CN105585494B - The method of methyl acetate carbonylation production vinyl acetate - Google Patents
The method of methyl acetate carbonylation production vinyl acetate Download PDFInfo
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Abstract
The present invention relates to the method that production vinyl acetate is carbonylated in methyl 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.The method of production vinyl acetate is carbonylated by using methyl acetate, comprises 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 alkaline-earth metal at least one and selected from least one of IVA 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 method that production vinyl acetate is carbonylated in methyl 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 carbonylation production vinyl acetate 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：Methyl acetate carbonylation production acetic acid
The method of ethene, comprises the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, exist in carbonylating catalyst
Lower progress carbonylation obtains ethylidene diacetate；(2) in the presence of catalyst for cracking, obtain ethylidene diacetate cracking
Vinyl acetate；Wherein, the carbonylating catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes choosing
From platinum cluster metal is at least one, at least one selected from alkali earth metal and in IVA and lanthanide element extremely
A kind of few metallic element.It is preferred that the active component simultaneously including platinum cluster metal, alkali earth metal, in IVA at least
A kind of metallic element and selected from least one of lanthanide element metallic element.Now IVA metallic element and group of the lanthanides gold
There is synergy between the metallic element of category in terms of the selectivity of vinyl acetate and yield is improved.
In above-mentioned technical proposal, the platinum cluster metal preferably is selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium.
In above-mentioned technical proposal, the alkali earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.
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 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 is simultaneously including platinum cluster metal, alkaline earth
Metallic element, IVA metals and lanthanide series metal；Such as the active component includes rhodium, strontium, tin (or lead) and lanthanum, or embrace include rhodium,
Strontium (or beryllium), tin, lead and lanthanum, either embrace include rhodium, strontium, beryllium, tin, lead, lanthanum (or cerium) or embrace include rhodium, strontium, beryllium, tin, lead, 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 alkali earth metal is preferably in the carbonylating catalyst
0.10~5.00g/L, more preferably 1.00~3.00g/L；In the carbonylating catalyst in IVA and lanthanide series metal metal
At least one constituent content be preferably 0.50~8.00g/L, more preferably 1.00~5.00g/L.The carbonylating catalyst
Load surface area per unit volume used is preferably 50~300m2/ g, more preferably 150~200m2/ g, pore volume are 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, comprise the following steps：
1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of alkali earth metal, IVA and group of the lanthanides
The solution of the compound of metal mixes with carrier in metal；
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, excessively ruthenic chloride, amine, two in ruthenic acid four
At least one of platinum chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid.The step 1. alkaline earth
Metallic compound preferably be selected from alkaline earth oxide, alkaline earth metal chloride, alkaline earth nitrate, alkali earth metal sulfate and
At least one of Alkaline Earth Metal Acetate.It is sub- that the compound of step 1. IVA metallic elements preferably is selected from germanium chloride, oxalic acid
At least one of tin, stannous chloride, lead acetate, plumbi nitras and basic lead acetate.The step 1. lanthanide metals chemical combination
Thing preferably is selected from lanthanum acetate, lanthanum chloride, lanthanum nitrate, cerous acetate, cerium chloride, cerous nitrate, praseodymium acetate, praseodymium chloride, acetic acid neodymium, chlorination
At least one of samarium, ytterbium chloride and lutecium chloride.2. the drying temperature is preferably 80~120 DEG C to step, more preferably 100~
120℃。
In above-mentioned technical proposal, by the composition of catalyst by the compound including platinum cluster metallic element, alkali earth metal
Compound, the compound of metal and carrier hybrid mode are not particularly limited in IVA and lanthanide series metal, their aqueous solution with
The opportunity of carrier contact is also not particularly limited.Such as the present invention will can included platinum cluster metal member by the composition of catalyst
The compound of metal, which first mixes, in the compound of element, the compound of alkali earth metal, IVA and lanthanide series metal is dissolved in water, also may be used
To be to sequentially form to be mixed after the aqueous solution by their compound to contact with carrier again, can be connect with different order and carrier
Touch and obtain the 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 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 platinum cluster metal of amount, alkali earth metal and selected from least one of IVA and lanthanide series metal metallic element, are advantageous to improve master
The activity and stability of catalyst, so as to improve the yield of vinyl acetate and selectivity.
Test result indicates that the vinyl acetate yield prepared by the present invention selectively reaches 83.23%, taken up to 60.32%
Preferable technique effect was obtained, active component is simultaneously including platinum cluster metal, alkaline-earth metal in especially described carbonylating catalyst
Element, selected from least one of IVA metallic elements and selected from least one of lanthanide series metal metallic element when, achieve more
Add prominent technique effect, 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 Rh containing 6.10g, the part of rhodium acetate two containing 2.90gSr and containing 2.90gSn
(Rh2(OAc)4)、Sr(OAc)2·0.5H2O and stannous oxalate (SnC2O4) it is sufficiently mixed the hydrochloric acid for being dissolved in that concentration is 8wt%
In, maceration extract 400ml is obtained, than surface is 165m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier
It is immersed in above-mentioned maceration extract, stands 2h in 100 DEG C of dryings, obtain the catalyst.The carbonylating catalyst is through ICP points
Analysis, Rh contents are 6.10g/L, Sr contents 2.90g/L, Sn content 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.32%, and selectivity is 83.23%, 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 Rh containing 6.10g, the part of rhodium acetate two containing 2.90gSr and containing 2.90gLa
(Rh2(OAc)4)、Sr(OAc)2·0.5H2O and La (OAc)3·5H2O, which is sufficiently mixed, to be 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, Rh contents
6.10g/L, Sr content 2.90g/L, La content 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.29%, and selectivity is 83.34%, 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.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of carbonylating catalyst：By Rh containing 6.10g and the part (Rh of the rhodium acetate containing 2.90gSr two2(OAc)4) and
Sr(OAc)2·0.5H2O, 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, Rh contents are 6.10g/L, Sr contents 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 51.16%, and selectivity is 72.44%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Rh, Sr and Sn work
Property component while catalyst performance ratio containing Rh, Sr and La active component will be more containing only the performance of Rh, Sr active constituent catalyst
Excellent, the selectivity and yield of vinyl acetate will be high.
【Embodiment 3】
The preparation of carbonylating catalyst：By Rh containing 5.00g, Ba containing 1.00g and RhCl containing 1.00gGe3·6H2O、
BaCl2And GeCl4It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
150m2/ g, pore volume 0.90, a diameter of 5.6mm spherical Al2O3It is dry in 80 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, Rh contents are 5.00g/L, Ba 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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 59.66%, and selectivity is 82.96%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 4】
The preparation of carbonylating catalyst：By the triphenylphosphine chlorine rhodium containing 10.00gRh, containing 3.00gCa and containing 5.00gSn
(C54H45ClP3Rh)、Ca(NO3)2And SnCl2It is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, obtains maceration extract
400ml, than surface it is 200m by 1.0L2/ g, pore volume 1.00, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 120 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is through icp analysis, Rh contents
10.00g/L, Ca content 3.00g/L, Sn content 5.00g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then pass to carbon monoxide and
Hydrogen improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control reaction until pressure 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.67%, and selectivity is 83.39%, 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 Rh containing 6.10g, the Rh (NO containing 2.90gMg and containing 2.90gSn3)3、MgSO4With
Sn(NO3)2It is sufficiently mixed and is dissolved in water outlet, obtain maceration extract 400ml, than surface is 165m by 1.0L2/ g, pore volume 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.
For the carbonylating catalyst through icp analysis, Rh contents are 6.10g/L, Mg contents 2.90g/L, Sn content 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.31%, and selectivity is 83.24%, 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 PdCl containing 6.10gPd, containing 2.90gBe and containing 2.90gPb2, BeO and Pb
(OAc)2·3H2O, 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 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, Pd contents are 6.10g/L, Be contents 2.90g/L, Pb
Content 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.07%, and selectivity is 83.03%, 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.
【Embodiment 7】
The preparation of carbonylating catalyst：By the ammonia palladium (Pd of dichloro four containing 6.10gPd, Be containing 2.90g and containing 2.90gPb
(NH3)4Cl2·H2O)、BeCl2With basic lead acetate (Pb (OAc)2·2Pb(OH)2) be sufficiently mixed and be dissolved in pure water, obtain
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 upper
State in maceration extract, stand 2h in 100 DEG C of dryings, obtain the catalyst.The carbonylating catalyst is through icp analysis, Pd contents
For 6.10g/L, Be contents 2.90g/L, Pb content 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.05%, and selectivity is 83.08%, 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 Pd (OAc) containing 6.10gPd, Be containing 2.90g and containing 2.90gSm2、BeCl2With
SmCl3·6H2O, which is sufficiently mixed, to be dissolved in the acetic acid that concentration is 10wt%, is obtained 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, Pd contents are 6.10g/L, Be contents 2.90g/L, Sm
Content 2.90g/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 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 141 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 56.84%, and selectivity is 80.15%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 9】
The preparation of carbonylating catalyst：By the RuCl containing 6.10gRu, Be containing 2.90g and the Ce containing 2.90g3·XH2O、
BeCl2And CeCl3·6H2O, 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 Ru contents are 6.10g/L, Be contents 2.90g/L, Ce content
2.90g/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 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.39%, and selectivity is 82.37%, 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 10】
The preparation of carbonylating catalyst：By the ammonium chloroplatinite ((NH containing 6.10gPt, containing 2.90gBe and containing 2.90gPr4)2PtCl4)、BeCl2And Cl3Pr·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 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, Pt contents are 6.10g/L, Be contents 2.90g/L, Pr
Content 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.18%, and selectivity is 83.14%, 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 11】
The preparation of carbonylating catalyst：By the OsCl containing 6.10gOs, containing 2.90gBe and containing 2.90gNd3·3H2O、BeCl2
With Nd (OAc)3·5H2O, 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, Os contents are 6.10g/L, Be contents 2.90g/L, Nd content 2.90g/
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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.20%, and selectivity is 83.17%, 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 the IrCl containing 6.10gIr, containing 2.90gBe and containing 2.90gYb3·XH2O、BeCl2
And YbCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 165m by 1.0L2/ g, pore volume are
0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.For the carbonylating catalyst through icp analysis, Ir contents are 6.10g/L, Be contents 2.90g/L, Yb content 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.14%, and selectivity is 83.22%, 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 the part (Rh of rhodium acetate two containing 6.10gRh, containing 2.90gSr and containing 2.90gLu2
(OAc)4)、Sr(OAc)2·0.5H2O and LuCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, 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 6.10g/L through icp analysis, Rh contents, and Sr contains
Measure 2.90g/L, Lu contents 2.90g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.35%, and selectivity is 83.36%, 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 Rh containing 6.10g, the acetic acid containing 2.90gSr, containing 1.33gSn and containing 1.57gLa
Part (the Rh of rhodium two2(OAc)4)、Sr(OAc)2·0.5H2O, stannous oxalate (SnC2O4) and La (OAc)3·5H2O is sufficiently mixed molten
Solution obtains maceration extract 400ml in the hydrochloric acid that concentration is 8wt%, than surface is 165m by 1.0L2/ g, pore volume 0.95, diameter
For 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.It is described
Carbonylating catalyst is through icp analysis, and Rh contents are 6.10g/L, Sr contents 2.90g/L, Sn content 1.33g/L, La content
1.57g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 61.21%, and selectivity is 84.29%, 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 being improved selected from IVA metals Sn and lanthanide series metal La
The yield and selectivity aspect of vinyl acetate have preferably synergy.
【Embodiment 15】
The preparation of carbonylating catalyst：By Rh containing 6.10g, the acetic acid containing 2.90gSr, containing 1.33gPb and containing 1.57gLa
Part (the Rh of rhodium two2(OAc)4)、Sr(OAc)2·0.5H2O, basic lead acetate (Pb (OAc)2·2Pb(OH)2) and La (OAc)3·
5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 165m by 1.0L2/ g, pore volume 0.95, diameter
For 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.It is described
Carbonylating catalyst is through icp analysis, and Rh contents are 6.10g/L, Sr contents 2.90g/L, Pb content 1.33g/L, La content
1.57g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 61.14%, and selectivity is 84.38%, 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 6.10g Rh, containing 2.90gSr, containing 0.71gSn, containing 0.62gPb and contain
1.57gLa part (the Rh of rhodium acetate two2(OAc)4)、Sr(OAc)2·0.5H2O, stannous oxalate (SnC2O4), basic lead acetate
(Pb(OAc)2·2Pb(OH)2) and La (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in the hydrochloric acid that concentration is 8wt%, is impregnated
Liquid 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 leaching
In stain liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is through icp analysis, Rh contents
6.10g/L, Sr content 2.90g/L, Sn content 0.71g/L, Pb content 0.62g/L, La content 1.57g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 62.82%, and selectivity is 85.55%, 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 is compared with embodiment 14, embodiment 15 as can be seen that other selected from IVA metal Sn and Pb and the present invention
Active component improve vinyl acetate yield and selectivity in terms of have preferably synergy.
【Embodiment 17】
The preparation of carbonylating catalyst：To contain 6.10g Rh, containing 2.90gBe, containing 0.71gSn, containing 0.62gPb and contain
1.57gLa part (the Rh of rhodium acetate two2(OAc)4)、BeCl2, stannous oxalate (SnC2O4), basic lead acetate (Pb (OAc)2·
2Pb(OH)2) and La (OAc)3·5H2O, 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 6.10g/L through icp analysis, Rh contents, and Be contains
Measure 2.90g/L, Sn contents 0.71g/L, Pb content 0.62g/L, La content 1.57g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 62.74%, and selectivity is 85.67%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 18】
The preparation of carbonylating catalyst：To contain 6.10g Rh, containing 1.43gSr, containing 1.47gBe, containing 0.71gSn, contain
The 0.62gPb and part (Rh of rhodium acetate two containing 1.57gLa2(OAc)4)、Sr(OAc)2·0.5H2O、BeCl2, stannous oxalate
(SnC2O4), basic lead acetate (Pb (OAc)2·2Pb(OH)2) and La (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in concentration and is
In 8wt% hydrochloric acid, maceration extract 400ml is obtained, than surface is 165m by 1.0L2/ g, pore volume 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
For agent through icp analysis, Rh contents are 6.10g/L, Sr contents 1.43g/L, Be content 1.47g/L, Sn content 0.71g/L, and Pb contains
Measure 0.62g/L, La contents 1.57g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 63.31%, and selectivity is 86.79%, 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.
The present embodiment can be seen that Be, Sr and its in the present invention in alkaline-earth metal compared with embodiment 16, embodiment 17
The favourable selectivity and yield for improving vinyl acetate of its active component collaboration, illustrates Rh, Be, Sr, Sn, Pb and La active component
Between exist well synergy.
【Embodiment 19】
The preparation of carbonylating catalyst：To contain 6.10g Rh, containing 1.43gSr, containing 1.47gBe, containing 0.71gSn, contain
The 0.62gPb and part (Rh of rhodium acetate two containing 1.57gCe2(OAc)4)、Sr(OAc)2·0.5H2O、BeCl2, stannous oxalate
(SnC2O4), basic lead acetate (Pb (OAc)2·2Pb(OH)2) and Ce (OAc)3·6H2O, which is sufficiently mixed, to be dissolved in concentration and is
In 8wt% hydrochloric acid, maceration extract 400ml is obtained, than surface is 165m by 1.0L2/ g, pore volume 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
For agent through icp analysis, Rh contents are 6.10g/L, Sr contents 1.43g/L, Be content 1.47g/L, Sn content 0.71g/L, and Pb contains
Measure 0.62g/L, Ce contents 1.57g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 63.40%, and selectivity is 86.78%, 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 6.10g Rh, containing 1.43gSr, containing 1.47gBe, containing 0.71gSn, contain
0.62gPb, the part (Rh of rhodium acetate two containing 0.77gLa and 0.80gCe2(OAc)4)、Sr(OAc)2·0.5H2O、BeCl2, oxalic acid
Stannous (SnC2O4), basic lead acetate (Pb (OAc)2·2Pb(OH)2)、La(OAc)3·5H2O and Ce (OAc)3·6H2O is fully mixed
Close and be dissolved in the hydrochloric acid that concentration is 8wt%, obtain maceration extract 400ml, than surface be 165m by 1.0L2/ g, pore volume 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 carbonylating catalyst is through icp analysis, and Rh contents are 6.10g/L, Sr contents 1.43g/L, Be content 1.47g/L, Sn content
0.71g/L, Pb content 0.62g/L, La content 0.77g/L, Ce content 0.80g/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 7.5MPa
Temperature is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is down to
Room temperature, obtained product will be reacted and be washed with water 3 times, organic matter enters oil phase, through rectification and purification removing solvent, ethyl acetate,
Acetaldehyde and other accessory substances, obtain ethylidene diacetate.
Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume
The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.40MPa in kettle after air, raising mixing speed to 600rpm,
Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 DEG C, after sustained response 45min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 64.22%, and selectivity is 87.84%, 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 La, Ce 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, Be, Sr, Sn, Pb, Ce and La activity
Synergy well between component be present.
Table 1
Table 2
Claims (10)
1. the method for methyl acetate carbonylation production vinyl acetate, comprises the following steps：(1) with methyl acetate, carbon monoxide and
Hydrogen is raw material, and carbonylation is carried out in the presence of carbonylating catalyst, co-catalyst and obtains ethylidene diacetate；(2) exist
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, the ratio surface of the carrier is 50~300m2/ g, pore volume is 0.80~1.20, living
Property component include at least one selected from platinum cluster metal, at least one and selected from IVA and lanthanide series metal member selected from alkaline-earth metal
At least one of element metallic element；The co-catalyst is iodide.
2. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that the platinum cluster gold
At least one of the category selected from platinum, palladium, osmium, iridium, ruthenium and rhodium.
3. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that the alkaline earth gold
Category is selected from least one of beryllium, magnesium, calcium, strontium and barium.
4. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that the IVA metals
Selected from least one of germanium, tin and lead.
5. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that the group of the lanthanides gold
Category is selected from least one of lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium.
6. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that platinum in catalyst
The content of cluster element is 3.00~15.00g/L, and the content of alkali earth metal is 0.10~5.00g/L.
7. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that institute in catalyst
At least one content for stating the metal in IVA and lanthanide series metal is 0.50~8.00g/L.
8. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that the iodide
For iodomethane.
9. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that the carbonylation
The temperature of reaction is 130~200 DEG C；The pressure of reaction is 3.0~10.0MPa；Carbon monoxide and hydrogen volume ratio are in reaction
0.10~10.0；The time of reaction is 3.0~10.0h.
10. the method for methyl acetate carbonylation production vinyl acetate according to claim 1, it is characterised in that carbonylation
The preparation method of catalyst, comprises the following steps：
1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of alkali earth metal, IVA and lanthanide series metal
The solution of the compound of middle metal 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 CN201410575050.2A patent/CN105585494B/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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