed after the aqueous solution by their compound and connect again with carrier
Touch, can contact with carrier to obtain the catalyst with different order.
The key of the inventive method is the selection of carbonylating catalyst, after carbonylating catalyst is obtained, by making
Carbonylating catalyst contacts with the co-catalyst and can be used to carbonylation.Carbonylating catalyst contacts with co-catalyst
Mode is not particularly limited, and the opportunity for contacting both is also not particularly limited.Such as it can be urged by present invention carbonylation
Agent is used to before chemically reacting make both contact form the catalyst, and both can also be made to be applied in catalyst of the present invention
Reaction system in contact make catalyst in-situ preparation.
The key of the present invention is the selection of carbonylating catalyst, and skilled person will know how true according to being actually needed
Determine the proportioning of suitable reaction temperature, reaction time, reaction pressure and material.But the temperature reacted in above-mentioned technical proposal
Preferably 130~200 DEG C；The pressure of reaction is preferably 3.0~10.0MPa；The time of reaction is preferably 3.0~10.0h.One oxygen
The mol ratio for changing carbon and hydrogen is preferably 0.10~10.0.
In the method for methyl acetate synthesis vinyl acetate of the present invention, after step (1) terminates, carbonylation can be mixed
Compound carries out separation acquisition target product ethylidene diacetate and carries out step (2) again, can also the double acetic acid Asias second of step (1) generation
Do not separated after ester and directly carry out step (2).The suitable catalyst for cracking of the known selection of those skilled in the art and determination are closed
Suitable cracking reaction temperature, time and material proportion.Conventional catalyst for cracking have Bronsted acid (such as HI, HBr, HCl, HF,
H2SO4、H3PO4、HNO3、H3BO3、HClO3、HBrO3、HIO3, polyphosphoric acid, alkyl sulfonic acid, benzene sulfonic acid etc.), lewis acid (such as
IIA, IIIA, IVA, VA, VIA, IIIB, IVB, VB, VIB, VIIB, VIII metal halogen compound).Preferred benzene sulphur in the present invention
Acid is used as catalyst for cracking, and suitable cracking temperature is preferably 100~180 DEG C；Cleavage reaction pressure preferably 0~1.0MPa；Split
It is preferably 10~60min to solve the reaction time；Benzene sulfonic acid catalyst for cracking accounts for the 3.0~7.0% of raw material total amount；The preferred acetic acid of solvent
At least one of with aceticanhydride.
Product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed
Row formula calculates the conversion ratio of methyl acetate and the yield and selectivity of vinyl acetate：
Compared with prior art, key of the invention is that the active component of step (1) carbonylating catalyst is included necessarily
Amount rhodium, alkali metal and selected from least one of IVA and VA metallic element, be advantageous to improve carbonylating catalyst activity and
Stability, so as to improve the yield of vinyl acetate and selectivity.
Test result indicates that the vinyl acetate yield prepared by the present invention selectively reaches 83.54%, taken up to 60.51%
Obtain active component in preferable technique effect, especially catalyst while include rhodium, alkali metal, at least one in IVA
Kind of metallic element and during selected from least one of VA metallic elements, achieves more prominent technique effect, can be used for vinegar
In the synthesis of sour ethene.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gSn3·3H2O、LiCl
With Sn (NO3)2It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume are
0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/L, Sn content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.51%, and selectivity is 83.54%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 2】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gBi3·3H2O、LiCl
And BiCl3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/L, Bi
Content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.47%, and selectivity is 83.67%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh and containing 1.54gLi3·3H2O and LiCl is sufficiently mixed molten
Solution obtains maceration extract 400ml in pure water, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm's is spherical
SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonylating catalyst
Through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 51.08%, and selectivity is 71.96%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Rh, Li and Sn work
Property component and meanwhile performance of the catalyst performance ratio containing only Rh and Li active constituent catalysts containing Rh, Li and Bi active component will
More excellent, the selectivity and yield of vinyl acetate will be high.
【Embodiment 3】
The preparation of carbonylating catalyst：By the Rh (OAc) containing 10.00gRh, containing 2.00gK and containing 5.00gSn3、K2SO4With
SnCl2·2H2O, which is sufficiently mixed, is dissolved in concentration in 10wt% aqueous acetic acids, to obtain maceration extract 400ml, 1.0L being compared into surface
For 200m2/ g, pore volume 1.00, a diameter of 5.6mm spherical Al2O3Carrier impregnation stands 3h in 120 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 10.00g/L, K contents 2.00g/
L, Sn content 5.00g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 61.05%, and selectivity is 83.27%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 4】
The preparation of carbonylating catalyst：By the Rh containing 6.82gRh, containing 1.54gRb and containing 3.53gSn2(SO4)3·4H2O、
RbNO3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt% with SnO, obtains maceration extract 400ml, 1.0L is compared into table
Face is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Rb contents 1.54g/
L, Sn content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.39%, and selectivity is 83.35%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 5】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gCs and containing 3.53gPb3·3H2O、CsOAc
With Pb (OAc)2·3H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, hole
Hold for 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Cs contents 1.54g/L, Pb content 3.53g/
L。
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.52%, and selectivity is 83.43%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 6】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gPb3·3H2O、LiCl
With Pb (NO3)2It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume are
0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/L, Pb content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.35%, and selectivity is 83.28%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 7】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gBi3·3H2O、LiCl
(BiO)2CO3·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g,
Pore volume is 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
The catalyst.The carbonylating catalyst is through icp analysis, and Rh contents are 6.82g/L, Li contents 1.54g/L, Bi content
3.53g/L。
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.25%, and selectivity is 83.33%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 8】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gBi3·3H2O、LiCl
And Bi2(SO4)3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/
L, Bi content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.44%, and selectivity is 83.61%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gBi3·3H2O、LiCl
And Bi2O3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/L, Bi
Content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.37%, and selectivity is 83.57%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 10】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gSb3·3H2O、LiCl
And Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume 0.94,
A diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.
For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/L, Sb content 3.53g/L
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.51%, and selectivity is 83.74%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 11】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gSb3·3H2O、LiCl
And Sb2O3It is sufficiently mixed and is dissolved in the aqueous solution of nitric acid that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/L, Sb
Content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 3.0MPa
Temperature is 130 DEG C, and the mol ratio of carbon monoxide and hydrogen is 1:After 10, sustained response 3.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 57.47%, and selectivity is 78.95%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 12】
The preparation of carbonylating catalyst：By the RhCl containing 6.82gRh, containing 1.54gLi and containing 3.53gSb3·3H2O、LiCl
And Sb2(SO4)3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li contents 1.54g/
L, Sb content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 10.0MPa
Temperature is 200 DEG C, and the mol ratio of carbon monoxide and hydrogen is 10:After 1, sustained response 10.0h, stop reaction.Reactor is dropped
To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification
Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 61.14%, and selectivity is 83.02%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 13】
The preparation of carbonylating catalyst：By containing 6.82gRh, containing 1.00gLi, containing 0.54gRb and containing 3.53gSb's
RhCl3·3H2O、LiCl、RbNO3And Cl3Sb, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared into surface
For 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Rh contents are 6.82g/L, Li content 1.00g/L,
Rb contents 0.54g/L, Sb content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 62.32%, and selectivity is 84.82%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 14】
The preparation of carbonylating catalyst：By containing 6.82gRh, containing 1.00gLi, containing 0.54gRb and containing 3.53gSn's
RhCl3·3H2O、LiCl、RbNO3And SnCl2·2H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L
It is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, and Rh contents are 6.82g/L, Li contents
1.00g/L, Rb content 0.54g/L, Sn content 3.53g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 62.48%, and selectivity is 85.04%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 15】
The preparation of carbonylating catalyst：To contain 6.82gRh, containing 1.00gLi, containing 0.54gRb, containing 2.15gSb and contain
1.38gSn RhCl3·3H2O、LiCl、RbNO3、Cl3Sb and SnCl2·2H2O, which is sufficiently mixed, to be dissolved in pure water, is impregnated
Liquid 400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned leaching
In stain liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is through icp analysis, Rh contents
6.82g/L, Li content 1.00g/L, Rb content 0.54g/L, Sb content 2.15g/L, Sn content 1.38g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 6.8MPa
Temperature is 172 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.30MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 140 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 64.34%, and selectivity is 87.32%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
The catalyst that the present invention uses, active component is simultaneously containing Rh, Li, Rb, Sb and Sn active component specific activity component
Containing Rh, Li and Sb, containing only Rh, Li and Sn, containing only Rh, Li, Rb and Sb, the performance of the catalyst containing only Rh, Li, Rb and Sn will be more
Excellent, the selectivity and yield of ethylidene diacetate will be high, and this is from embodiment 15, embodiment 10, embodiment 1, the and of embodiment 13
The data of embodiment 14, which can be seen that, illustrates that collaboration well be present between five kinds of active components of Rh, Li, Rb, Sb and Sn makees
With.
Table 1
Table 2
Claims (10)
1. the method used in vinyl acetate synthesis, comprises the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material,
Carbonylation is carried out in the presence of carbonylating catalyst, co-catalyst and obtains ethylidene diacetate；(2) deposited in catalyst for cracking
Under, ethylidene diacetate cracking is set to obtain vinyl acetate；Wherein, the carbonylating catalyst uses SiO2、Al2O3Or its
Mixture is carrier, and active component includes rhodium, alkali metal and urged selected from least one of IVA and VA metallic element, described help
Agent is iodide.
2. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that the alkali metal be selected from lithium, sodium,
At least one of potassium, rubidium and caesium.
3. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that the IVA metals are selected from germanium, tin
At least one of with lead.
4. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that the VA metals are selected from antimony and bismuth
At least one of.
5. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that the content of rhodium is in catalyst：
3.00~15.00g/L, the content of alkali metal are：0.10~3.00g/L.
6. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that described in catalyst selected from IVA and
At least one content of metal is 0.50~8.00g/L in VA.
7. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that the iodide are iodomethane.
8. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that the temperature of the carbonylation
Spend for 130~200 DEG C.
9. the method used in vinyl acetate synthesis according to claim 1, the pressure of reaction is 3.0~10.0MPa;Reaction
Middle carbon monoxide and hydrogen volume ratio is 0.10~10.0;The time of reaction is 3.0~10.0h.
10. the method used in vinyl acetate synthesis according to claim 1, it is characterised in that the preparation of carbonylating catalyst
Method, comprise the following steps：
1. the solution of metallic compound and carrier in rhodium compound, alkali metal compound, IVA and VA are mixed by the composition of catalyst
Close；
2. dry.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0108539A1 (en) * | 1982-10-30 | 1984-05-16 | BP Chemicals Limited | Preparation of esters |
| US4659865A (en) * | 1979-09-13 | 1987-04-21 | Mitsubishi Gas Chemical Co., Inc. | Process for producing ethylidenediacetate |
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
| US4659865A (en) * | 1979-09-13 | 1987-04-21 | Mitsubishi Gas Chemical Co., Inc. | Process for producing ethylidenediacetate |
| EP0108539A1 (en) * | 1982-10-30 | 1984-05-16 | BP Chemicals Limited | Preparation of esters |
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