CN105523929B - The method of methyl acetate hydroformylation synthesizing vinyl acetate - Google Patents
The method of methyl acetate hydroformylation synthesizing vinyl acetate Download PDFInfo
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Abstract
The present invention relates to the method for methyl acetate hydroformylation synthesizing vinyl acetate, 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 for methyl acetate hydroformylation synthesizing 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 selected from iron series element, selected from IIIB elements are at least one and technical scheme selected from least one of IVA and alkali metal 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 for methyl acetate hydroformylation synthesizing 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 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
Methyl acetate hydroformylation synthesizing vinyl acetate method, this method has vinyl acetate high income and the high spy of selectivity
Point.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Methyl acetate hydroformylation synthetic vinegar
The method of sour ethene, comprises the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, deposited in carbonylating catalyst
Ethylidene diacetate is obtained in lower progress carbonylation；(2) in the presence of catalyst for cracking, obtain ethylidene diacetate cracking
Obtain vinyl acetate；Wherein, the carbonylating catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes
At least one selected from iron series element, IIIB elements and selected from least one of IVA and alkali metal metallic element.It is it is preferred that described
Active component is simultaneously including iron series element, IIIB elements, selected from least one of IVA metallic elements and in alkali metal
At least one metallic element.Now the selection of vinyl acetate is being improved between IVA metallic element and the metallic element of alkali metal
Property and yield in terms of have synergy.
In above-mentioned technical proposal, the iron series element preferably is selected from least one of iron, cobalt and nickel.More preferably cobalt and nickel.
In above-mentioned technical proposal, the IIIB elements preferably are selected from least one of scandium, yttrium, lanthanum, cerium and samarium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component IIIB elements be more preferably yttrium and
Samarium metal.
In above-mentioned technical proposal, the IVA metals preferably are selected from least one of germanium, tin and lead.
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, as most preferred technical scheme, the active component is simultaneously including iron series element, IIIB
Element, IVA metals and alkali metal；Such as the active component includes cobalt, yttrium, tin (or lead) and rubidium, or including cobalt, yttrium (or
Samarium), tin, lead and rubidium, either including cobalt, yttrium, samarium, tin, lead and rubidium or including cobalt, nickel, yttrium, samarium, tin, lead and rubidium.
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 IIIB elements is preferably 0.10~5.00g/L in the carbonylating catalyst, more
Preferably 1.00~4.00g/L；At least one content of metal is preferred in IVA and alkali metal in the carbonylating catalyst
For 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.It is above-mentioned
Iodide described in technical scheme are preferably iodomethane.
In above-mentioned technical proposal, preparation method that the carbonylating catalyst can use comprises the following steps：
1. by the composition of catalyst by metal in the compound of iron series element, the compound of IIIB elements, IVA and alkali metal
The solution of compound mixed with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. iron series element preferably be selected from carbonyl cobalt, cobalt nitrate, cobalt chloride,
At least one of cobalt acetate, ferrocene, carbonyl nickel, nickel chloride and nickel acetate.The compound of step 1. IIIB elements is excellent
Selected from acetic acid scandium, scandium chloride, yttrium chloride, yttrium nitrate, yttrium sulfate, lanthanum chloride, lanthanum nitrate, cerous acetate, cerous nitrate, cerium chloride and chlorine
Change at least one of samarium.1. the IVA metallic compounds preferably are selected from germanium tetrachloride, tetraethyl germanium, stannous chloride, nitric acid to step
At least one of stannous, stannous oxide, lead acetate, plumbi nitras and basic lead carbonate.1. the alkali metal compound is excellent for step
In alkali metal oxide, alkali metal chloride, alkali nitrates, alkali metal sulfates and alkali metal acetate at least
It is a kind of.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 IIIB elements,
The compound of metal is not particularly limited with carrier hybrid mode in IVA and alkali metal, what their aqueous solution contacted with carrier
Opportunity is also not particularly limited.Such as can by the present invention by catalyst composition by the compound including iron series element,
The compound of metal, which first mixes, in the compounds of IIIB elements, IVA and alkali metal is dissolved in water or the compound by them
Sequentially form to be mixed after the aqueous solution and contacted again with carrier, can contact with carrier to obtain the catalyst with different order.
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 contacts with co-catalyst does not have
There is special limitation, the opportunity for contacting both is also not particularly limited.Such as it can 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 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
The iron series element of amount, IIIB elements and selected from least one of IVA and alkali metal metallic element, are advantageous to improve 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 81.14%, taken up to 58.29%
Obtain active component in preferable technique effect, especially catalyst while include iron series element, IIIB elements, in IVA
At least one metallic element and during selected from least one of alkali metal metallic element, achieve more prominent technology effect
Fruit, it can be used in the synthesis of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of carbonylating catalyst：By Co containing 8.60g, the CoCl containing 3.40gY and containing 3.10gSn2·6H2O、Y
(NO3)3·6H2O and SnCl2·2H2O, which is sufficiently mixed, to be dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, will
1.0L is 165m than surface2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation is quiet in above-mentioned maceration extract
2h is put in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is 8.60g/L through icp analysis, Co contents, and Y contains
Measure 3.40g/L, Sn contents 3.10g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 58.29%, and selectivity is 81.14%, 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 Co containing 8.60g, the CoCl containing 3.40gY and containing 3.10gRb2·6H2O、Y
(NO3)3·6H2O and RbNO3It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 165m by 1.0L2/ g,
Pore volume is 0.95, 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 8.60g/L, Y contents 3.40g/L, Rb content
3.10g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 58.37%, and selectivity is 81.03%, 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 Co containing 8.60g and the CoCl containing 3.40gY2·6H2O and Y (NO3)3·6H2O fills
Point mixed dissolution obtains maceration extract 400ml in pure water, than surface is 165m by 1.0L2/ g, pore volume 0.95 are 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
For base catalyst through icp analysis, Co contents are 8.60g/L, Y contents 3.40g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 50.30%, and selectivity is 70.47%, 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 Co, Y and Sn work
Property component while catalyst performance ratio containing Co, Y and Rb active component will be more containing only the performance of Co, Y active constituent catalyst
Excellent, the selectivity and yield of vinyl acetate will be high.
【Embodiment 3】
The preparation of carbonylating catalyst：By Ni containing 7.00g, Sc containing 1.00g and the Ge containing 1.00g NiCl2·6H2O、Sc
(OAc)3·6H2O and GeCl4It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 150m2/ g, pore volume 0.90, a diameter of 5.6mm spherical Al2O3Carrier impregnation in above-mentioned maceration extract, stand 2h in
80 DEG C of dryings, obtain the catalyst.The carbonylating catalyst is through icp analysis, and Ni contents are 7.00g/L, Sc contents
1.00g/L, Ge 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, 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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 57.70%, and selectivity is 80.77%, 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 Ni containing 12.00g, the Ni (OAc) containing the 4.00gSc and Sn containing 5.00g2、
ScCl3·6H2O and SnO, 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 200m2/ g, pore volume 1.00, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 120 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Ni contents are 12.00g/L, Sc content 4.00g/L,
Sn contents 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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 58.63%, and selectivity is 81.52%, 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 Ni containing 8.60g, the Ni (CO) containing the 3.40gY and Ge containing 3.10g4、YCl3·
6H2O and tetraethyl germanium ((CH3CH2)4Ge) it is sufficiently mixed and is dissolved in ether, obtain maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Ni contents are 8.60g/L, Y contents 3.40g/L, and Ge contains
Measure 3.10g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 58.24%, and selectivity is 81.37%, 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 ferrocene (Fe containing 8.60gFe, Y containing 3.40g and the Sn containing 3.10g
(C5H5)2)、Y2(SO4)3·8H2O and Sn (NO3)2It is sufficiently mixed and is dissolved in the nitric acid that concentration is 8wt%, obtains maceration extract
400ml, than surface it is 165m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is through icp analysis, Fe contents
8.60g/L, Y content 3.40g/L, Sn content 3.10g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 81.26%, 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 Co containing 8.60gCo, La containing 3.40g and the Pb containing 3.10g2(CO)8、
LaCl3·7H2O and Pb (OAc)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 0.95, 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 8.60g/L, La contents
3.40g/L, Pb content 3.10g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 58.30%, and selectivity is 81.35%, 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 8】
The preparation of carbonylating catalyst：By the Co (NO containing 8.60gCo, La containing 3.40g and the Pb containing 3.10g3)2·6H2O、
La(OAc)3·5H2O and Pb (NO3)2·3H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared into surface
For 165m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Co contents are 8.60g/L, La content 3.40g/L,
Pb contents 3.10g/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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 55.86%, and selectivity is 79.09%, 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 Co containing 8.60g, the Co (OAc) containing 3.40gCe and containing 3.10gPb2·4H2O、
Ce(OAc)3·6H2O and basic lead carbonate (2PbCO3-Pb(OH)2) be sufficiently mixed be dissolved in concentration be 8wt% nitric acid in, obtain
Than surface it is 165m by 1.0L to maceration extract 400ml2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst contains through icp analysis, Co
Measure as 8.60g/L, Ce contents 3.40g/L, Pb content 3.10g/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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 59.07%, and selectivity is 81.02%, 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 10】
The preparation of carbonylating catalyst：By Co containing 8.60g, the CoCl containing 3.40gCe and containing 3.10gNa2·6H2O、Ce
(NO3)3·6H2O and Na2O, which is sufficiently mixed, to be dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 165m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.For the carbonylating catalyst through icp analysis, Co contents are 8.60g/L, Ce contents 3.40g/
L, Na content 3.10g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 81.11%, 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 Co containing 8.60g, the CoCl containing 3.40gCe and containing 3.10gK2·6H2O、
CeCl3·6H2O and K2SO4It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 165m by 1.0L2/ g, hole
Hold for 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.For the carbonylating catalyst through icp analysis, Co contents are 8.60g/L, Ce contents 3.40g/L, K content 3.10g/
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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 81.17%, 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 Co containing 8.60g, the CoCl containing 3.40gSm and containing 3.10gLi2·6H2O、
SmCl3·6H2O and LiCl, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 165m by 1.0L2/ g, hole
Hold for 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.For the carbonylating catalyst through icp analysis, Co contents are 8.60g/L, Sm contents 3.40g/L, Li content 3.10g/
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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 81.21%, 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 Co containing 8.60g, the CoCl containing 3.40gSm and containing 3.10gCs2·6H2O、
SmCl3·6H2O and CsOAc, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 165m by 1.0L2/ g,
Pore volume is 0.95, 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 8.60g/L, Sm contents 3.40g/L, Cs content
3.10g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 58.26%, and selectivity is 81.34%, 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 Co containing 8.60g, containing 3.40gY, containing 1.80gSn and containing 1.30gRb's
CoCl2·6H2O、Y(NO3)3·6H2O、SnCl2·2H2O and RbNO3It 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 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst contains through icp analysis, Co
Measure as 8.60g/L, Y contents 3.40g/L, Sn content 1.80g/L, Rb content 1.30g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 59.49%, and selectivity is 82.53%, 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 present embodiment is compared with embodiment 1, embodiment 2 as can be seen that IIIB metals Y and alkali metal Rb is improving acetic acid second
The yield and selectivity of alkene have preferably synergy.
【Embodiment 15】
The preparation of carbonylating catalyst：By Co containing 8.60g, containing 3.40gY, containing 1.80gPb and containing 1.30gRb's
CoCl2·6H2O、Y(NO3)3·6H2O、Pb(NO3)2·3H2O and RbNO3It is sufficiently mixed and is dissolved in pure water, obtains maceration extract
400ml, than surface it is 165m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is through icp analysis, Co contents
8.60g/L, Y content 3.40g/L, Pb content 1.80g/L, Rb content 1.30g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 59.56%, and selectivity is 82.46%, 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 16】
The preparation of carbonylating catalyst：To contain 8.60g Co, containing 3.40gY, containing 0.70gSn, containing 1.10gPb and contain
1.30gRb CoCl2·6H2O、Y(NO3)3·6H2O、SnCl2·2H2O、Pb(NO3)2·3H2O and RbNO3It is sufficiently mixed dissolving
In the hydrochloric acid that concentration is 8wt%, maceration extract 400ml is obtained, than surface is 165m by 1.0L2/ g, pore volume 0.95 are 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
For base catalyst through icp analysis, Co contents are 8.60g/L, Y contents 3.40g/L, Sn content 0.70g/L, Pb content 1.10g/L,
Rb contents 1.30g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 60.96%, 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.
The present embodiment is compared with embodiment 14, embodiment 15 as can be seen that IVA metal Sn and Pb is other living with the present invention
Property component improve vinyl acetate yield and selectivity have preferably synergy.
【Embodiment 17】
The preparation of carbonylating catalyst：To contain 8.60g Co, containing 3.40gSm, containing 0.70gSn, containing 1.10gPb and contain
1.30gRb CoCl2·6H2O、SmCl3·6H2O、SnCl2·2H2O、Pb(NO3)2·3H2O and RbNO3It is sufficiently mixed and is dissolved in
Concentration is in 8wt% hydrochloric acid, obtains maceration extract 400ml, than surface is 165m by 1.0L2/ g, pore volume 0.95 are 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
For base catalyst through icp analysis, Co contents are 8.60g/L, Sm contents 3.40g/L, Sn content 0.70g/L, Pb content 1.10g/
L, Rb content 1.30g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 61.04%, and selectivity is 83.79%, 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 18】
The preparation of carbonylating catalyst：To contain 8.60g Co, containing 2.13gY, containing 1.27gSm, containing 0.70gSn, contain
The 1.10gPb and CoCl containing 1.30gRb2·6H2O、Y(NO3)3·6H2O、SmCl3·6H2O、SnCl2·2H2O、Pb(NO3)2·
3H2O and RbNO3It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
165m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Co contents are 8.60g/L, Y contents 2.13g/L, and Sm contains
Measure 1.27g/L, Sn contents 0.70g/L, Pb content 1.10g/L, Rb content 1.30g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 62.47%, and selectivity is 84.55%, 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 present embodiment can be seen that Y, Sm and its in the present invention in IIIB metals compared with embodiment 16, embodiment 17
The favourable selectivity and yield for improving vinyl acetate of its active component collaboration, illustrates Co, Y, Sm, Sn, Pb and Rb active component
Between exist well synergy.
【Embodiment 19】
The preparation of carbonylating catalyst：To contain 8.60g Ni, containing 2.13gY, containing 1.27gSm, containing 0.70gSn, contain
The 1.10gPb and NiCl containing 1.30gRb2·6H2O、Y(NO3)3·6H2O、SmCl3·6H2O、SnCl2·2H2O、Pb(NO3)2·
3H2O and RbNO3It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
165m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.For the carbonylating catalyst through icp analysis, Ni contents are 8.60g/L, Y contents 2.13g/L, and Sm contains
Measure 1.27g/L, Sn contents 0.70g/L, Pb content 1.10g/L, Rb content 1.30g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 62.36%, and selectivity is 84.71%, 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 20】
The preparation of carbonylating catalyst：To contain 5.70g Co, Ni containing 2.90g, containing 2.13gY, containing 1.27gSm, contain
0.70gSn, the CoCl containing 1.10gPb and containing 1.30gRb2·6H2O、NiCl2·6H2O、Y(NO3)3·6H2O、SmCl3·6H2O、
SnCl2·2H2O、Pb(NO3)2·3H2O and RbNO3It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract
400ml, than surface it is 165m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is through icp analysis, Co contents
5.70g/L, Ni content are 2.90/L, Y contents 2.13g/L, Sm content 1.27g/L, Sn content 0.70g/L, Pb content 1.10g/
L, Rb content 1.30g/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 7.2MPa
Temperature is 180 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 7.0h, 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 0.35MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 146 DEG C, after sustained response 50min, 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 63.74%, and selectivity is 86.34%, 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 present embodiment can be seen that Co, Ni and its in the present invention in iron series element compared with embodiment 18, embodiment 19
The favourable selectivity and yield for improving vinyl acetate of its active component collaboration, illustrates Co, Ni, Y, Sm, Sn, Pb and Rb activearm
/ presence acts synergistically well.
Table 1
Table 2
Claims (8)
1. the method for methyl acetate hydroformylation synthesizing vinyl acetate, comprises the following steps：(1) with methyl acetate, carbon monoxide
It is raw material with hydrogen, carbonylation is carried out in the presence of carbonylating catalyst, co-catalyst and obtains ethylidene diacetate；(2)
In the presence of catalyst for cracking, ethylidene diacetate cracking is set to obtain vinyl acetate；Wherein, the carbonylating catalyst uses
SiO2、Al2O3Or its mixture is carrier, active component include at least one selected from iron series element, selected from IIIB elements extremely
Rubidium at least one of few a kind of and the tin in IVA and lead and alkali metal；The co-catalyst is iodide.
2. the method for methyl acetate hydroformylation synthesizing vinyl acetate according to claim 1, it is characterised in that the iron system
Element is selected from least one of iron, cobalt and nickel.
3. the method for methyl acetate hydroformylation synthesizing vinyl acetate according to claim 1, it is characterised in that the IIIB
Element is selected from least one of scandium, yttrium, lanthanum, cerium and samarium.
4. the method for methyl acetate hydroformylation synthesizing vinyl acetate according to claim 1, it is characterised in that in catalyst
The content of iron series element is 3.00~15.00g/L, and the content of IIIB elements is 0.10~5.00g/L.
5. the method for methyl acetate hydroformylation synthesizing vinyl acetate according to claim 1, it is characterised in that in catalyst
At least one content of the metal in IVA and alkali metal is 0.50~8.00g/L.
6. the method for methyl acetate hydroformylation synthesizing vinyl acetate according to claim 1, it is characterised in that the iodate
Thing is iodomethane.
7. the method for methyl acetate hydroformylation synthesizing vinyl acetate according to claim 1, it is characterised in that the carbonyl
The temperature for changing reaction is 130~200 DEG C；The pressure of reaction is 3.0~10.0MPa；Carbon monoxide and hydrogen volume ratio in reaction
For 0.10~10.0；The time of reaction is 3.0~10.0h.
8. the method for methyl acetate hydroformylation synthesizing vinyl acetate according to claim 1, it is characterised in that carbonylation is anti-
The preparation method of catalyst is answered, is comprised the following steps：
1. by the composition of catalyst by the change of metal in the compound of iron series element, the compound of IIIB elements, IVA and alkali metal
The solution of compound mixes 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 |
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2014
- 2014-10-24 CN CN201410573622.3A patent/CN105523929B/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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