CN105585497B - The production method of vinyl acetate - Google Patents
The production method of vinyl acetate Download PDFInfo
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- CN105585497B CN105585497B CN201410575138.4A CN201410575138A CN105585497B CN 105585497 B CN105585497 B CN 105585497B CN 201410575138 A CN201410575138 A CN 201410575138A CN 105585497 B CN105585497 B CN 105585497B
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Abstract
The present invention relates to the production method of vinyl acetate, mainly solves the problems, such as that methyl acetate is successively low through being carbonylated, cracking the yield of vinyl acetate and selectivity when route prepares vinyl acetate.By using the production 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 metalloid element at least one and selected from least one of IIB 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 production 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 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.
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 double acetic acid Asias second 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.Double vinegar during ethylidene diacetate is prepared be present in the above method
The problem of sour ethyl yield is low and selective not high.
The content of the invention
The problem of technical problems to be solved by the invention are that vinyl acetate yield is low and selectivity is not high, there is provided Yi Zhongxin
Vinyl acetate production 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 production 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 metalloid element at least one and selected from least one of IIB and lanthanide element metallic element.
It is preferred that the active component simultaneously including platinum cluster metallic element, metalloid element, selected from least one of IIB metallic elements and
Selected from least one of lanthanide series metal metallic element.Now between IIB metallic element and the metallic element of lanthanide series metal
The selectivity and yield aspect for improving vinyl acetate have synergy.
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 metalloid element preferably is selected from least one of boron, arsenic and tellurium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component metalloid element is more preferably boron
With tellurium metalloid.
In above-mentioned technical proposal, the IIB metals preferably are selected from least one of zinc, cadmium and mercury.
In above-mentioned technical proposal, the 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,
Metalloid element, IIB metals and lanthanide series metal；Such as the active component includes rhodium, boron, zinc (or cadmium) and cerium, or including
Rhodium, boron (or tellurium), zinc, cadmium and cerium, either including rhodium, boron, tellurium, zinc, cadmium and cerium (or lutetium) or including rhodium, boron, tellurium, zinc,
Cadmium, cerium and lutetium.
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 metalloid element is preferably 0.10 in the carbonylating catalyst
~5.00g/L, more preferably 1.00~4.00g/L；Metal is extremely in IIB 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 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 optional preparation method of the carbonylating catalyst, comprise the following steps：
1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of metalloid element, IIB metals and lanthanum
It is that the solution of the compound of metal mixes 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, 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.Step is 1. described accurate golden
The compound of category element preferably is selected from boric acid, ammonium pentaborate, dimethylamino monoborane, arsenic acid, arsenic trichloride, ammonium tellurate, titanium dioxide
At least one of tellurium and telluric acid.Step 1. the IIB metallic compounds preferably be selected from zinc gluconate, zinc citrate, zinc acetate,
At least one of cadmium acetate, cadmium nitrate, caddy and mercuric sulfate.1. the lanthanide metals compound preferably is selected from vinegar to step
Sour lanthanum, lanthanum chloride, lanthanum nitrate, cerous acetate, cerium chloride, cerous nitrate, praseodymium acetate, praseodymium chloride, acetic acid neodymium, samarium trichloride, ytterbium chloride and
At least one of lutecium chloride.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 compound including platinum cluster metallic element, metalloid element
Compound, the compound of IIB 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.Such as the present invention can pressed to the composition of catalyst by including platinum cluster metallic element
Compound, the compound of metalloid element, the compound of IIB 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 contact with carrier to obtain institute with different order
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 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 metallic element of amount, metalloid element and selected from least one of IIB and lanthanide metals metallic element, are advantageous to
The activity and stability of catalyst are improved, so as to improve the yield of vinyl acetate and selectivity.
Test result indicates that the yield of the vinyl acetate prepared by the present invention selectively reaches 83.49% up to 60.33%,
Preferable technique effect is achieved, active component is simultaneously including platinum cluster metal, metalloid in especially described carbonylating catalyst
Element, selected from least one of IIB 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 6.30g, the RhCl containing 2.90gB and containing 3.00gZn3·3H2O, five boron
Sour ammonium ((NH4)B5O8·8H2) and zinc gluconate (C O12H22O14Zn3·3H2O) it is sufficiently mixed and is dissolved in pure water, is soaked
Stain liquid 400ml, than surface it is 165m by 1.0L2/ g, pore volume 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, obtains the catalyst.The carbonylating catalyst is analyzed through ICP and ICP-MS,
Rh contents are 6.30g/L, B content 2.90g/L, Zn content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 60.33%, and selectivity is 83.49%, 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 6.30g, the RhCl containing 2.90gB and containing 3.00gCe3·3H2O, five boron
Sour ammonium ((NH4)B5O8·8H2) and Ce (OAc) O3·5H2O, 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 analyzed through ICP and ICP-MS, and Rh contents are
6.30g/L, B content 2.90g/L, Ce content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 60.38%, and selectivity is 83.26%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of carbonylating catalyst：By Rh containing 6.30g and the RhCl containing 2.90gB3·3H2O and ammonium pentaborate ((NH4)
B5O8·8H2O) it is sufficiently mixed and is dissolved in pure water, obtain 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.The carbonylating catalyst is analyzed through ICP and ICP-MS, and Rh contents are 6.30g/L, B 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 51.54%, and selectivity is 72.37%, 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.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Rh, B and Zn work
Property component while catalyst performance ratio containing Rh, B and Ce active component will be more containing only Rh, B activity component catalyst performance
Excellent, the selectivity and yield of vinyl acetate will be high.
【Embodiment 3】
The preparation of carbonylating catalyst：By Rh containing 5.00g, B containing 1.00g and the Zn containing 1.00g triphenylphosphine chlorine rhodium
(C54H45ClP3Rh), boric acid (H3BO3) and zinc citrate Zn3(C6H5O7)2·2H2It is 10wt% that O, which is sufficiently mixed and is dissolved in concentration,
Acetic acid in, obtain maceration extract 400ml, than surface be 150m by 1.0L2/ g, pore volume 0.90, a diameter of 5.6mm's is spherical
Al2O3Carrier impregnation stands 2h in 80 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The carbonylating catalyst warp
ICP and ICP-MS analyses, Rh contents are 5.00g/L, B content 1.00g/L, Zn content 1.00g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 59.47%, and selectivity is 82.62%, 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 part of rhodium acetate two containing 10.00gRh, containing the 4.00gAs and Cd containing 5.00g
(Rh2(OAc)4), arsenic acid (H3AsO4·0.5H2) and Cd (OAc) O2·2H2O, which is sufficiently mixed, to be dissolved in pure water, 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, As content 4.00g/L, Cd content 5.00g/L.
The synthesis of vinyl acetate：
Step (1)：By 1.5mol acetic acid, 0.05mol carbonylating catalysts, 0.10mol iodomethane and 0.45mol tumers
Ester is added in 500ml titanium reactors, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 60.74%, and selectivity is 83.59%, 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 6.30g, the Rh (NO containing the 2.90gTe and Cd containing 3.00g3)3, ammonium tellurate
((NH4)2TeO4) and Cd (NO3)2·4H2O, 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, Rh contents are 6.30g/L, Te contents 2.90g/L, Cd
Content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 60.45%, and selectivity is 83.25%, 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 6.30gPd, containing 2.90gTe and containing 3.00gCd2、TeO2And CdCl2
It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtain maceration extract 400ml, than surface is 165m by 1.0L2/ g, pore volume
For 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained described in above-mentioned maceration extract
Catalyst.For the carbonylating catalyst through icp analysis, Pd contents are 6.30g/L, Te contents 2.90g/L, Cd content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 60.15%, 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 7】
The preparation of carbonylating catalyst：By the ammonia palladium (Pd of dichloro four containing 6.30gPd, containing 2.90gTe and containing 3.00gHg
(NH3)4Cl2·H2O)、H6TeO6And HgSO4It is sufficiently mixed and is dissolved in the salt 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 6.30g/L through icp analysis, Pd contents, and Te contains
Measure 2.90g/L, Hg 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 60.03%, and selectivity is 83.05%, 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 6.30gPd, B containing 2.90g and containing 3.00gSm2, five boric acid
Ammonium ((NH4)B5O8·8H2) and SmCl O3·6H2O, which is sufficiently mixed, to be dissolved in the acetic acid that concentration is 10wt%, 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 analyzed through ICP and ICP-MS, and Pd contains
Measure as 6.30g/L, B content 2.90g/L, Sm content 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, 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 143 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 55.78%, and selectivity is 80.73%, 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 6.30gRu, B containing 2.90g and the La containing 3.00g3·XH2O, five boron
Sour ammonium ((NH4)B5O8·8H2) and LaCl O3·7H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L ratios
Surface is 165m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 2h in
100 DEG C of dryings, obtain the catalyst.The carbonylating catalyst is analyzed through ICP and ICP-MS, and Ru contents are 6.30g/L, B
Content 2.90g/L, La content 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, 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 143 DEG C, after sustained response 40min, stops reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed vinyl acetate is 60.25%, and selectivity is 82.95%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 10】
The preparation of carbonylating catalyst：By the ammonium chloroplatinite ((NH containing 6.30gPt, containing 2.90gB and containing 3.00gPr4)2PtCl4), ammonium pentaborate ((NH4)B5O8·8H2) and Cl O3Pr·6H2O, 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 analyzed through ICP and ICP-MS, and Pt contains
Measure as 6.30g/L, B content 2.90g/L, Pr content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 83.09%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 11】
The preparation of carbonylating catalyst：By the OsCl containing 6.30gOs, containing 2.90gB and containing 3.00gNd3·3H2O, five boric acid
Ammonium ((NH4)B5O8·8H2) and Nd (OAc) O3·5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, by 1.0L
It is 165m than surface2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in above-mentioned maceration extract
In 100 DEG C of dryings, the catalyst is obtained.The carbonylating catalyst is analyzed through ICP and ICP-MS, and Os contents are 6.30g/L,
B content 2.90g/L, Nd content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 60.21%, 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 12】
The preparation of carbonylating catalyst：By the IrCl containing 6.30gIr, containing 2.90gB and containing 3.00gYb3·XH2O, five boric acid
Ammonium ((NH4)B5O8·8H2) and YbCl O3·6H2O, 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 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 analyzed through ICP and ICP-MS, and Ir contents are 6.30g/L, B content
2.90g/L, Yb content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 83.14%, 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 13】
The preparation of carbonylating catalyst：By the RhCl containing 6.30gRh, containing 2.90gB and containing 3.00gLu3·3H2O, five boric acid
Ammonium ((NH4)B5O8·8H2) and LuCl O3·6H2O, 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 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 analyzed through ICP and ICP-MS, and Rh contents are 6.30g/L, B content
2.90g/L, Lu content 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, 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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 83.33%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 14】
The preparation of carbonylating catalyst：By Rh containing 6.30g, containing 2.90gB, containing 1.45gZn and containing 1.55gCe's
RhCl3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), zinc gluconate (C12H22O14Zn3·3H2) and Ce (OAc) O3·
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 analyzed through ICP and ICP-MS, and Rh contents are 6.30g/L, B content 2.90g/L, Zn content 1.45g/L, and Ce contains
Measure 1.55g/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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 61.40%, and selectivity is 84.42%, 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 IIB metals Zn and lanthanide series metal Ce is improving acetic acid
The yield and selectivity aspect of ethene have preferably synergy.
【Embodiment 15】
The preparation of carbonylating catalyst：By Rh containing 6.30g, containing 2.90gB, containing 1.45gCd and containing 1.55gCe's
RhCl3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O)、Cd(NO3)2·4H2O and Ce (OAc)3·5H2O is sufficiently mixed dissolving
In pure water, maceration extract 400ml is obtained, than surface is 165m by 1.0L2/ g, pore volume 0.95, 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
Analyzed through ICP and ICP-MS, Rh contents are 6.30g/L, B content 2.90g/L, Cd content 1.45g/L, Ce content 1.55g/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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 61.35%, and selectivity is 84.44%, 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.
【Embodiment 16】
The preparation of carbonylating catalyst：To contain 6.30g Rh, containing 2.90gB, containing 0.78gZn, containing 0.67gCd and contain
1.55gCe RhCl3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), zinc gluconate (C12H22O14Zn3·3H2O)、Cd
(NO3)2·4H2O and Ce (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 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.The carbonylating catalyst is analyzed through ICP and ICP-MS, and Rh contents are 6.30g/L, B content
2.90g/L, Zn content 0.78g/L, Cd content 0.67g/L, Ce content 1.55g/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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 62.85%, and selectivity is 85.75%, 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 IIB metal Zn and Cd is other living with the present invention
Property component improve vinyl acetate yield and selectivity in terms of have preferably synergy.
【Embodiment 17】
The preparation of carbonylating catalyst：To contain 6.30g Rh, containing 2.90gTe, containing 0.78gZn, containing 0.67gCd and contain
1.55gCe RhCl3·3H2O, ammonium tellurate ((NH4)2TeO4), zinc gluconate (C12H22O14Zn3·3H2O)、Cd(NO3)2·
4H2O and Ce (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, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.The carbonylating catalyst is through icp analysis, and Rh contents are 6.30g/L, Te contents 2.90g/L, Zn content
0.78g/L, Cd content 0.67g/L, Ce content 1.55g/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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 62.90%, and selectivity is 85.70%, 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 6.30g Rh, containing 1.34gB, containing 1.56gTe, containing 0.78gZn, contain
The 0.67gCd and RhCl containing 1.55gCe3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), ammonium tellurate ((NH4)2TeO4), Portugal
Grape saccharic acid zinc (C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O and Ce (OAc)3·5H2O, which is sufficiently mixed, to be dissolved in pure water,
Maceration extract 400ml is obtained, than surface is 165m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation
In above-mentioned maceration extract, 2h is stood in 100 DEG C of dryings, obtains the catalyst.The carbonylating catalyst is through ICP and ICP-MS
Analysis, Rh contents are 6.30g/L, B content 1.34g/L, Te content 1.56g/L, Zn content 0.78g/L, Cd content 0.67g/L,
Ce contents 1.55g/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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 63.43%, and selectivity is 86.81%, 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 compared with embodiment 16, embodiment 17 as can be seen that in metalloid B, Te with it is of the invention in it is other
The favourable selectivity and yield for improving vinyl acetate of active component collaboration, illustrates that Rh, B, Te, Zn, Cd and Ce activearm divide it
Between exist well synergy.
【Embodiment 19】
The preparation of carbonylating catalyst：To contain 6.30g Rh, containing 1.34gB, containing 1.56gTe, containing 0.78gZn, contain
The 0.67gCd and RhCl containing 1.55gLu3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), ammonium tellurate ((NH4)2TeO4), Portugal
Grape saccharic acid zinc (C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O and LuCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, is obtained
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 and ICP-MS points
Analysis, Rh contents are 6.30g/L, B content 1.34g/L, Te content 1.56g/L, Zn content 0.78g/L, Cd content 0.67g/L, Lu
Content 1.55g/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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 63.54%, and selectivity is 86.74%, for convenience of description and compares, will urge
Preparation condition, reaction condition, material inlet amount, the yield of vinyl acetate and the selectivity of agent are listed in Tables 1 and 2 respectively.
【Embodiment 20】
The preparation of carbonylating catalyst：To contain 6.30g Rh, containing 1.34gB, containing 1.56gTe, containing 0.78gZn, contain
0.67gCd, the RhCl containing 0.70gCe and containing 0.85gLu3·3H2O, ammonium pentaborate ((NH4)B5O8·8H2O), ammonium tellurate
((NH4)2TeO4), zinc gluconate (C12H22O14Zn3·3H2O)、Cd(NO3)2·4H2O、Ce(OAc)3·5H2O and LuCl3·
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 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 analyzed through ICP and ICP-MS, and Rh contents are 6.30g/L, B content 1.34g/L, Te content 1.56g/L, and Zn contains
Measure 0.78g/L, Cd contents 0.67g/L, Ce content 0.70g/L, Lu content 0.85g/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 7.3MPa
Temperature is 175 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 143 DEG C, after sustained response 40min, 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 64.57%, and selectivity is 87.68%, 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 Ce, Lu 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, B, Te, Zn, Cd, Ce and Lu activearm
/ presence acts synergistically well.
Table 1
Table 2
Claims (10)
1. the production 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, and active component includes at least one selected from platinum cluster metal, at least one selected from metalloid element and be selected from
At least one of IIB and at least one of lanthanide element metallic element；The co-catalyst is iodide.
2. the production method of vinyl acetate according to claim 1, it is characterised in that the platinum cluster metal be selected from platinum, palladium, osmium,
At least one of iridium, ruthenium and rhodium.
3. the production method of vinyl acetate according to claim 1, it is characterised in that the metalloid element be selected from boron, arsenic and
At least one of tellurium.
4. the production method of vinyl acetate according to claim 1, it is characterised in that the IIB metals are selected from zinc, cadmium and mercury
At least one of.
5. the production 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.
6. the production 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 metalloid element is 0.10~5.00g/L.
7. the production method of vinyl acetate according to claim 1, it is characterised in that described in catalyst selected from IIB metals and
At least one of lanthanide series metal content is 0.50~8.00g/L.
8. the production method of vinyl acetate according to claim 1, it is characterised in that the iodide are iodomethane.
9. the production 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.
10. the production method of vinyl acetate according to claim 1, it is characterised in that the preparation side of carbonylation reaction catalyst
Method, comprise the following steps：
It is 1. by the composition of catalyst that the compound of platinum cluster metallic element, the compound of metalloid element, IIB metals and group of the lanthanides is golden
The solution of the compound of category 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 CN201410575138.4A patent/CN105585497B/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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