CN105585487B - The synthetic method of vinyl acetate - Google Patents
The synthetic method of vinyl acetate Download PDFInfo
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Abstract
The present invention relates to the synthetic method of 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 synthetic method of 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 platinum cluster metal, the technical scheme selected from VIB at least one and selected from least one of IB and lanthanide element 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 synthetic method of 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.
It is (entitled via US4,429,150 by the preparation method of methyl acetate synthesis ethylidene diacetate：
Manufacture of ethylidene diacetate) it is disclosed, i.e., with methyl acetate or methyl ether, carbon monoxide and hydrogen
For raw material, catalyst is using the sub- second of the double acetic acid of synthesis in the presence of VIII halide or acetate and phosphorous polar solvent
Ester.US5,354,886 is (entitled：Catalysts on inorganic carriers for producing
Ethylidene diacetate) mention RhCl3Or rhodium compound is supported on diatomite, titanium oxide, magnesia, aluminum oxide
With loaded catalyst is made on zinc oxide.Using methyl acetate, carbon monoxide and hydrogen as raw material, under polar solvent conditions,
The reaction synthesis ethylidene diacetate under above-mentioned catalyst.There are double vinegar during ethylidene diacetate is prepared in the above method
The problem of sour ethyl 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
Vinyl acetate synthetic method, this method have vinyl acetate high income and selectivity it is high the characteristics of.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The synthetic method of vinyl acetate, including
Following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, carry out being carbonylated instead in the presence of carbonylating catalyst
Ethylidene diacetate should be obtained；(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 is included selected from platinum cluster metal extremely
Lack one kind, selected from VIB at least one and selected from least one of IB and lanthanide element metallic element.It is preferred that described
Active component is simultaneously including platinum cluster metallic element, vib metal element, selected from least one of IB metallic elements and selected from group of the lanthanides
At least one of metal metallic element.Now acetic acid second is being improved between IB metallic element and the metallic element of lanthanide series metal
There is synergy in terms of the selectivity and yield of alkene.
In above-mentioned technical proposal, the platinum cluster metallic element preferably is selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium.
In above-mentioned technical proposal, the vib metal element preferably is selected from least one of chromium, molybdenum and tungsten.
In above-mentioned technical proposal, the IB metals preferably are selected from least one of copper, silver and gold.
In above-mentioned technical proposal, the lanthanide series metal preferably is selected from least one of lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component simultaneously including platinum cluster metallic element,
Vib metal element, IB metals and lanthanide series metal；Such as described active component, which is embraced, includes rhodium, chromium, copper (or gold) and lanthanum, or embraces and include
Rhodium, chromium (or molybdenum), copper, gold and lanthanum, either embrace include rhodium, chromium, molybdenum, copper, gold, lanthanum (or cerium) or embrace include rhodium, chromium, molybdenum, copper, gold,
Lanthanum and cerium.
In above-mentioned technical proposal, in the carbonylating catalyst content of platinum cluster metallic element be preferably 3.00~
15.00g/L, more preferably 5.00~10.00g/L；The content of vib metal element is preferably 0.10 in the carbonylating catalyst
~5.00g/L, more preferably 1.00~4.00g/L；Metal is extremely in IB and lanthanide series in the carbonylating catalyst
A kind of few content is preferably 0.50~8.00g/L, more preferably 1.00~5.00g/L.Load used in the carbonylating catalyst
Surface area per unit volume is preferably 50~300m2/ g, more preferably 150~200m2/ g, pore volume is preferably 0.80~1.20, more preferably
0.90~1.00.Iodide described in above-mentioned technical proposal are preferably iodomethane.
In above-mentioned technical proposal, the adoptable preparation method of carbonylating catalyst comprises the following steps：
1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of vib metal element, IB metals and lanthanum
It is that the solution of the compound of metal is mixed with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. platinum cluster metal preferably is selected from radium chloride, the part of rhodium acetate two, three
Phenylphosphine chlorine rhodium, rhodium nitrate, palladium bichloride, the ammonia palladium of dichloro four, palladium, ammonium chloropalladite, ruthenic chloride, cross ruthenic acid four in amine, two
At least one of platinum chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid.The step 1. VIB
The compound of metallic element preferably is selected from chromium chloride, chromic nitrate, chromic acetate, molybdenum chloride, ammonium molybdate, ammonium tungstate and ammonium paratungstate
It is at least one.1. the IB metallic compounds preferably are selected from basic copper carbonate, copper citrate, copper chloride, silver ammino solution, trifluoro to step
At least one of silver acetate, gold chloride and tetra chlorauric acid ammonium.1. the lanthanide metals compound preferably is selected from acetic acid to step
Lanthanum, lanthanum chloride, lanthanum nitrate, cerous acetate, cerium chloride, cerous nitrate, praseodymium acetate, praseodymium chloride, acetic acid neodymium, samarium trichloride, ytterbium chloride and chlorine
Change at least one of lutetium.2. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~120 DEG C.
In above-mentioned technical proposal, by the composition of catalyst by the compound including platinum cluster metallic element, vib metal element
Compound, the compound of IB metals and lanthanide series metal and carrier hybrid mode are not particularly limited, their aqueous solution and carrier
The opportunity of contact is also not particularly limited.For example the present invention can pressed to the composition of catalyst by including platinum cluster metallic element
Compound, the compound of vib metal element, the compound of IB metals and lanthanide series metal first mix be dissolved in water or by it
Compound sequentially form to be mixed after the aqueous solution and contacted again with carrier, can be contacted with different order with carrier and obtain institute
State catalyst.
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 platinum cluster metallic element of amount, vib metal element and selected from least one of IB and lanthanide metals metallic element, are conducive to
The activity and stability of catalyst are improved, 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 83.48%, taken up to 60.30%
Preferable technique effect was obtained, active component is simultaneously including platinum cluster metal, vib metal member in especially described carbonylating catalyst
Element, selected from least one of IB metallic elements and selected from least one of lanthanide series metal metallic element when, achieve 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：RhCl by Rh containing 6.20g, containing 3.00gCr and containing 3.10gCu3·3H2O、
CrCl3·6H2O and copper citrate (Cu2C6H4O7·2.5H2O) it is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains
Maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation is upper
State in maceration extract, stand 2h in 100 DEG C of dryings, obtain the catalyst.The carbonylating catalyst is through icp analysis, Rh contents
For 6.20g/L, Cr contents 3.00g/L, Cu 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, 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 7.2MPa, 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 142 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 60.30%, and selectivity is 83.48%, 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：RhCl by Rh containing 6.20g, containing 3.00gCr and containing 3.10gLa3·3H2O、
CrCl3·6H2O and La (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume is 0.95, 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 Rh contents are 6.20g/L, Cr contents 3.00g/L, La
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, 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 7.2MPa, 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 142 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 60.24%, and selectivity is 83.55%, 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 Rh containing 6.20g and the RhCl containing 3.00gCr3·3H2O and CrCl3·6H2O fills
Point mixed dissolution obtains maceration extract 400ml in pure water, 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, obtains the catalyst in above-mentioned maceration extract.The carbonyl
Base catalyst is through icp analysis, and Rh contents are 6.20g/L, Cr contents 3.00g/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 7.2MPa, 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 142 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 51.13%, and selectivity is 82.71%, 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 Rh, Cr and Cu work
Property component, while the catalyst performance ratio containing Rh, Cr and La active component will be more containing only the performance of Rh, Cr active constituent catalyst
Excellent, the selectivity and yield of vinyl acetate will be high.
【Embodiment 3】
The preparation of carbonylating catalyst：Triphenylphosphine chlorine rhodium by Rh containing 5.00g, containing the 1.00gCr and Cu containing 1.00g
(C54H45ClP3Rh)、Cr(NO3)3·9H2O and CuCl2It is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, is impregnated
Liquid 400ml, by 1.0L than surface be 150m2/ g, pore volume is 0.90, a diameter of 5.6mm spherical Al2O3Carrier impregnation is above-mentioned
In maceration extract, 2h is stood in 80 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, Rh contents
5.00g/L, Cr content 1.00g/L, Cu 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 7.2MPa, 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 142 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 59.58%, and selectivity is 82.71%, 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 the part of rhodium acetate two containing 10.00gRh, containing 4.00gCr and containing 5.00gAg
(Rh2(OAc)4)、Cr(OAc)3·6H2O and silver ammino solution ([Ag (NH3)2] OH) be sufficiently mixed and be dissolved in pure water, 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, Rh contents
10.00g/L, Cr content 4.00g/L, Ag 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 7.2MPa, 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 142 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 60.61%, and selectivity is 83.40%, 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 5】
The preparation of carbonylating catalyst：Rh (NO by Rh containing 6.20g, containing the 3.00gMo and Ag containing 3.10g3)3, ammonium molybdate
((NH4)6Mo7O24·4H2) and silver trifluoroacetate (C O2F3O2Ag) it is sufficiently mixed and is dissolved in pure water, obtains maceration extract 400ml,
By 1.0L than surface be 165m2/ g, pore volume is 0.95, 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, and Rh contents are 6.20g/L, Mo
Content 3.00g/L, Ag 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, 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 7.2MPa, 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 142 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 60.32%, and selectivity is 83.44%, 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 PdCl containing 6.20gPd, containing 3.00gMo and containing 3.10gAu2, molybdic acid
(H2MoO4) and gold chloride (HAuCl4) be sufficiently mixed be dissolved in concentration be 8wt% hydrochloric acid in, obtain maceration extract 400ml, will
1.0L is 165m than surface2/ g, pore volume is 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, the catalyst is obtained.The carbonylating catalyst is 6.20g/L through icp analysis, Pd contents, and Mo contains
Measure 3.00g/L, Au 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, 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 7.2MPa, 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 142 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 60.14%, and selectivity is 83.10%, 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 the ammonia palladium (Pd of dichloro four containing 6.20gPd, containing 3.00gW and containing 3.10gAu
(NH3)4Cl2·H2O), ammonium tungstate ((NH4)10W12O41·4H2) and tetra chlorauric acid ammonium (NH O4AuCl4·2H2O) it is sufficiently mixed molten
Solution obtains maceration extract 400ml in hot water, by 1.0L than surface be 165m2/ g, pore volume is 0.95, and a diameter of 5.6mm's is spherical
SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonylating catalyst
Through icp analysis, Pd contents are 6.20g/L, W content 3.00g/L, Au 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, 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 7.2MPa, 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 142 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 60.09%, and selectivity is 83.04%, 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 the Pd (OAc) containing 6.20gPd, W containing 3.00g and containing 3.10gSm2, para-tungstic acid
Ammonium ((NH4)10H2(W2O7)6) and SmCl3·6H2O, 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 165m2/ g, pore volume is 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, the catalyst is obtained.The carbonylating catalyst is through icp analysis, Pd contents
6.20g/L, W content 3.00g/L, Sm 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, 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 142 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 56.65%, and selectivity is 79.97%, 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 the RuCl containing 6.20gRu, Cr containing 3.00g and the Ce containing 3.10g3·XH2O、
CrCl3·6H2O and CeCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume is 0.95, 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 Ru contents are 6.20g/L, Cr contents 3.00g/L, Ce
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, 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 142 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 60.27%, and selectivity is 82.82%, 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 the ammonium chloroplatinite ((NH containing 6.20gPt, containing 3.00gCr and containing 3.10gPr4)2PtCl4)、CrCl3·6H2O and Cl3Pr·6H2O, 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 0.95, 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 Pt contents are 6.20g/L, Cr contents 3.00g/
L, Pr 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, 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 7.2MPa, 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 142 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 60.13%, and selectivity is 83.11%, 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 11】
The preparation of carbonylating catalyst：By the OsCl containing 6.20gOs, containing 3.00gCr and containing 3.10gNd3·3H2O、
CrCl3·6H2O and Nd (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume is 0.95, 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 Os contents are 6.20g/L, Cr contents 3.00g/L, Nd
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, 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 7.2MPa, 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 142 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 60.19%, and selectivity is 83.17%, 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 the IrCl containing 6.20gIr, containing 3.00gCr and containing 3.10gYb3·XH2O、
CrCl3·6H2O and YbCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume is 0.95, 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 Ir contents are 6.20g/L, Cr contents 3.00g/L, Yb
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, 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 7.2MPa, 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 142 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 60.17%, and selectivity is 83.20%, 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 the RhCl containing 6.20gRh, containing 3.00gCr and containing 3.10gLu3·3H2O、
CrCl3·6H2O and LuCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume is 0.95, 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 Rh contents are 6.20g/L, Cr contents 3.00g/L, Lu
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, 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 7.2MPa, 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 142 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 60.30%, and selectivity is 83.37%, 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 14】
The preparation of carbonylating catalyst：By Rh containing 6.20g, containing 3.00gCr, containing 1.49gCu and containing 1.61gLa's
RhCl3·3H2O、CrCl3·6H2O, copper citrate (Cu2C6H4O7·2.5H2) and La (OAc) O3·5H2O, which is sufficiently mixed, to be dissolved in
Concentration for 8wt% hydrochloric acid in, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.95, 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 Rh contents are 6.20g/L, Cr contents 3.00g/L, Cu content 1.49g/L, La content 1.61g/
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 7.2MPa, 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 142 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 61.22%, and selectivity is 84.56%, 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 IB Ni metals and lanthanide series metal La are improving acetic acid
The yield and selectivity aspect of ethene have preferably synergy.
【Embodiment 15】
The preparation of carbonylating catalyst：By Rh containing 6.20g, containing 3.00gCr, containing 1.49gAu and containing 1.61gLa's
RhCl3·3H2O、CrCl3·6H2O, tetra chlorauric acid ammonium (NH4AuCl4·2H2) and La (OAc) O3·5H2O, which is sufficiently mixed, to be dissolved in
In pure water, obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.95, a diameter of 5.6mm spherical SiO2
Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonylating catalyst is through ICP
Analysis, Rh contents are 6.20g/L, Cr contents 3.00g/L, Au content 1.49g/L, La content 1.61g/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 7.2MPa, 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 142 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 61.34%, and selectivity is 84.51%, 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 16】
The preparation of carbonylating catalyst：6.20g Rh will be contained, containing 3.00gCr, containing 0.74gCu, containing 0.75gAu and contained
1.61gLa RhCl3·3H2O、CrCl3·6H2O, copper citrate (Cu2C6H4O7·2.5H2O), tetra chlorauric acid ammonium
(NH4AuCl4·2H2) and La (OAc) O3·5H2O, which is sufficiently mixed, to be dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract
400ml, by 1.0L than surface be 165m2/ g, pore volume is 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, the catalyst is obtained.The carbonylating catalyst is through icp analysis, Rh contents
6.20g/L, Cr content 3.00g/L, Cu content 0.74g/L, Au content 0.75g/L, La content 1.61g/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 7.2MPa, 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 142 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 62.86%, 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.
The present embodiment is compared with embodiment 14, embodiment 15 as can be seen that IB Ni metals and Au and the present invention are other living
Property component improve vinyl acetate yield and selectivity in terms of have preferably synergy.
【Embodiment 17】
The preparation of carbonylating catalyst：6.20g Rh will be contained, containing 3.00gMo, containing 0.74gCu, containing 0.75gAu and contained
1.61gLa RhCl3·3H2O, ammonium molybdate ((NH4)6Mo7O24·4H2O), copper citrate (Cu2C6H4O7·2.5H2O), tetrachloro
Auric acid ammonium (NH4AuCl4·2H2) and La (OAc) O3·5H2O, which is sufficiently mixed, to be dissolved in the hydrochloric acid that concentration is 8wt%, is soaked
Stain liquid 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation is above-mentioned
In maceration extract, 2h is stood in 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is through icp analysis, Rh contents
6.20g/L, Mo content 3.00g/L, Cu content 0.74g/L, Au content 0.75g/L, La content 1.61g/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 7.2MPa, 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 142 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 62.92%, and selectivity is 85.66%, 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 18】
The preparation of carbonylating catalyst：To contain 6.20g Rh, containing 1.56gCr, containing 1.44gMo, containing 0.74gCu, contain
The 0.75gAu and RhCl containing 1.61gLa3·3H2O、CrCl3·6H2O, ammonium molybdate ((NH4)6Mo7O24·4H2O), copper citrate
(Cu2C6H4O7·2.5H2O), tetra chlorauric acid ammonium (NH4AuCl4·2H2) and La (OAc) O3·5H2O, which is sufficiently mixed, is dissolved in concentration
In 8wt% hydrochloric acid, to obtain maceration extract 400ml, by 1.0L than surface be 165m2/ g, pore volume is 0.95, 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 carbonylation
Catalyst is through icp analysis, and Rh contents are 6.20g/L, Cr contents 1.56g/L, Mo content 1.44g/L, Cu content 0.74g/L, Au
Content 0.75g/L, La content 1.61g/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 7.2MPa, 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 142 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 63.49%, and selectivity is 86.83%, 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.
The present embodiment can be seen that Cr, Mo and its in the present invention in vib metal compared with embodiment 16, embodiment 17
The favourable selectivity and yield for improving vinyl acetate of its active component collaboration, illustrates Rh, Cr, Mo, Cu, Au and LaActive component
Between exist well synergy.
【Embodiment 19】
The preparation of carbonylating catalyst：To contain 6.20g Rh, containing 1.56gCr, containing 1.44gMo, containing 0.74gCu, contain
The 0.75gAu and RhCl containing 1.61gCe3·3H2O、CrCl3·6H2O, ammonium molybdate ((NH4)6Mo7O24·4H2O), copper citrate
(Cu2C6H4O7·2.5H2O), tetra chlorauric acid ammonium (NH4AuCl4·2H2) and CeCl O3·6H2O, 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 0.95, 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 Rh contents are 6.20g/L, Cr contents 1.56g/L, Mo content 1.44g/L, Cu content 0.74g/L, and Au contains
Measure 0.75g/L, Ce contents 1.61g/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 7.2MPa, 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 142 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 63.51%, and selectivity is 86.77%, 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 20】
The preparation of carbonylating catalyst：To contain 6.20g Rh, containing 1.56gCr, containing 1.44gMo, containing 0.74gCu, contain
0.75gAu, the RhCl containing 0.80gLa and containing 0.81gCe3·3H2O、CrCl3·6H2O, ammonium molybdate ((NH4)6Mo7O24·
4H2O), copper citrate (Cu2C6H4O7·2.5H2O), tetra chlorauric acid ammonium (NH4AuCl4·2H2O)、La(OAc)3·5H2O and
CeCl3·6H2O, which is sufficiently mixed, to be dissolved in the hydrochloric acid that concentration is 8wt%, is obtained maceration extract 400ml, is than surface by 1.0L
165m2/ g, pore volume is 0.95, 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 Rh contents are 6.20g/L, Cr contents 1.56g/L, Mo
Content 1.44g/L, Cu content 0.74g/L, Au content 0.75g/L, La content 0.80g/L, Ce content 0.81g/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 7.2MPa, 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 142 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 64.47%, and selectivity is 87.74%, 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 can be seen that Ce, La and its in the present invention in lanthanide series metal compared with embodiment 18, embodiment 19
The favourable selectivity and yield for improving vinyl acetate of its active component collaboration, illustrates Rh, Cr, Mo, Cu, Au, La and Ce activity
There is synergy well between component.
Table 1
Table 2
Claims (9)
1. the synthetic method of vinyl acetate, comprises the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, in carbonyl
Carbonylation is carried out in the presence of base catalyst, co-catalyst and obtains ethylidene diacetate；(2) exist in catalyst for cracking
Under, ethylidene diacetate cracking is obtained vinyl acetate；Wherein, the carbonylating catalyst uses SiO2、Al2O3Or it is mixed
Compound is carrier, active component includes selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium, selected from VIB it is at least one, with
And selected from least one of IB and selected from least one of lanthanide element metallic element；The co-catalyst is iodate
Thing.
2. the synthetic method of vinyl acetate according to claim 1, it is characterised in that the vib metal is selected from chromium, molybdenum and tungsten
At least one of.
3. the synthetic method of vinyl acetate according to claim 1, it is characterised in that the IB metals are in copper, silver and gold
At least one.
4. the synthetic method of vinyl acetate according to claim 1, it is characterised in that the lanthanide element be selected from lanthanum,
At least one of cerium, praseodymium, neodymium, samarium, ytterbium and lutetium.
5. the synthetic method of vinyl acetate according to claim 1, it is characterised in that the content of platinum cluster metal is in catalyst
3.00~15.00g/L, the content of vib metal element is 0.10~5.00g/L.
6. the synthetic method of vinyl acetate according to claim 1, it is characterised in that described in catalyst selected from IB metals and
At least one of lanthanide series metal content is 0.50~8.00g/L.
7. the synthetic method of vinyl acetate according to claim 1, it is characterised in that the iodide are iodomethane.
8. the synthetic method of vinyl acetate according to claim 1, it is characterised in that the temperature of the carbonylation is 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；Reaction
Time be 3.0~10.0h.
9. the synthetic method of vinyl acetate according to claim 1, it is characterised in that the preparation side of carbonylation reaction catalyst
Method, comprises the following steps：
1. it is by the composition of catalyst that the compound of platinum cluster metallic element, the compound of vib metal element, IB metals and group of the lanthanides is golden
The solution of the compound of category is mixed with carrier；
2. dry.
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|---|---|---|---|---|
| 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 CN201410573565.9A patent/CN105585487B/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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3976249A4 (en) * | 2019-05-28 | 2023-06-14 | Enerkem Inc. | Vapor phase methanol carbonylation catalyst |
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