CN105585494A - Method for producing vinyl acetate through methyl acetate carbonylation - Google Patents
Method for producing vinyl acetate through methyl acetate carbonylation Download PDFInfo
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Abstract
The invention relates to a method for producing vinyl acetate through methyl acetate carbonylation. 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 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 platinum-group elements, at least one selected from alkaline earth metals and at least one metal element selected from IVA and lanthanide-series metal elements. 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 methyl acetate carbonylation and produce the method for 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 newMethyl acetate carbonylation is produced the method for vinyl acetate, 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: methyl acetate carbonylation is produced acetic acid secondThe method of alkene, comprises the following steps: (1) is taking methyl acetate, carbon monoxide and hydrogen as raw material, in carbonylation catalysisAgent is carried out carbonylation and is obtained ethylidene diacetate under existing; (2), under catalyst for cracking exists, make two acetic acid AsiaEthyl ester cracking obtains vinyl acetate; Wherein, described carbonylating catalyst adopts SiO2、Al2O3Or its mixture is for carryingBody, active component comprise be selected from platinum bunch metal at least one, be selected from least one of alkali earth metal and be selected from IVAWith at least one metallic element in lanthanide element. Preferred described active component comprises platinum bunch metal, alkaline earth gold simultaneouslyBelong to element, be selected from least one metallic element in IVA and be selected from least one metallic element in lanthanide element.Now between the metallic element of IVA and the metallic element of lanthanide series metal, improving aspect the selective and yield of vinyl acetateThere is synergy.
In technique scheme, preferably at least one in platinum, palladium, osmium, iridium, ruthenium and rhodium of described platinum bunch metal.
In technique scheme, described alkali earth metal is at least one in beryllium, magnesium, calcium, strontium and barium preferably.
In technique scheme, preferably at least one in germanium, tin and lead of described IVA metal.
In technique scheme, described lanthanide series metal is at least one in lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium preferably.
In technique scheme, as most preferred technical scheme, described active component comprises platinum bunch metal, alkaline earth simultaneouslyMetallic element, IVA metal and lanthanide series metal; For example described active component comprises rhodium, strontium, tin (or plumbous) and lanthanum, orPerson embraces and draws together rhodium, strontium (or beryllium), tin, lead and lanthanum, or embraces and draw together rhodium, strontium, beryllium, tin, lead, lanthanum (or cerium), orEmbrace and draw together rhodium, strontium, beryllium, tin, lead, lanthanum and cerium.
In technique scheme, in described carbonylating catalyst, the content of platinum bunch metallic element is preferably 3.00～15.00g/L,More preferably 5.00～10.00g/L; In described carbonylating catalyst, the content of alkali earth metal is preferably 0.10～5.00g/L,More preferably 1.00～3.00g/L; In described carbonylating catalyst, be selected from least one unit of metal in IVA and lanthanide series metalCellulose content is preferably 0.50～8.00g/L, more preferably 1.00～5.00g/L. The carrier ratio that described carbonylating catalyst is usedSurface is preferably 50～300m2/ g, more preferably 150～200m2/ g, pore volume is preferably 0.80～1.20, more preferably0.90～1.00. Described in technique scheme, iodide are preferably iodomethane.
In technique scheme, the adoptable preparation method of described carbonylating catalyst, comprises the steps:
1. press the composition of catalyst by the compound of the compound of platinum bunch metallic element, alkali earth metal, IVA and group of the lanthanidesIn metal, the solution of the compound of metal mixes with carrier;
2. dry.
In technique scheme, step 1. the compound of described platinum bunch metal preferably from radium chloride, acetic acid rhodium two parts, threePhenylphosphine chlorine rhodium, rhodium nitrate, palladium bichloride, dichloro four ammonia palladiums, palladium, ammonium chloropalladite, ruthenic chloride, mistake ruthenic acid fourAt least one in interior amine, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid.Step 1. described alkaline earth metal compound preferably from alkaline earth oxide, alkaline earth metal chloride, alkaline earth nitrate,At least one in alkali earth metal sulfate and Alkaline Earth Metal Acetate. The step 1. compound of described IVA metallic element is excellentBe selected from least one in germanium chloride, stannous oxalate, stannous chloride, lead acetate, plumbi nitras and basic lead acetate. Step1. described lanthanide metals compound preferably from lanthanum acetate, lanthanum chloride, lanthanum nitrate, cerous acetate, cerium chloride, cerous nitrate,At least one in praseodymium acetate, praseodymium chloride, acetic acid neodymium, samarium trichloride, ytterbium chloride and lutecium chloride. Step is described dry temperature 2.Degree is preferably 80～120 DEG C, more preferably 100～120 DEG C.
In technique scheme, compound, the alkali earth metal of platinum bunch metallic element will be comprised by the composition of catalystIn compound, IVA and lanthanide series metal, the compound of metal and carrier hybrid mode are not particularly limited, their aqueous solutionAlso be not particularly limited the opportunity contacting with carrier. For example the present invention will be able to comprised to platinum bunch gold by the composition of catalystIn the compound of genus element, compound, IVA and the lanthanide series metal of alkali earth metal, the compound of metal first mixes and is dissolved inWater, can be also that their compound is formed successively after the aqueous solution and mixes and contact with carrier, can also be different suitableOrder contacts with carrier and obtains described catalyst.
The key of the inventive method is carbonylating catalyst, after obtaining carbonylating catalyst, by carbonylation is urgedAgent contacts and can be used for carbonylation with described co-catalyst. The mode that carbonylating catalyst contacts with co-catalyst does not haveThere is special restriction, to be also not particularly limited the opportunity that both contact. For example can be by carbonylating catalyst of the present inventionForm described catalyst for making both contact before chemical reaction, can also make both applied at catalyst of the present inventionIn reaction 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 necessarilyAmount platinum bunch metal, alkali earth metal and be selected from IVA and lanthanide series metal at least one metallic element, be conducive to carryThe activity of high major catalyst and stability, thus the yield that has improved vinyl acetate is with selective.
Experimental result shows, the prepared vinyl acetate yield of the present invention reaches 60.32%, selectively reaches 83.23%, obtainsGood technique effect, in especially described carbonylating catalyst, active component comprises platinum bunch metal, alkaline-earth metal simultaneouslyElement, when being selected from least one metallic element in IVA and being selected from least one metallic element in lanthanide series metal, obtainMore outstanding technique effect, can be in vinyl acetate synthetic. Below by embodiment, the present invention is done into oneStep is set forth.
Detailed description of the invention
[embodiment 1]
The preparation of carbonylating catalyst: will contain 6.10gRh, contain 2.90gSr and acetic acid rhodium two parts containing 2.90gSn(Rh2(OAc)4)、Sr(OAc)2·0.5H2O and stannous oxalate (SnC2O4) fully mixed dissolution be 8wt% in concentrationIn hydrochloric acid, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is 0.95, 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 Rh content is 6.10g/L, Sr content 2.90g/L, Sn content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.32% as calculated, is selectively 83.23%, 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 6.10gRh, contain 2.90gSr and acetic acid rhodium two parts containing 2.90gLa(Rh2(OAc)4)、Sr(OAc)2·0.5H2O and La (OAc)3·5H2The abundant mixed dissolution of O, in pure water, is floodedLiquid 400ml is 165m by 1.0L specific surface2/ g, pore volume is 0.95, 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, Rh content is 6.10g/L, Sr content 2.90g/L, La content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.29% as calculated, is selectively 83.34%, 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 table 2。
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of carbonylating catalyst: will contain 6.10gRh and the acetic acid rhodium two part (Rh containing 2.90gSr2(OAc)4)And Sr (OAc)2·0.5H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, by 1.0L specific surface is165m2/ g, pore volume is 0.95, 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 Rh content is 6.10g/L,Sr content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 51.16% as calculated, is selectively 72.44%, 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 Rh, Sr and SnActive component, simultaneously containing the catalyst performance of Rh, Sr and La active component than only containing Rh, Sr 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 5.00gRh, contain 1.00gBa and the RhCl containing 1.00gGe3·6H2O、 BaCl2And GeCl4In the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtain maceration extract 400ml, by 1.0L ratioSurface is 150m2/ g, pore volume is 0.90, the spherical Al that diameter is 5.6mm2O3Carrier impregnation in above-mentioned maceration extract,Leave standstill 2h in 80 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Rh content is 5.00g/L,Ba content 1.00g/L, Ge 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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 59.66% as calculated, is selectively 82.96%, 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 10.00gRh, contain 3.00gCa and the triphenylphosphine chlorine rhodium containing 5.00gSn(C54H45ClP3Rh)、Ca(NO3)2And SnCl2In the acetic acid that fully mixed dissolution is 10wt% in concentration, soakedStain liquid 400ml is 200m by 1.0L specific surface2/ g, pore volume is 1.00, the spherical SiO that diameter is 5.6mm2CarrierBe immersed in above-mentioned maceration extract, leave standstill 2h in 120 DEG C dry, obtain described catalyst. Described carbonylating catalyst warpIcp analysis, Rh content is 10.00g/L, Ca content 3.00g/L, Sn 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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.67% as calculated, is selectively 83.39%, 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 5]
The preparation of carbonylating catalyst: will contain 6.10gRh, contain 2.90gMg and the Rh (NO containing 2.90gSn3)3、MgSO4And Sn (NO3)2Fully mixed dissolution, in water outlet, obtains maceration extract 400ml, is 165m by 1.0L specific surface2/g，Pore volume is 0.95, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h dry in 100 DEG CDry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Rh content is 6.10g/L, Mg content 2.90g/L,Sn content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.31% as calculated, is selectively 83.24%, 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 6]
The preparation of carbonylating catalyst: will contain 6.10gPd, contain 2.90gBe and the PdCl containing 2.90gPb2, BeO andPb(OAc)2·3H2In the hydrochloric acid that the abundant mixed dissolution of O is 8wt% in concentration, obtain maceration extract 400ml, by 1.0L ratioSurface is 165m2/ g, pore volume is 0.95, 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 Pd content is6.10g/L, Be content 2.90g/L, Pb content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.07% as calculated, is selectively 83.03%, 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 6.10gPd, contain 2.90gBe and the dichloro four ammonia palladium (Pd containing 2.90gPb(NH3)4Cl2·H2O)、BeCl2And basic lead acetate (Pb (OAc)2·2Pb(OH)2) fully mixed dissolution in pure water,Obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is 0.95, 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, Pd content is 6.10g/L, Be content 2.90g/L, Pb content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.05% as calculated, is selectively 83.08%, 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 6.10gPd, contain 2.90gBe and the Pd (OAc) containing 2.90gSm2、BeCl2And SmCl3·6H2In the acetic acid that the abundant mixed dissolution of O is 10wt% in concentration, obtain maceration extract 400ml, by 1.0L ratioSurface is 165m2/ g, pore volume is 0.95, 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 Pd content is6.10g/L, Be content 2.90g/L, Sm content 2.90g/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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 141 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 56.84% as calculated, is selectively 80.15%, 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 6.10gRu, contain 2.90gBe and the RuCl containing 2.90gCe3·XH2O、BeCl2And CeCl3·6H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, by 1.0L specific surface is165m2/ g, pore volume is 0.95, 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 Ru content is 6.10g/L,Be content 2.90g/L, Ce content 2.90g/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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.39% as calculated, is selectively 82.37%, 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 6.10gPt, contain 2.90gBe and the ammonium chloroplatinite containing 2.90gPr((NH4)2PtCl4)、BeCl2And Cl3Pr·6H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, will1.0L specific surface is 165m2/ g, pore volume is 0.95, the spherical SiO that diameter is 5.6mm2Carrier impregnation is at above-mentioned dippingIn liquid, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Pt containsAmount is 6.10g/L, Be content 2.90g/L, Pr content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.18% as calculated, is selectively 83.14%, 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 6.10gOs, contain 2.90gBe and the OsCl containing 2.90gNd3·3H2O、BeCl2And Nd (OAc)3·5H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, by 1.0L specific surface is165m2/ g, pore volume is 0.95, 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 Os content is 6.10g/L,Be content 2.90g/L, Nd content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.20% as calculated, is selectively 83.17%, 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 6.10gIr, contain 2.90gBe and the IrCl containing 2.90gYb3·XH2O、BeCl2And YbCl3·6H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface2/g，Pore volume is 0.95, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h dry in 100 DEG CDry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Ir content is 6.10g/L, Be content 2.90g/L,Yb content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.14% as calculated, is selectively 83.22%, 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 6.10gRh, contain 2.90gSr and acetic acid rhodium two parts containing 2.90gLu(Rh2(OAc)4)、Sr(OAc)2·0.5H2O and LuCl3·6H2The abundant mixed dissolution of O, in pure water, obtains maceration extract400ml is 165m by 1.0L specific surface2/ g, pore volume is 0.95, 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, Rh content is 6.10g/L, Sr content 2.90g/L, Lu content 2.90g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 60.35% as calculated, is selectively 83.36%, 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 14]
The preparation of carbonylating catalyst: will contain 6.10gRh, contain 2.90gSr, contain 1.33gSn and the acetic acid containing 1.57gLaRhodium two part (Rh2(OAc)4)、Sr(OAc)2·0.5H2O, stannous oxalate (SnC2O4) and La (OAc)3·5H2O is abundantIn the hydrochloric acid that mixed dissolution is 8wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, holeAppearance is 0.95, 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 Rh content is 6.10g/L, Sr content 2.90g/L,Sn content 1.33g/L, La content 1.57g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 61.21% as calculated, is selectively 84.29%, 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 2 relatively can find out, is selected from IVA metal Sn and lanthanide series metal La existsThe yield and the selective aspect that improve vinyl acetate have good synergy.
[embodiment 15]
The preparation of carbonylating catalyst: will contain 6.10gRh, contain 2.90gSr, contain 1.33gPb and the acetic acid containing 1.57gLaRhodium two part (Rh2(OAc)4)、Sr(OAc)2·0.5H2O, basic lead acetate (Pb (OAc)2·2Pb(OH)2) and La (OAc)3·5H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is0.95, 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 Rh content is 6.10g/L, Sr content 2.90g/L,Pb content 1.33g/L, La content 1.57g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 61.14% as calculated, is selectively 84.38%, 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 16]
The preparation of carbonylating catalyst: will be containing 6.10gRh, containing 2.90gSr, containing 0.71gSn, containing 0.62gPb with containing 1.57gLaAcetic acid rhodium two part (Rh2(OAc)4)、Sr(OAc)2·0.5H2O, stannous oxalate (SnC2O4), basic lead acetate(Pb(OAc)2·2Pb(OH)2) and La (OAc)3·5H2In the hydrochloric acid that the abundant mixed dissolution of O is 8wt% in concentration,To maceration extract 400ml, be 165m by 1.0L specific surface2/ g, pore volume is 0.95, the spherical SiO that diameter is 5.6mm2CarryBody is immersed in above-mentioned maceration extract, leave standstill 2h in 100 DEG C dry, obtain described catalyst. Described carbonylating catalyst warpIcp analysis, Rh content is 6.10g/L, Sr content 2.90g/L, Sn content 0.71g/L, Pb content 0.62g/L, LaContent 1.57g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 62.82% as calculated, is selectively 85.55%, 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 table2。
The present embodiment and embodiment 14, embodiment 15 relatively can find out, are selected from IVA metal Sn and Pb and the present inventionOther active component has good synergy at the yield of raising vinyl acetate with selectively.
[embodiment 17]
The preparation of carbonylating catalyst: will be containing 6.10gRh, containing 2.90gBe, containing 0.71gSn, containing 0.62gPb and containingThe acetic acid rhodium two part (Rh of 1.57gLa2(OAc)4)、BeCl2, stannous oxalate (SnC2O4), basic lead acetate (Pb (OAc)2·2Pb(OH)2) and La (OAc)3·5H2In the hydrochloric acid that the abundant mixed dissolution of O is 8wt% in concentration, obtain maceration extract400ml is 165m by 1.0L specific surface2/ g, pore volume is 0.95, 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, Rh content is 6.10g/L, Be content 2.90g/L, and Sn content 0.71g/L, Pb content 0.62g/L, La containsAmount 1.57g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 62.74% as calculated, is selectively 85.67%, 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 18]
The preparation of carbonylating catalyst: will be containing 6.10gRh, containing 1.43gSr, containing 1.47gBe, containing 0.71gSn, containing 0.62gPbWith the acetic acid rhodium two part (Rh containing 1.57gLa2(OAc)4)、Sr(OAc)2·0.5H2O、BeCl2, stannous oxalate (SnC2O4)、Basic lead acetate (Pb (OAc)2·2Pb(OH)2) and La (OAc)3·5H2The abundant mixed dissolution of O is 8wt% in concentrationIn hydrochloric acid, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is 0.95, 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 Rh content is 6.10g/L, Sr content 1.43g/L, Be content 1.47g/L, SnContent 0.71g/L, Pb content 0.62g/L, La content 1.57g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 63.31% as calculated, is selectively 86.79%, 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 16, embodiment 17, in alkaline-earth metal in Be, Sr and the present inventionSelective and the yield of the collaborative favourable raising vinyl acetate of other active component, illustrated Rh, Be, Sr, Sn, Pb andBetween La active component, there is well synergy.
[embodiment 19]
The preparation of carbonylating catalyst: will be containing 6.10gRh, containing 1.43gSr, containing 1.47gBe, containing 0.71gSn, containing 0.62gPbWith the acetic acid rhodium two part (Rh containing 1.57gCe2(OAc)4)、Sr(OAc)2·0.5H2O、BeCl2, stannous oxalate (SnC2O4)、Basic lead acetate (Pb (OAc)2·2Pb(OH)2) and Ce (OAc)3·6H2The abundant mixed dissolution of O is 8wt% in concentrationIn hydrochloric acid, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/ g, pore volume is 0.95, 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 Rh content is 6.10g/L, Sr content 1.43g/L, Be content 1.47g/L, SnContent 0.71g/L, Pb content 0.62g/L, Ce content 1.57g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 63.40% as calculated, is selectively 86.78%, 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 20]
The preparation of carbonylating catalyst: will containing 6.10gRh, containing 1.43gSr, containing 1.47gBe, containing 0.71gSn, containing 0.62gPb,Containing the acetic acid rhodium two part (Rh of 0.77gLa and 0.80gCe2(OAc)4)、Sr(OAc)2·0.5H2O、BeCl2, oxalic acid AsiaTin (SnC2O4), basic lead acetate (Pb (OAc)2·2Pb(OH)2)、La(OAc)3·5H2O and Ce (OAc)3·6H2OIn the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtaining maceration extract 400ml, is 165m by 1.0L specific surface2/g，Pore volume is 0.95, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 2h dry in 100 DEG CDry, obtain described catalyst. Described carbonylating catalyst is through icp analysis, and Rh content is 6.10g/L, Sr content 1.43G/L, Be content 1.47g/L, Sn content 0.71g/L, Pb content 0.62g/L, La content 0.77g/L, Ce content0.80g/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 7.5MPa improves mixing speed to 1200rpm, and agitating heating is warming up to reaction simultaneouslyTemperature, controlling reaction temperature is 174 DEG C, the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 8.0h, 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 0.40MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 142 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 64.22% as calculated, is selectively 87.84%, 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 18, embodiment 19, La, Ce and the present invention in lanthanide series metalIn the selective and yield of the collaborative favourable raising vinyl acetate of other active component, illustrated Rh, Be, Sr, Sn, Pb,Between Ce and La active component, there is well synergy.
Table 1
Table 2
Claims (10)
1. methyl acetate carbonylation is produced the method for vinyl acetate, comprises the following steps: (1) is with methyl acetate, carbon monoxideWith hydrogen be raw material, under carbonylating catalyst, co-catalyst exist, carry out carbonylation and obtain ethylidene diacetate;(2), under catalyst for cracking exists, make ethylidene diacetate cracking obtain vinyl acetate; Wherein, described carbonylation is urgedAgent adopts SiO2、Al2O3Or its mixture is carrier, active component comprise be selected from platinum bunch metal at least one,Be selected from alkaline-earth metal at least one and be selected from IVA and lanthanide element at least one metallic element; Described helpingCatalyst is iodide.
2. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that described platinum bunch goldBelong at least one that is selected from platinum, palladium, osmium, iridium, ruthenium and rhodium.
3. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that described alkaline earth goldBelong at least one being selected from beryllium, magnesium, calcium, strontium and barium.
4. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that described IVA goldBelong at least one being selected from germanium, tin and lead.
5. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that described group of the lanthanides goldBelong at least one being selected from lanthanum, cerium, praseodymium, neodymium, samarium, ytterbium and lutetium.
6. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that platinum in catalystThe content of bunch element is 3.00～15.00g/L, and the content of alkali earth metal is 0.10～5.00g/L.
7. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that institute in catalystStating and being selected from least one content of metal in IVA and lanthanide series metal is 0.50～8.00g/L.
8. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that described iodideFor iodomethane.
9. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that described carbonylationThe temperature of reaction is 130～200 DEG C; The pressure of reaction is 3.0～10.0MPa; Carbon monoxide and hydrogen volume in reactionThan being 0.10～10.0; The time of reaction is 3.0～10.0h.
10. the method that methyl acetate carbonylation is produced vinyl acetate according to claim 1, is characterized in that carbonylationThe preparation method of catalyst, comprises the steps:
1. press the composition of catalyst by the compound of the compound of platinum bunch metallic element, alkali earth metal, IVA and group of the lanthanidesIn metal, the solution of the compound of metal mixes with carrier;
2. dry.
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| EP0108539A1 (en) * | 1982-10-30 | 1984-05-16 | BP Chemicals Limited | Preparation of esters |
| US4659865A (en) * | 1979-09-13 | 1987-04-21 | Mitsubishi Gas Chemical Co., Inc. | Process for producing ethylidenediacetate |
| US5138093A (en) * | 1975-03-10 | 1992-08-11 | Eastman Kodak Company | Process for preparing ethylidene diacetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114096347A (en) * | 2019-05-28 | 2022-02-25 | 埃讷肯公司 | Gas phase methanol carbonylation catalyst |
| EP3976249A4 (en) * | 2019-05-28 | 2023-06-14 | Enerkem Inc. | Vapor phase methanol carbonylation catalyst |
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