CN105585496A - Method for synthesizing vinyl acetate - Google Patents
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Abstract
The invention relates to a method for synthesizing vinyl acetate. When vinyl acetate is prepared from methyl acetate through the route of carbonylation and cracking, vinyl acetate yield and selectivity are low. The invention mainly aims at solving the problems. The vinyl acetate synthesis method comprises the following steps: methyl acetate carbonylation is carried out, such that ethylene diacetate is obtained; and ethylene diacetate is cracked, such that vinyl acetate is obtained. A carbonylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and has active components comprising at least one selected from iron-series elements, alkaline earth metal and at least one metal element selected from IB and VA. With the technical scheme, the technical problem is well solved. The method can be used in industrial production of vinyl acetate.
Description
Technical field
The present invention relates to the method for the synthesis of vinyl acetate.
Background technology
Vinyl acetate, vinyl acetate (vinylacetate is called for short VAC or VAM), is at room temperature water white transparencyInflammable liquid, with sweet ether fragrance. It is one of Organic Chemicals that output is larger in the world, is widely used in lifeProduce polyvinyl acetate (PVAc), polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resins,A series of chemical industry such as acetal resin and fiber product, be widely used in all trades and professions.
Inside and outside the producing country of vinyl acetate, all adopt ethene vapor phase method and acetylene in gas phase method technique, belong to petrochemical process roadLine, after C1 chemistry rises, the eighties in 20th century, U.S. Ha Erkang (Halcon) company and BP (BP)Company successively proposes to be prepared by methyl alcohol and synthesis gas new technology-carbonyl process synthesizing vinyl acetate of vinyl acetate. This technique is notRely on petrochemical materials, but by the carbonylation of methyl acetate and synthesis gas, the sub-second of the two acetic acid of synthetic intermediateEster (EDDA), then produce vinyl acetate and acetic acid through thermal cracking. The novel part of whole technique is adding of methyl acetateHydroformylation reaction, catalyst is with radium chloride and use beta-picoline and iodomethane modification, and carbon monoxide inserts reaction and isThe key point of whole technology.
(title is US Patent No. 5354886: CatalystsoninorganiccarriersforproducingethylideneDiacetate) mention RhCl3Or rhodium compound loads on diatomite, titanium oxide, magnesia, aluminium oxide and oxidationOn zinc, make loaded catalyst. Taking methyl acetate, carbon monoxide and hydrogen as raw material, under polar solvent condition,The synthetic ethylidene diacetate of reaction under above-mentioned catalyst. (title is US4843170: ProcessforproduingvinylAcetate) in, mention and utilize halogen acids, sulfuric acid, nitric acid, polyphosphoric acid, benzene sulfonic acid, alkyl sulfonic acid etc. as two acetic acid AsiaEthyl ester cracking is for the catalyst of vinyl acetate. Said method exists vinyl acetate yield low in synthesizing vinyl acetate processWith selective not high problem.
Summary of the invention
Technical problem to be solved by this invention is the low and selective not high problem of vinyl acetate yield, provides a kind of newVinyl acetate is prepared method used, and the method has vinyl acetate yield height and selective high feature.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: vinyl acetate is prepared method used,Comprise the following steps: (1), taking methyl acetate, carbon monoxide and hydrogen as raw material, is entered under carbonylating catalyst existsRow carbonylation obtains ethylidene diacetate; (2) under catalyst for cracking exists, ethylidene diacetate cracking is obtainedObtain vinyl acetate; Wherein, described carbonylating catalyst adopts SiO2、Al2O3Or its mixture is carrier, active groupPoint comprise chosen from Fe series elements at least one, alkaline-earth metal and be selected from IB and VA at least one metallic element.Preferred described active component comprises iron series element, alkaline-earth metal simultaneously, is selected from least one metallic element and choosing in IBAt least one metallic element in VA. Now between the metallic element of IB and the metallic element of VA, improving acetic acid secondSelective and the yield aspect of alkene has synergy.
In technique scheme, at least one in the excellent chosen from Fe of described iron series element, cobalt and nickel.
In technique scheme, described alkaline-earth metal is at least one in beryllium, magnesium, calcium, strontium and barium preferably.
In technique scheme, preferably at least one in copper, silver and gold of described IB metal.
In technique scheme, preferably at least one in antimony and bismuth of described VA metal.
As preferred technical scheme, described active component comprise simultaneously iron series element (for example iron series element can be butBe not limited to cobalt, nickel, cobalt and nickel), at least one in alkaline-earth metal and gold element and antimony element, and alkaline-earth metalComprise beryllium and strontium simultaneously; As more preferred technical scheme, described active component comprises iron series element (for example iron simultaneouslySeries elements can be but be not limited to cobalt, nickel, cobalt and nickel), alkaline-earth metal, gold element and antimony element, and alkaline-earth metal withTime comprise beryllium and strontium; As most preferred technical scheme, described active component comprise simultaneously iron series element, alkaline-earth metal,Gold element and antimony element, and alkaline-earth metal comprises beryllium and strontium simultaneously, iron series element comprises cobalt and nickel simultaneously.
In technique scheme, in described carbonylating catalyst, the content of iron series element is preferably 3.00～15.00g/L, more excellentElect 7.0～12.0g/L as; In described carbonylating catalyst, the content of alkaline-earth metal is preferably 0.10～5.00g/L, more preferably1.00～4.00g/L; In described carbonylating catalyst, being selected from least one content of metal in IB and VA is preferably0.50～8.00g/L, more preferably 1.0～5.0g/L. Described carbonylating catalyst carrier specific surface used is preferably50～300m2/ g, more preferably 150～200m2/ g, pore volume is preferably 0.80～1.20, and more preferably 0.90～1.00. Above-mentionedDescribed in technical scheme, iodide are preferably iodomethane.
In technique scheme, the preparation method that described carbonylating catalyst can adopt, comprises the steps:
1. press the composition of catalyst by the change of metal in the compound of the compound of iron series element, alkaline-earth metal, IB and VAThe solution of compound mixes with carrier;
2. dry.
In technique scheme, step 1. described iron series element compound preferably from ferrocene, carbonyl cobalt, cobalt acetate,At least one in cobalt nitrate, cobalt chloride, carbonyl nickel and nickel chloride. Step 1. described alkaline earth metal compound preferably from alkaliSoil metal oxide, alkaline earth metal chloride, alkaline earth nitrate, alkali earth metal sulfate and Alkaline Earth Metal AcetateIn at least one. Step 1. described IB metallic compound preferably from cupric tetramminosulfate, copper nitrate, copper chloride, nitreAt least one in acid silver, silver acetate, silver ammino solution, gold chloride and tetra chlorauric acid ammonium. Step is metal in described VA 1.Compound is at least one in basic bismuth carbonate, bismuth sulfate, bismuth chloride, antimony sulfate and antimony chloride preferably. Step is institute 2.State baking temperature and be preferably 80～120 DEG C, more preferably 100～120 DEG C.
In technique scheme, by the composition of catalyst by comprise iron series element compound, alkaline-earth metal compound,In IB and VA, the compound of metal and carrier hybrid mode are not particularly limited, their aqueous solution contact with carrier timeMachine is also not particularly limited. For example the present invention will can comprised to compound, the alkali of iron series element by the composition of catalystIn compound, IB and the VA of earth metal, the compound of metal first mixes water-solublely, can be also that their compound is complied withAfter the inferior formation aqueous solution, mix again and contact with carrier, can also different order contact with carrier and obtain described catalyst.
Key of the present invention is carbonylating catalyst, after obtaining carbonylating catalyst, by making carbonylating catalystContact and can be used for carbonylation with described co-catalyst. The mode that carbonylating catalyst contacts with co-catalyst does not have spyNot Xian Zhi, to be also not particularly limited the opportunity that both contact. For example carbonylating catalyst of the present invention can be used forBefore chemical reaction, make both contact and form described catalyst, can also make both in the applied reaction of catalyst of the present inventionIn system, contact generates catalyst original position.
Key of the present invention is the selection of carbonylating catalyst, those skilled in the art will know that and how to determine according to actual needsThe proportioning of suitable reaction temperature, reaction time, reaction pressure and material. But, the temperature of reacting in technique schemeDegree is 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.The mol ratio of carbon monoxide and hydrogen is preferably 0.10～10.0.
In the method for methyl acetate synthesis vinyl acetate of the present invention, after step (1) finishes, can be to carbonylationMixture separates acquisition target product ethylidene diacetate and carries out step (2) again, also can step (1) generate twoAfter acetic acid ethyl, do not separate and directly carry out step (2). Those skilled in the art know the suitable cracking and catalyzing of selectionAgent and definite suitable cracking reaction temperature, time and material proportion. Conventional catalyst for cracking have Bronsted acid (as HI,HBr、HCl、HF、H2SO4、H3PO4、HNO3、H3BO3、HClO3、HBrO3、HIO3, polyphosphoric acid, alkaneBase sulfonic acid, benzene sulfonic acid etc.), lewis acid (as IIA, IIIA, IVA, VA, VIA, IIIB, IVB, VB, VIB,VIIB, VIII metal halogen compound). In the present invention preferably benzene sulfonic acid as catalyst for cracking, suitable cracking temperatureBe preferably 100～180 DEG C; Cleavage reaction pressure is 0～1.0MPa preferably; The cracking reaction time is preferably 10～60min;Benzene sulfonic acid catalyst for cracking accounts for 3.0～7.0% of raw material total amount; At least one in the preferred acetic acid of solvent and aceticanhydride.
Product of the present invention adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis after cooling, decompression, separation,Calculate the conversion ratio of methyl acetate and the yield of vinyl acetate and selective by following formula:
Compared with prior art, key of the present invention is that the active component of step (1) carbonylating catalyst comprises necessarilyIron series element, the alkaline-earth metal of amount and be selected from IB and VA at least one metallic element, be conducive to improve catalystActivity and stability, thus the yield that has improved vinyl acetate is with selective.
Experimental result shows, the yield of the prepared vinyl acetate of the present invention reaches 58.25%, selectively reaches 81.36%, getsObtained good technique effect, especially in carbonylating catalyst active component comprise simultaneously iron series element, alkaline-earth metal,When being selected from least one metallic element in IB and being selected from least one metallic element in VA, obtain more outstandingTechnique effect, can be in vinyl acetate synthetic. Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 3.20gBe and the Co containing 1.85gAu2(CO)8、BeCl2And NH4AuCl4·2H2In the acetic acid that the abundant mixed dissolution of O is 10wt% in concentration, obtain maceration extract 400ml, by 1.0LSpecific surface is 170m2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is9.35g/L, Be content 3.20g/L, Au content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.25% as calculated, is selectively 81.36%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 2]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 3.20gBe and the Co containing 1.85gSb2(CO)8、BeCl2And Cl3In the acetic acid that the abundant mixed dissolution of Sb is 10wt% in concentration, obtain maceration extract 400ml, by 1.0L specific surfaceFor 170m2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 9.35g/L,Be content 3.20g/L, Sb content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.18% as calculated, is selectively 81.49%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of carbonylating catalyst: will contain 8.60gCo and the Co containing 3.20gBe2(CO)8And BeCl2Fully mixBeing dissolved in the acetic acid that concentration is 10wt%, obtaining maceration extract 400ml, is 170m by 1.0L specific surface2/ g, pore volumeBe 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry,Obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 9.35g/L, Be content 3.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 50.37% as calculated, is selectively 70.52%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
By finding out compared with embodiment 1～2, the catalyst that the present invention adopts, uses simultaneously containing Co, Be and AuActive component, simultaneously containing the catalyst performance of Co, Be and Sb active component than only containing Co, Be active constituent catalystPerformance more excellent, the selective and yield of vinyl acetate is all wanted height.
[embodiment 3]
The preparation of carbonylating catalyst: will contain 7.00gCo, contain 1.00gMg and the Co (OAc) containing 1.00gAu2·4H2O、MgSO4·7H2O and HAuCl4Fully mixed dissolution, in pure water, obtains maceration extract 400ml, by 1.0L specific surface is150m2/ g, pore volume is 0.90, the spherical Al that diameter is 5.6mm2O3Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2hIn 80 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 7.00g/L,Mg content 1.00g/L, Au content 1.00g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 56.44% as calculated, is selectively 80.87%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 4]
The preparation of carbonylating catalyst: will contain 12.00gFe, contain 4.00gCa and the ferrocene containing 5.00gCu(Fe(C5H5)2), CaO and cupric tetramminosulfate (Cu (NH3)4SO4) nitre that fully mixed dissolution is 8wt% in concentrationIn acid, obtaining maceration extract 400ml, is 200m by 1.0L specific surface2/ g, pore volume is 1.00, diameter is 5.6mmSpherical SiO2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 120 DEG C dry, obtain described catalyst. Described carbonylBase catalyst is through icp analysis, and Fe content is 12.00g/L, Ca content 4.00g/L, Cu content 5.00g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MP after air with argon gasa, improve mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.60% as calculated, is selectively 81.02%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 5]
The preparation of carbonylating catalyst: will contain 9.35gNi, contain 3.20gBa and the Ni (NO containing 1.85gAg3)2·6H2O、Ba(NO3)2In pure water, obtaining maceration extract 400ml with the abundant mixed dissolution of AgOAc, is 170 by 1.0L specific surfacem2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in100 DEG C dry, obtains described catalyst. Described carbonylating catalyst is through icp analysis, and Ni content is 9.35g/L, BaContent 3.20g/L, Ag content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.28% as calculated, is selectively 81.55%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table 2。
[embodiment 6]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 3.20gSr and the CoCl containing 1.85gAg2·6H2O、Sr(OAc)2·1/2H2O and silver ammino solution ([Ag (NH3)2] OH) and fully mixed dissolution in pure water, obtain maceration extract400ml is 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnationIn above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through ICPAnalyze, Co content is 9.35g/L, Sr content 3.20g/L, Ag content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.42% as calculated, is selectively 81.39%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 7]
The preparation of carbonylating catalyst: will contain 9.35gNi, contain 3.20gSr and the NiCl containing 1.85gBi2·6H2O、Sr(OAc)2·0.5H2O and basic bismuth carbonate ((BiO)2CO3·0.5H2O) fully mixed dissolution, in pure water, is floodedLiquid 400ml is 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier soaksStain in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through ICPAnalyze, Ni content is 9.35g/L, Sr content 3.20g/L, Bi content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.37% as calculated, is selectively 81.33%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 8]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 3.20gSr and the Co (NO containing 1.85gBi3)2·6H2O、Sr(OAc)2·0.5H2O and Bi2(SO4)3In the aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, floodedLiquid 400ml is 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier soaksStain in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through ICPAnalyze, Co content is 9.35g/L, Sr content 3.20g/L, Bi content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 3.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 130 DEG C, the mol ratio of carbon monoxide and hydrogen is 1:10, after sustained response 3.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 55.97% as calculated, is selectively 78.20%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 9]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 3.20gSr and the Co (NO containing 1.85gBi3)2·6H2O、Sr(OAc)2·1/2H2O and BiCl3In the aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, obtain maceration extract400ml is 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnationIn above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through ICPAnalyze, Co content is 9.35g/L, Sr content 3.20g/L, Bi content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 10.0MPa improves mixing speed to 1200rpm, and agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 200 DEG C, and the mol ratio of carbon monoxide and hydrogen is 10:1, after sustained response 10.0h,Stop reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, warpRectification and purification, except desolventizing, ethyl acetate, acetaldehyde and other accessory substances, obtains ethylidene diacetate.
Step (2): it is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.72% as calculated, is selectively 80.88%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 10]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 3.20gSr and the Co containing 1.85gSb2(CO)8、Sr(OAc)2·1/2H2O and Cl3In the acetic acid that the abundant mixed dissolution of Sb is 10wt% in concentration, obtain maceration extract 400ml,Be 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation is above-mentionedIn maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis,Co content is 9.35g/L, Sr content 3.20g/L, Sb content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.31% as calculated, is selectively 81.42%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 11]
The preparation of carbonylating catalyst: will contain 9.35gNi, contain 3.20gSr and the NiCl containing 1.85gSb2·6H2O、Sr(OAc)2·1/2H2O and Sb2(SO4)3In the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtain maceration extract400ml is 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnationIn above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through ICPAnalyze, Ni content is 9.35g/L, Sr content 3.20g/L, Sb content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.35% as calculated, is selectively 81.34%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 12]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 3.20gSr and the Co containing 1.85gAu2(CO)8、Sr(OAc)2·1/2H2O and NH4AuCl4·2H2In the acetic acid that the abundant mixed dissolution of O is 10wt% in concentration, soakedStain liquid 400ml is 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2CarrierBe immersed in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst warpIcp analysis, Co content is 9.35g/L, Sr content 3.20g/L, Au content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 58.24% as calculated, is selectively 81.26%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 13]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 1.08gBe, contain 2.12gSr and contain 1.85gAu'sCo2(CO)8、BeCl2、Sr(OAc)2·1/2H2O and NH4AuCl4·2H2The abundant mixed dissolution of O is 10wt% in concentrationAcetic acid in, obtain maceration extract 400ml, be 170m by 1.0L specific surface2/ g, pore volume is 0.97, diameter is 5.6mmSpherical SiO2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. DescribedCarbonylating catalyst is through icp analysis, and Co content is 9.35g/L, Be content 1.08g/L, Sr content 2.12g/L, AuContent 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 59.52% as calculated, is selectively 82.74%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment and embodiment 1, embodiment 12 relatively can find out, alkaline-earth metal Be and Sr are improving vinyl acetateYield and selectively there is good synergy.
[embodiment 14]
The preparation of carbonylating catalyst: will contain 9.35gCo, contain 1.08gBe, contain 2.12gSr and contain 1.85gSb'sCo2(CO)8、BeCl2、Sr(OAc)2·1/2H2O and Cl3In the acetic acid that the abundant mixed dissolution of Sb is 10wt% in concentration,Obtaining maceration extract 400ml, is 170m by 1.0L specific surface2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalystThrough icp analysis, Co content is 9.35g/L, Be content 1.08g/L, Sr content 2.12g/L, Sb content 1.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 59.43% as calculated, is selectively 82.81%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 15]
The preparation of carbonylating catalyst: will be containing 9.35gCo, containing 1.08gBe, containing 2.12gSr, containing 1.00gSb and containingThe Co of 0.85gAu2(CO)8、BeCl2、Sr(OAc)2·1/2H2O、Cl3Sb and NH4AuCl4·2H2O fully mixes moltenIn the acetic acid that solution is 10wt% in concentration, obtaining maceration extract 400ml, is 170m by 1.0L specific surface2/ g, pore volume is0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry,To described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 9.35g/L, Be content 1.08g/L,Sr content 2.12g/L, Sb content 1.00g/L, Au content 0.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 61.02% as calculated, is selectively 83.26%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment and embodiment 13, embodiment 14 relatively can find out, alkaline-earth metal Be and Sr and be selected from IB'sIn Au and VA, metal Sb is improving the yield of vinyl acetate and is selectively having good synergy.
[embodiment 16]
The preparation of carbonylating catalyst: will be containing 9.35gNi, containing 1.08gBe, containing 2.12gSr, containing 1.00gSb and containingThe NiCl of 0.85gAu2·6H2O、BeCl2、Sr(OAc)2·1/2H2O、Cl3Sb and NH4AuCl4·2H2O fully mixesBeing dissolved in pure water, obtaining maceration extract 400ml, is 170m by 1.0L specific surface2/ g, pore volume is 0.97, diameter isThe spherical SiO of 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst.Described carbonylating catalyst is through icp analysis, and Ni content is 9.35g/L, Be content 1.08g/L, and Sr content 2.12g/L,Sb content 1.00g/L, Au content 0.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 60.96% as calculated, is selectively 83.35%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
[embodiment 17]
The preparation of carbonylating catalyst: will be containing 6.23gCo, containing 3.12gNi, containing 1.08gBe, containing 2.12gSr, containing 1.00gSb and containing the Co of 0.85gAu2(CO)8、NiCl2·6H2O、BeCl2、Sr(OAc)2·1/2H2O、Cl3Sb and NH4AuCl4·2H2In the acetic acid that the abundant mixed dissolution of O is 10wt% in concentration, obtain maceration extract 400ml, by 1.0L specific surface be170m2/ g, pore volume is 0.97, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2hIn 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Co content is 6.23g/L,Ni content 3.12g/L, Be content 1.08g/L, Sr content 2.12g/L, Sb content 1.00g/L, Au content 0.85g/L.
Synthesizing of vinyl acetate:
Step (1): by 1.5mol acetic acid, 0.05mol carbonylating catalyst, 0.10mol iodomethane and 0.45mol vinegarAcid methyl esters adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes intoCarbon monoxide and hydrogen are until pressure 8.2MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 176 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, 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 to volumeThe rectification process tower of reactor, first discharges in still and is pressurized to 0.35MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 148 DEG C, after sustained response 45min,Stop reaction.
Product analysis: reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, liquid phase adopt gas-chromatography-GC-MS (GC-MASS) is analyzed.
The yield of vinyl acetate is 62.39% as calculated, is selectively 84.59%, for convenience of explanation and relatively, will urgeThe yield of the preparation condition of agent, reaction condition, material feeding amount, vinyl acetate and selectively list in respectively table 1 and table2。
The present embodiment is compared and can be found out with embodiment 15, embodiment 16, alkali earth metal be selected from IB andWhen in VA, metallic element is identical, when iron series element is selected from Co, Ni simultaneously, the selective and yield of ethylidene diacetate is all wantedHeight, has illustrated between Co, Ni, Be, Sr, Sb and Au active component and has existed well and act synergistically.
Table 1
Table 2
Claims (10)
1. for the synthesis of the method for vinyl acetate, comprise the following steps: (1) is taking methyl acetate, carbon monoxide and hydrogen as formerMaterial, carries out carbonylation at carbonylating catalyst, co-catalyst and obtains ethylidene diacetate under existing; (2) in crackingUnder catalyst exists, make ethylidene diacetate cracking obtain vinyl acetate; Wherein, described carbonylating catalyst adopts SiO2、Al2O3Or its mixture is carrier, active component comprise chosen from Fe series elements at least one, alkaline-earth metal and being selected fromAt least one metallic element in IB and VA; Described co-catalyst is iodide.
2. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that described iron series element chosen from Fe,At least one in cobalt and nickel.
3. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that described alkaline-earth metal be selected from beryllium,At least one in magnesium, calcium, strontium and barium.
4. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that described IB metal is selected from copper, silverWith at least one in gold.
5. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that described VA metal be selected from antimony andAt least one in bismuth.
6. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that containing of iron series element in catalystAmount is: 3.00～15.00g/L, the content of alkaline-earth metal is: 0.10～5.00g/L.
7. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that being selected from described in catalyst IB andIn VA, at least one content of metal is 0.50～8.00g/L.
8. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that described iodide are iodomethane.
9. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that the temperature of described carbonylationIt is 130～200 DEG C; The pressure of reaction is 3.0～10.0MPa; In reaction carbon monoxide and hydrogen volume ratio be 0.10～10.0; The time of reaction is 3.0～10.0h.
10. according to claim 1 for the synthesis of the method for vinyl acetate, it is characterized in that the system of carbonylation reaction catalystPreparation Method, comprises the steps:
1. press the composition of catalyst by the change of metal in the compound of the compound of iron series element, alkaline-earth metal, IB and VAThe solution of compound mixes with carrier;
2. dry.
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019229592A1 (en) * | 2018-05-29 | 2019-12-05 | Sabic Global Technologies B.V. | Process for production of diol esters from esters of mono alcohols |
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