CN105585500A - Method of preparing vinyl acetate from methyl acetate - Google Patents
Method of preparing vinyl acetate from methyl acetate Download PDFInfo
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- CN105585500A CN105585500A CN201410577444.1A CN201410577444A CN105585500A CN 105585500 A CN105585500 A CN 105585500A CN 201410577444 A CN201410577444 A CN 201410577444A CN 105585500 A CN105585500 A CN 105585500A
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Abstract
The invention relates to a method of preparing vinyl acetate from methyl acetate and mainly solves the problems of low yield and low selectivity of the vinyl acetate when methyl acetate is successively subjected to carbonylation and pyrolysis to prepare the vinyl acetate. In the technical scheme, the method mainly includes the following steps: 1) carbonylating the methyl acetate to obtain ethylidene diacetate; and 2) pyrolyzing the ethylidene diacetate to obtain the vinyl acetate. A carbonylation catalyst includes a main catalyst and a co-catalyst, wherein the main catalyst includes a carrier and an active component, a rhodium compound being the active component, and the co-catalyst is an iodide, and the carrier is silicon dioxide which is modified by modifying metal elements and has an aluminum coating on the surface. The content of aluminum is 1.00-10.00 g/L, the content of the modifying metal elements is 0.010-1.00 g/L, and the modifying metal elements include at least one metal element in the IVB group.
Description
Technical field
The present invention relates to methyl acetate and prepare the method for vinyl acetate.
Background technology
Vinyl acetate (VAc) is one of 50 kinds of industrial chemicals of world wide production maximum, is total to by autohemagglutination or with other monomerPoly-, can generate polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) emulsion, vinyl acetate-ethylene copolymerization emulsions (VAE)Or the derivative such as copolymer resins (EVA), vinyl acetate-chloride copolymer (EVC). These derivatives are widely used inThe cementing agent of adhesive, building coating, paper or fabric, coating, ink, leather processing, fiber process, emulsifying agent,The aspect such as water-solubility membrane and soil conditioner.
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 is prepared 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 is prepared the side of vinyl acetateMethod, comprises the following steps: (1), taking methyl acetate, carbon monoxide and hydrogen as raw material, exists at carbonylating catalystUnder carry out carbonylation obtain ethylidene diacetate; (2) under catalyst for cracking exists, ethylidene diacetate is splitSeparate and obtain vinyl acetate; Wherein, described carbonylating catalyst comprises major catalyst and co-catalyst, major catalyst comprise carryBody, active component; Active component adopts the compound of rhodium; Described co-catalyst is iodide; Described carrier is its surfaceContain aluminized coating and with the element modified silica of modified metal; Described aluminium content is 1.00～10.00g/L; Modification goldGenus constituent content is 0.010～1.00g/L; Described modified metal element is selected from least one in IVB metallic element.
The compound of rhodium described in technique scheme is preferably RhCl3. Described iodide are preferably iodomethane. Described aluminiumCoating material is selected from least one in aluminium hydroxide, boehmite, boehmite and aluminum phosphate. More preferably described aluminiumCoating comprises aluminium hydroxide and aluminum phosphate simultaneously. Described IVB metallic element is selected from least one in Ti, Zr and Hf.More preferably described IVB metallic element comprises Hf and Zr simultaneously.
In technique scheme, the optional preparation method of described major catalyst, comprises the steps:
1. described aluminized coating raw material and Ludox are mixed to get to coating liquid;
2. above-mentioned coating liquid is coated to silica surface, dry, roasting obtains described catalyst carrier precursor I;
3. be immersed in catalyst carrier precursor I dry obtaining by being mixed with the aqueous solution containing the compound of IVB metallic elementDescribed catalyst carrier II;
4. press the composition of catalyst by RhCl3II mixes with catalyst carrier;
5. standing, dry, roasting, obtains described major catalyst.
In technique scheme step 3. described baking temperature be preferably 80～120 DEG C. More preferably 100～120 DEG C.
The key of the inventive method is the selection of major catalyst, after obtaining major catalyst, by make major catalyst withDescribed co-catalyst contact can obtain the carbonylating catalyst described in the present invention. Major catalyst contacts with co-catalystMode is not particularly limited, to be also not particularly limited the opportunity that both contact. For example can be by 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.
The present inventor finds, in technique scheme, activity component impregnation is used to aluminum phosphate, hydrogen-oxygen at the same timeChange aluminium do the catalyst that obtains on aluminized coating raw material and the compound modified carrier with Hf and Zr be no matter selectively orIt is best that vinyl acetate yield has all reached.
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 step (1) carbonylating catalyst carrier uses containing aluminized coating and useIVB metallic element carries out after modification, is conducive to improve activity and the stability of major catalyst, thereby has improved vinyl acetateYield and selective.
Experimental result shows, the prepared vinyl acetate yield of the present invention reaches 60.38%, selectively reaches 83.35%, getsObtained good technique effect. Especially use aluminum phosphate and aluminium hydroxide to do at step (1) carbonylating catalyst carrierAluminized coating raw material and with containing Hf with when collaborative containing the modification of Zr metallic element, has obtained more outstanding technique effect. BelowBy embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminium-hydroxide powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.6gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L catalystPrecursor carrier I is upper, and 100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 60.38% as calculated, is selectively 83.35%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[comparative example 1]
For the comparative example of [embodiment 1].
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, the spherical SiO that is 5.6mm by 1.0L diameter2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG CDry, in N2 atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst divides through ICPAnalyse, Rh content is 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 50.27% as calculated, is selectively 75.78%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[comparative example 2]
For the comparative example of [embodiment 1].
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminium-hydroxide powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier II. Described carrier is through using icp analysis, Al content 3.40g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 54.63% as calculated, is selectively 80.20%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[comparative example 3]
For the comparative example of [embodiment 1].
The preparation of carbonylating catalyst carrier II: by the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6LBe immersed in the spherical SiO that 1.0L diameter is 5.6mm2On carrier, 100 DEG C dry obtains described catalyst carrier II. InstituteState carrier through using icp analysis, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: the RhCl33H2O containing 7.20gRh is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 54.78% as calculated, is selectively 80.42%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
By finding out compared with embodiment 1, the catalyst carrier that the present invention adopts is used containing aluminized coating and use simultaneouslyIVB metallic element carries out the Performance Ratio of modification rear catalyst without the carrier of any modification, than only using the compound modified of aluminiumCarrier, more excellent than the performance of the catalyst of only making with the metal-modified carrier of IVB, vinyl acetate selectively withIt is high that yield is all wanted, and these data from embodiment 1, comparative example 1～3 can be found out, compound and IVB containing aluminium have been describedBetween metal, there is good synergy.
[comparative example 4]
For the comparative example of [embodiment 1].
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminium-hydroxide powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L catalysisIn agent carrier precursor I, 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 4h, obtain described catalyst carrierII. Described carrier is through using icp analysis, Al content 3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 55.04% as calculated, is selectively 80.36%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
By finding out compared with embodiment 1, carrier, only carries out carrier containing after the modification of IVB metallic element at dippingThe performance of dry its catalyst of preparing is better than the catalyst performance to taking roasting to prepare after carrier drying, and this is from implementingThe data of example 1, comparative example 4 can be found out.
[comparative example 5]
For the comparative example of [embodiment 1].
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminium-hydroxide powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier II. Described carrier is through using icp analysis, Al content 3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 6.80gRh3·3H2O, containing the basic zirconium chloride of 0.60gZr(ZrOCl2·8H2O) be dissolved in pure water, obtain maceration extract 500ml, by catalyst carrier II dipping described in 1.0LIn above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, described in obtainingMajor catalyst. Described major catalyst is through icp analysis, and Rh content is 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 54.43% as calculated, is selectively 80.53%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
By finding out compared with embodiment 1, together with the active component containing IVB metal and catalyst, flood,The performance of catalyst does not obtain good effect, and these data from embodiment 1, comparative example 5 can be found out. Explanation containsThe compound of aluminium and containing having good synergy between IVB metal.
[embodiment 2]
The preparation of carbonylating catalyst carrier II: be that 35wt% silicon is molten by boehmite powder and concentration containing 3.40gAlGlue 10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, urges described in obtainingAgent precursor carrier I. By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L and urgesAgent precursor carrier I is upper, and 100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, and Al containsAmount 3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 60.40% as calculated, is selectively 83.14%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 3]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by boehmite powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L catalysisIn agent carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 83.17%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 4]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L catalysisIn agent carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 60.51% as calculated, is selectively 83.48%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 5]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. Titanium tetrachloride hydrochloric acid solution 0.6L containing 0.60gTi is immersed in 1.0L catalyst carrier precursor I,100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content 3.40g/L, Ti content0.60g/L。
The preparation of carbonylation major catalyst: the RhCl33H2O containing 7.20gRh is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 60.34% as calculated, is selectively 83.26%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 6]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. The hydrochloric acid solution 0.6L of the hafnium tetrachloride containing 0.60gHf is immersed in to 1.0L catalyst carrier precursor IUpper, 100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content 3.40g/L, HfContent 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 60.43% as calculated, is selectively 83.37%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 7]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox 5.0g by the aluminum phosphate powder concn containing 1.00gAlFully be mixed to get coating liquid, coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2On carrier,Under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalyst carrierPrecursor I. By the basic zirconium chloride (ZrOCl containing 0.10gZr2·8H2O) aqueous solution 0.1L is immersed in 1.0L catalyst carrierIn precursor I, 80 DEG C dry obtains described catalyst carrier II. Described carrier is through with icp analysis, Al content 1.00g/L,Zr content 0.10g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 59.56% as calculated, is selectively 82.98%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 8]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 10.00gAl40.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 1.00gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L catalysisIn agent carrier precursor I, 120 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content10.00g/L, Zr content 1.00g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 60.55% as calculated, is selectively 83.19%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 9]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminum phosphate powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.2gZr2·8H2O), acid-soluble containing the hafnium tetrachloride salt of 0.4gHfLiquid 0.6L is immersed in 1.0L catalyst carrier precursor I, and 100 DEG C dry obtains described catalyst carrier II. Described carrierThrough using icp analysis, Al content 3.40g/L, Zr content 0.20g/L, Hf content 0.40g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 62.70% as calculated, is selectively 85.45%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
Find out on year-on-year basis by embodiment 9 and embodiment 4 and embodiment 6, in the selective and yield side of improving vinyl acetateFace, Zr and Hf have synergy.
[embodiment 10]
The preparation of carbonylating catalyst carrier II: by containing the aluminum phosphate powder of 2.00gAl, containing the aluminium hydroxide of 1.40gAlPowder and concentration are that 35wt% Ludox 10.0g is fully mixed to get coating liquid, coating liquid are sprayed to 1.0L uniformly straightFootpath is on the spherical sio2 carrier of 5.6mm, under ventilation condition, places 1h, and 100 DEG C dry, then at 450 DEG C of barsRoasting 4h under part, obtains described catalyst carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) waterSolution 0.6L is immersed in 1.0L catalyst carrier precursor I, and 100 DEG C dry obtains described catalyst carrier II. Described yearBody is through using icp analysis, Al content 3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 62.61% as calculated, is selectively 85.27%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
Find out on year-on-year basis by embodiment 10 and embodiment 1 and embodiment 4, improving the selective and yield of vinyl acetateAspect, aluminium hydroxide and aluminum phosphate have synergy.
[embodiment 11]
The preparation of carbonylating catalyst carrier II: by containing the aluminum phosphate powder of 2.00gAl, containing the aluminium hydroxide of 1.40gAlPowder and concentration are that 35wt% Ludox 10.0g is fully mixed to get coating liquid, coating liquid are sprayed to 1.0L uniformly straightFootpath is the spherical SiO of 5.6mm2On carrier, under ventilation condition, place 1h, 100 DEG C dry, then at 450 DEG C of barsRoasting 4h under part, obtains described catalyst carrier precursor I. By containing the basic zirconium chloride (ZrOCl28H2O) of 0.60gZr,Hafnium tetrachloride hydrochloric acid solution 0.6L containing 0.40gHf is immersed in 1.0L catalyst carrier precursor I, 100 DEG C of dry obtainingDescribed catalyst carrier II. Described carrier is through with icp analysis, Al content 3.40g/L, and Zr content 0.20g/L, Hf containsAmount 0.40g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 7.5MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 168 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2:1, after sustained response 7.5h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 64.80% as calculated, is selectively 87.44%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
Find out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, improving the selective and yield of vinyl acetateAspect, aluminium hydroxide, aluminum phosphate and Zr, Hf have synergy.
[embodiment 12]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminium-hydroxide powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L catalysisIn agent carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 3.0MPa improves mixing speed to 1500rpm, agitating heating is warming up to instead simultaneouslyAnswer temperature, controlling reaction temperature is 130 DEG C, and the mol ratio of carbon monoxide and hydrogen is 1:10, after sustained response 3.0h,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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 53.22% as calculated, is selectively 82.65%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
[embodiment 13]
The preparation of carbonylating catalyst carrier II: be 35wt% Ludox by aluminium-hydroxide powder and concentration containing 3.40gAl10.0g is fully mixed to get coating liquid, and coating liquid is sprayed to the spherical SiO that 1.0L diameter is 5.6mm uniformly2CarryOn body, under ventilation condition, place 1h, 100 DEG C dry, and then roasting 4h under 450 DEG C of conditions, obtains described catalysisAgent carrier precursor I. By the basic zirconium chloride (ZrOCl containing 0.60gZr2·8H2O) aqueous solution 0.6L is immersed in 1.0L catalysisIn agent carrier precursor I, 100 DEG C dry obtains described catalyst carrier II. Described carrier is through using icp analysis, Al content3.40g/L, Zr content 0.60g/L.
The preparation of carbonylation major catalyst: by the RhCl containing 7.20gRh3·3H2O is dissolved in pure water, obtains maceration extract580ml, is immersed in catalyst carrier II described in 1.0L in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, at N2In atmosphere, be warming up to 500 DEG C of roasting 5h, obtain described major catalyst. Described major catalyst is through icp analysis, Rh contentFor 7.20g/L.
Synthesizing of vinyl acetate:
Step (1): by 0.5mol acetic acid, 0.02mol carbonylation major catalyst, 0.02mol iodomethane and 0.15molMethyl acetate adds in 500ml titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then logicalEnter carbon monoxide and hydrogen until pressure 10.0MPa improves mixing speed to 1500rpm, agitating heating is warming up to simultaneouslyReaction temperature, controlling reaction temperature is 200 DEG C, the mol ratio of carbon monoxide and hydrogen is 10:1, sustained response 10.0hAfter, 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,Except desolventizing, ethyl acetate, acetaldehyde and other accessory substances, obtain ethylidene diacetate through rectification and purification.
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 0.30MPa after air with argon gas, improves mixing speed extremely600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 145 DEG C, after sustained response 40min,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 83.03%, for convenience of explanation and relatively, will carryThe yield of the preparation condition of body modified condition, catalyst, reaction condition, material feeding amount, vinyl acetate and selectively dividingDo not list in table 1 and table 2.
Table 1
Table 2
Claims (10)
1. the method for methyl acetate synthesis vinyl acetate, comprises the following steps: (1) is with methyl acetate, carbon monoxide and hydrogenFor raw material, under carbonylating catalyst exists, carry out carbonylation and obtain ethylidene diacetate; (2) at cracking and catalyzingUnder agent exists, make ethylidene diacetate cracking obtain vinyl acetate; Wherein, described carbonylating catalyst comprises major catalystAnd co-catalyst, major catalyst comprises carrier, active component; Active component adopts the compound of rhodium; Described co-catalystFor iodide; Described carrier is that aluminized coating is contained and with the element modified silica of modified metal in its surface; Described aluminium containsAmount is 1.00～10.00g/L; Modified metal constituent content is 0.010～1.00g/L; Described modified metal element is selected from IVBAt least one in metallic element.
2. method according to claim 1, the compound that it is characterized in that described rhodium is RhCl3。
3. method according to claim 1, is characterized in that described iodide are iodomethane.
4. method according to claim 1, it is characterized in that described aluminized coating raw material be selected from aluminium hydroxide, boehmite,At least one in boehmite and aluminum phosphate.
5. method according to claim 1, is characterized in that described IVB metallic element is selected from Ti, Zr and HfAt least one.
6. method according to claim 1, the temperature that it is characterized in that described carbonylation is 130～200 DEG C.
7. method according to claim 1, the pressure that it is characterized in that described carbonylation is 3.0～10.0MPa.
8. method according to claim 1, is characterized in that carbon monoxide and hydrogen volume ratio in described carbonylationBe 0.10～10.0.
9. method according to claim 1, the time that it is characterized in that described carbonylation is 3.0～10.0h.
10. method according to claim 1, is characterized in that comprising the steps: the preparation method of major catalyst
1. described aluminized coating raw material and Ludox are mixed to get to coating liquid;
2. above-mentioned coating liquid is coated to silica surface, dry, roasting obtains described catalyst carrier precursor I;
3. be immersed in catalyst carrier precursor I dry obtaining by being mixed with the aqueous solution containing the compound of IVB metallic elementDescribed catalyst carrier II;
4. press the composition of catalyst by RhCl3II mixes with catalyst carrier;
5. standing, dry, roasting, obtains described major catalyst.
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| 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 |
| CN101124043A (en) * | 2004-12-20 | 2008-02-13 | 国际人造丝公司 | Modified support materials for catalysts |
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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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