CN105585490B - method for preparing vinyl acetate - Google Patents
method for preparing vinyl acetate Download PDFInfo
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- CN105585490B CN105585490B CN201410573640.1A CN201410573640A CN105585490B CN 105585490 B CN105585490 B CN 105585490B CN 201410573640 A CN201410573640 A CN 201410573640A CN 105585490 B CN105585490 B CN 105585490B
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Abstract
The present invention relates to the method for preparing vinyl acetate, the yield of vinyl acetate and the problem of low selectivity when mainly solving to prepare vinyl acetate through carbonylation, cracking route after methyl acetate elder generation.By using the method for preparing vinyl acetate, 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 at least one, lanthanide series and the technical scheme selected from least one of IIB and alkaline-earth metal metallic element selected from iron series 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 for preparing vinyl acetate.
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 larger Organic Chemicals of yield in the world, is widely used in production poly-
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
Proposition 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, catalysis
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 and being made using halogen acids, sulfuric acid, nitric acid, polyphosphoric acid, benzene sulfonic acid, alkyl sulfonic acid etc.
The catalyst of vinyl acetate is prepared for ethylidene diacetate cracking.There is acetic acid second during synthesizing vinyl acetate in the above method
The problem of alkene yield is low and selective not high.
The content of the invention
There is provided a kind of new for the problem of technical problems to be solved by the invention are low vinyl acetate yield and not high selectivity
The method for preparing vinyl acetate, 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 for preparing vinyl acetate,
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 includes being selected from iron series element
At least one, lanthanide series and selected from least one of IIB and alkaline-earth metal metallic element.It is preferred that the active component is same
When include iron series element, lanthanide series, selected from least one of IIB metallic elements and selected from least one of alkaline-earth metal
Metallic element.Now vinyl acetate selectivity and yield are being improved between IIB metallic element and the metallic element of alkaline-earth metal
Aspect has synergy.
In above-mentioned technical proposal, the iron series element preferably is selected from least one of iron, cobalt and nickel.
In above-mentioned technical proposal, the lanthanide series preferably is selected from least one in lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium
Kind.In above-mentioned technical proposal, as most preferred technical scheme, the active component lanthanide series is more preferably lanthanum and samarium gold
Category.
In above-mentioned technical proposal, the IIB metals preferably are selected from least one of zinc, cadmium and mercury.
In above-mentioned technical proposal, the alkaline-earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including iron series element, group of the lanthanides
Element, selected from least one of IIB metals element and selected from least one of alkaline-earth metal element when；Such as described activity
Component includes cobalt, lanthanum, samarium, zinc and strontium, either including cobalt, lanthanum, samarium, zinc, barium and strontium or including cobalt, nickel, lanthanum, samarium, zinc, barium
And strontium.
In above-mentioned technical proposal, the content of iron series element is preferably 3.00~15.00g/L in the carbonylating catalyst,
More preferably 7.00~12.00g/L；The content of lanthanide series is preferably 0.10~5.00g/L in the carbonylating catalyst, more
Preferably 1.00~3.00g/L；At least one content of metal is excellent in IIB and alkaline-earth metal in the carbonylating catalyst
Elect 0.50~8.00g/L, more preferably 1.00~5.00g/L as.Load surface area per unit volume used in the carbonylating catalyst is preferred
For 50~300m2/ g, more preferably 150~200m2/ g, pore volume is preferably 0.80~1.20, and more preferably 0.90~1.00.On
State the preferably iodomethane of iodide described in technical scheme.
In above-mentioned technical proposal, the preparation method that the carbonylating catalyst can be used comprises the following steps：
1. will be golden in the compound of iron series element, the compound of lanthanide series, IIB and alkaline-earth metal by the composition of catalyst
The solution of the compound of category is mixed with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. iron series element preferably be selected from ferrocene, carbonyl cobalt, cobalt acetate,
At least one of cobalt nitrate, cobalt chloride, carbonyl nickel and nickel chloride.The compound of the step 1. lanthanide series preferably is selected from acetic acid
Lanthanum, lanthanum chloride, lanthanum nitrate, cerous acetate, cerous nitrate, cerium chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, ytterbium chloride, Europium chloride and chlorine
Change at least one of lutetium.Step 1. the IIB metallic compounds preferably be selected from zinc chloride, zinc acetate, zinc citrate, cadmium acetate,
At least one of caddy, cadmium nitrate, mercurous nitrate and mercuric sulfate.1. the alkaline earth metal compound preferably is selected from alkaline earth to step
In metal oxide, alkaline earth metal chloride, alkaline earth nitrate, alkali earth metal sulfate and Alkaline Earth Metal Acetate extremely
Few one kind.2. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
In above-mentioned technical proposal, by catalyst composition by the compound including iron series element, the compound of lanthanide series,
The compound of metal is not particularly limited with carrier hybrid mode in IIB and alkaline-earth metal, and their aqueous solution is contacted with carrier
Opportunity be also not particularly limited.For example can by the present invention by catalyst composition by the compound including iron series element,
The compound of metal, which is first mixed, in the compound of lanthanide series, IIB and alkaline-earth metal is dissolved in water or the chemical combination by them
Thing is sequentially formed to be mixed after the aqueous solution and contacted again with carrier, can be contacted with different order with carrier and be obtained the catalysis
Agent.
The key of the inventive method is carbonylating catalyst, after carbonylating catalyst is obtained, by making carbonylation
Catalyst contacts with the co-catalyst and can be used to carbonylation.The mode that carbonylating catalyst is contacted with co-catalyst does not have
There is special limitation, the opportunity for contacting both is also not particularly limited.It can for example be used by carbonylating catalyst of the present invention
Contact both before chemical reaction and form the catalyst, the reaction that both can also be made to be applied in catalyst of the present invention
Contact makes catalyst in-situ preparation in system.
The key of the present invention is the selection of carbonylating catalyst, and skilled person will know how true according to actual needs
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 sub- second of the double acetic acid of step (1) generation
Do not separated after ester and directly carry out step (2).Those skilled in the art know the suitable catalyst for cracking of selection and determine to close
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 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, using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis, is pressed after cooling, decompression, separation
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 includes necessarily
The iron series element of amount, lanthanide series and selected from least one of IIB and alkaline-earth metal metallic element, are conducive to improving catalyst
Activity and stability, so as to improve the yield and selectivity of vinyl acetate.
Test result indicates that, the vinyl acetate yield prepared by the present invention selectively reaches 81.36%, taken up to 58.27%
Active component in preferable technique effect, especially carbonylating catalyst was obtained while including iron series element, lanthanide series, being selected from
At least one of IIB metallic elements and during selected from least one of alkaline-earth metal metallic element, are achieved more prominent
Technique effect, in the synthesis that can be used for vinyl acetate.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of carbonylating catalyst：Co (OAc) by Co containing 8.98g, La containing 2.75g and containing 3.25gZn2·4H2O、
La(OAc)3·5H2O and zinc citrate (Zn3(C6H5O7)2·2H2O) it is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains
Than surface it is 165m by 1.0L to maceration extract 400ml2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst contains through icp analysis, Co
Measure as 8.98g/L, La contents 2.75g/L, Zn content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.27%, and selectivity is 81.36%, for convenience of description and is compared, and will be urged
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：Co (OAc) by Co containing 8.98g, La containing 2.75g and containing 3.25gSr2·4H2O、
La(OAc)3·5H2O and Sr (OAc)2·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L ratios
Surface is 165m2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 2h in
100 DEG C of dryings, obtain the catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, La contents
2.75g/L, Sr content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.36%, and selectivity is 81.29%, for convenience of description and is compared, and will be urged
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 Co containing the 8.98g and La containing 2.75g Co (OAc)2·4H2O and La
(OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is
0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings in above-mentioned maceration extract, obtains described urge
Agent.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, La contents 2.75g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 50.55%, and selectivity is 70.63%, for convenience of description and is compared, and will be urged
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.
By can be seen that the catalyst that the present invention is used compared with embodiment 1~2, using simultaneously containing Co, La and Zn work
Property component, while the catalyst performance ratio containing Co, La and Sr active component will be more containing only the performance of Co, La active constituent catalyst
Excellent, the selectivity and yield of vinyl acetate will be high.
【Embodiment 3】
The preparation of carbonylating catalyst：By Co containing 7.00g, Ce containing 1.00g and the Zn containing 1.00g Co2(CO)8、Ce
(OAc)3·6H2O and Zn (OAc)2·2H2O, which is sufficiently mixed, to be dissolved in the acetic acid that concentration is 10wt%, obtains maceration extract
400ml, by 1.0L than surface be 150m2/ g, pore volume is 0.90, a diameter of 5.6mm spherical Al2O3Carrier impregnation is in above-mentioned leaching
In stain liquid, 2h is stood in 80 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, Co contents
7.00g/L, Ce content 1.00g/L, Zn content 1.00g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.34%, and selectivity is 80.83%, for convenience of description and is compared, and will be urged
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 Fe containing 12.00g, Ce containing 3.00g and the Cd containing 5.00g ferrocene (Fe
(C5H5)2)、CeCl3·6H2O and Cd (OAc)2·2H2O, which is sufficiently mixed, to be dissolved in the nitric acid that concentration is 8wt%, is impregnated
Liquid 400ml, by 1.0L than surface be 200m2/ g, pore volume is 1.00, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned leaching
In stain liquid, 2h is stood in 120 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, Fe contents
12.00g/L, Ce content 3.00g/L, Cd 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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.25%, and selectivity is 81.42%, for convenience of description and is compared, and will be urged
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：CoCl by Co containing 8.98g, containing the 2.75gCe and Cd containing 3.25g2·6H2O、Ce
(NO3)3·6H2O and CdCl2Be sufficiently mixed and be dissolved in pure water, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g,
Pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
The catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, Ce contents 2.75g/L, Cd content
3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.39%, and selectivity is 81.24%, for convenience of description and is compared, and will be urged
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 Ni (NO containing 8.98gNi, Pr containing 2.75g and the Hg containing 3.25g3)2·6H2O、
Pr(OAc)3·5H2O and HgSO4It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L
It is 165m than surface2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, Pr contents
2.75g/L, Hg content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.41%, and selectivity is 81.31%, for convenience of description and is compared, and will be urged
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 Ni containing 8.98g, Nd containing 2.75g and the Be containing 3.25g NiCl2·6H2O、Nd
(OAc)3·5H2O and BeCl2Be sufficiently mixed and be dissolved in pure water, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g,
Pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
The catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, Nd contents 2.75g/L, Be content
3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.22%, and selectivity is 81.30%, for convenience of description and is compared, and will be urged
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 Co containing 8.98g, Yb containing 2.75g and the Mg containing 3.25g Co (NO3)2·
6H2O、YbCl3·6H2O and MgSO4It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h dry in 100 DEG C in above-mentioned maceration extract
It is dry, obtain the catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, Yb contents 2.75g/L, Mg
Content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 3.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 55.63%, and selectivity is 78.19%, for convenience of description and is compared, and will be urged
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 Co containing 8.98g, Eu containing 2.75g and the Co (NO containing 3.25gCa3)2·6H2O、
EuCl3·6H2O and CaO, which are sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L
It is 165m than surface2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, Eu contents
2.75g/L, Ca content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 10.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
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 is obtained is washed with water 3 times, and 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.70%, and selectivity is 80.98%, for convenience of description and is compared, and will be urged
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 Co containing 8.98g, Lu containing 2.75g and the Ba containing 3.25g Co2(CO)8、
LuCl3·6H2O and Ba (NO3)2It is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, maceration extract 400ml is obtained, by 1.0L
It is 165m than surface2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, Lu contents
2.75g/L, Ba content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.15%, and selectivity is 81.40%, for convenience of description and is compared, and will be urged
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 Co containing 8.98g, La containing 2.75g and the CoCl containing 3.25gSr2·6H2O、La
(OAc)3·5H2O and Sr (OAc)2·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared into table
Face is 165m2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, La contents 2.75g/
L, Sr content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.20%, and selectivity is 81.41%, for convenience of description and is compared, and will be urged
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 Co containing 8.98g, Sm containing 2.75g and the Sr containing 3.25g Co (OAc)2·
4H2O、SmCl3·6H2O and Sr (OAc)2·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L ratios
Surface is 165m2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 2h in
100 DEG C of dryings, obtain the catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, Sm contents
2.75g/L, Sr content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.31%, and selectivity is 81.37%, for convenience of description and is compared, and will be urged
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 Co containing 8.98g, Sm containing 2.75g and the Zn containing 3.25g Co (OAc)2·
4H2O、SmCl3·6H2O and zinc citrate (Zn3(C6H5O7)2·2H2O) it is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%,
Obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, Co
Content is 8.98g/L, Sm contents 2.75g/L, Zn content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.28%, and selectivity is 81.38%, for convenience of description and is compared, and will be urged
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 Co containing 8.98g, La containing 2.75g, the Co containing the 1.38gZn and Sr containing 1.87g
(OAc)2·4H2O、La(OAc)3·5H2O, zinc citrate (Zn3(C6H5O7)2·2H2) and Sr (OAc) O2·0.5H2O is fully mixed
Close be dissolved in concentration be 8wt% hydrochloric acid in, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.98,
A diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.
The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, La contents 2.75g/L, Zn content 1.38g/L, Sr content
1.87g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 59.24%, and selectivity is 82.75%, for convenience of description and is compared, and will be urged
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 present embodiment is compared with embodiment 1, embodiment 2 as can be seen that IIB metals Zn and alkaline-earth metal Sr is improving acetic acid
The yield and selectivity of ethene have preferably synergy.
【Embodiment 15】
The preparation of carbonylating catalyst：By Co containing 8.98g, La containing 1.32g, the Co containing 1.43gSm and containing 3.25gZn
(OAc)2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O and zinc citrate (Zn3(C6H5O7)2·2H2O) it is sufficiently mixed dissolving
In concentration for 8wt% hydrochloric acid in, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.98, a diameter of
5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonyl
Base catalyst is through icp analysis, and Co contents are 8.98g/L, La contents 1.32g/L, Sm content 1.43g/L, Zn content 3.25g/
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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 58.48%, and selectivity is 82.53%, for convenience of description and is compared, and will be urged
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 present embodiment is compared with embodiment 1, embodiment 13 as can be seen that lanthanide series metal La and Sm is improving double vinyl acetates
Yield and selectivity have preferably synergy.
【Embodiment 16】
The preparation of carbonylating catalyst：By Co containing 8.98g, La containing 1.32g, the Co containing 1.43gSm and containing 3.25gSr
(OAc)2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O and Sr (OAc)2·0.5H2O, which is sufficiently mixed, to be dissolved in concentration and is
In 8wt% hydrochloric acid, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.98, a diameter of 5.6mm's
Spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonylation is urged
Agent is through icp analysis, and Co contents are 8.98g/L, La contents 1.32g/L, Sm content 1.43g/L, Sr content 3.25g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 59.34%, and selectivity is 82.51%, for convenience of description and is compared, and will be urged
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 17】
The preparation of carbonylating catalyst：8.98g Co, La containing 1.32g will be contained, containing 1.43gSm, containing 1.38gZn and contained
1.87gSr Co (OAc)2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate (Zn3(C6H5O7)2·2H2O) and
Sr(OAc)2·0.5H2O, which is sufficiently mixed, to be dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into surface
For 165m2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, La content 1.32g/L,
Sm contents 1.43g/L, Zn content 1.38g/L, Sr content 1.87g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 60.85%, and selectivity is 84.03%, for convenience of description and is compared, and will be urged
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 present embodiment is compared with embodiment 15, embodiment 16 as can be seen that when lanthanide series metal in catalyst activity component
During selected from La, Sm, and during selected from IIB metals Zn and selected from alkaline-earth metal Sr, the selectivity and yield of vinyl acetate will be high, say
Understand between Co, La, Sm, Zn and Sr active component there is synergy well.
【Embodiment 18】
The preparation of carbonylating catalyst：8.98g Co, La containing 1.32g will be contained, containing 1.43gSm, containing 1.38gZn and contained
1.87gBa Co (OAc)2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate (Zn3(C6H5O7)2·2H2O) and
Ba(NO3)2Be sufficiently mixed be dissolved in concentration be 8wt% hydrochloric acid in, obtain maceration extract 400ml, by 1.0L than surface be 165m2/
G, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.The carbonylating catalyst is through icp analysis, and Co contents are 8.98g/L, La contents 1.32g/L, Sm content
1.43g/L, Zn content 1.38g/L, Ba content 1.87g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 61.02%, and selectivity is 84.11%, for convenience of description and is compared, and will be urged
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 19】
The preparation of carbonylating catalyst：To contain 8.98g Co, La containing 1.32g, containing 1.43gSm, containing 1.38gZn, contain
The 1.14gSr and Co (OAc) containing 0.73gBa2·4H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate (Zn3
(C6H5O7)2·2H2O)、Sr(OAc)2·0.5H2O and Ba (NO3)2It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains
Than surface it is 165m by 1.0L to maceration extract 400ml2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst contains through icp analysis, Co
Measure as 8.98g/L, La contents 1.32g/L, Sm content 1.43g/L, Zn content 1.38g/L, Sr content 1.14g/L, Ba content
0.73g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 62.76%, and selectivity is 85.62%, for convenience of description and is compared, and will be urged
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 present embodiment is compared with embodiment 17, embodiment 18 as can be seen that catalyst activity component iron series element, group of the lanthanides
Element and selected from IIB metals fix when, the favourable selectivity and yield for improving vinyl acetate of alkaline-earth metal Sr and Ba collaboration, explanation
There is synergy well between Co, La, Sm, Zn, Ba and Sr active component.
【Embodiment 20】
The preparation of carbonylating catalyst：To contain 8.98g Ni, La containing 1.32g, containing 1.43gSm, containing 1.38gZn, contain
The 1.14gSr and NiCl containing 0.73gBa2·6H2O、La(OAc)3·5H2O、SmCl3·6H2O, zinc citrate (Zn3
(C6H5O7)2·2H2O)、Sr(OAc)2·0.5H2O and Ba (NO3)2It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains
Than surface it is 165m by 1.0L to maceration extract 400ml2/ g, pore volume is 0.98, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst contains through icp analysis, Ni
Measure as 8.98g/L, La contents 1.32g/L, Sm content 1.43g/L, Zn content 1.38g/L, Sr content 1.14g/L, Ba content
0.73g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 62.57%, and selectivity is 85.73%, for convenience of description and is compared, and will be urged
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 21】
The preparation of carbonylating catalyst：To contain 5.98g Co, Ni containing 3.00g, La containing 1.32g, containing 1.43gSm, contain
1.38gZn, the Co (OAc) containing 1.14gSr and containing 0.73gBa2·4H2O、NiCl2·6H2O、La(OAc)3·5H2O、SmCl3·
6H2O, zinc citrate (Zn3(C6H5O7)2·2H2O)、Sr(OAc)2·0.5H2O and Ba (NO3)2It is sufficiently mixed and is dissolved in concentration and is
In 8wt% hydrochloric acid, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.98, a diameter of 5.6mm's
Spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonylation is urged
Agent is through icp analysis, and Co contents are 5.98g/L, and Ni contents are 3.00g/L, La contents 1.32g/L, Sm content 1.43g/L, Zn
Content 1.38g/L, Sr content 1.14g/L, Ba content 0.73g/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, is first discharged with argon gas in kettle and is pressurized to 2.0MPa after air, then pass to carbon monoxide and
Hydrogen is until pressure 8.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction
Temperature is 176 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, will react obtained product and is washed with water 3 times, organic matter enters oil phase, through rectification and purification remove 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, is first discharged with argon gas and is pressurized to 0.40MPa in kettle after air, improves mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, after controlling reaction temperature is 147 DEG C, 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 64.03%, and selectivity is 86.80%, for convenience of description and is compared, and will be urged
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 present embodiment is compared with embodiment 19, embodiment 20 as can be seen that lanthanide series, choosing in catalyst activity component
When being fixed from IIB metals and alkaline-earth metal, the favourable selectivity and yield for improving vinyl acetate of iron series element Co and Ni collaboration is said
Understand between Co, Ni, La, Sm, Zn, Ba and Sr active component there is synergy well.
Table 1
Table 2
Claims (10)
1. the method for preparing vinyl acetate, 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 the active component is simultaneously including iron series element, lanthanide series, selected from least one of IIB metals member
Element and selected from least one of alkaline-earth metal metallic element；The co-catalyst is iodide.
2. the method for being used to prepare vinyl acetate according to claim 1, it is characterised in that the iron series element is selected from iron, cobalt
At least one of with nickel.
3. according to claim 1 be used for prepare vinyl acetate method, it is characterised in that the lanthanide series be selected from lanthanum,
At least one of cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium.
4. the method for being used to prepare vinyl acetate according to claim 1, it is characterised in that the IIB metals are selected from zinc, cadmium
At least one of with mercury.
5. according to claim 1 be used for prepare vinyl acetate method, it is characterised in that the alkaline-earth metal be selected from beryllium,
At least one of magnesium, calcium, strontium and barium.
6. the method for being used to prepare vinyl acetate according to claim 1, it is characterised in that iron series element contains in catalyst
Measure and be：3.00~15.00g/L, the content of lanthanide series is：0.10~5.00g/L.
7. the method for being used to prepare vinyl acetate according to claim 1, it is characterised in that described in catalyst selected from IIB and
At least one content of metal is 0.50~8.00g/L in alkaline-earth metal.
8. the method for being used to prepare vinyl acetate according to claim 1, it is characterised in that the iodide are iodomethane.
9. the method for being used to prepare vinyl acetate according to claim 1, it is characterised in that the temperature of the carbonylation
For 130~200 DEG C；The pressure of reaction is 3.0~10.0MPa；Carbon monoxide and hydrogen volume ratio are 0.10~10.0 in reaction；
The time of reaction is 3.0~10.0h.
10. the method for being used to prepare vinyl acetate according to claim 1, it is characterised in that the system of carbonylation reaction catalyst
Preparation Method, comprises the following steps：
1. by the composition of catalyst by metal in the compound of iron series element, the compound of lanthanide series, IIB and alkaline-earth metal
The solution of compound is mixed with carrier；
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 |
-
2014
- 2014-10-24 CN CN201410573640.1A patent/CN105585490B/en active Active
Patent Citations (3)
| 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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