CN103664588B - The preparation method of vinyl acetate between to for plastic - Google Patents
The preparation method of vinyl acetate between to for plastic Download PDFInfo
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- CN103664588B CN103664588B CN201210355557.8A CN201210355557A CN103664588B CN 103664588 B CN103664588 B CN 103664588B CN 201210355557 A CN201210355557 A CN 201210355557A CN 103664588 B CN103664588 B CN 103664588B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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Abstract
The present invention relates to and a kind ofly prepare the method for vinyl acetate between to for plastic by dme and synthetic gas through catalyzed reaction.The key step of described method is: under catalyzer existence condition, by dme and synthesis gas reaction, obtains target compound; Described catalyzer is primarily of Primary Catalysts, promotor and methyl iodide composition, and in the gross weight of described catalyzer for 100wt%, Primary Catalysts accounts for 1wt% ~ 25wt%, and promotor accounts for 5wt% ~ 35wt%, and methyl iodide accounts for 40wt% ~ 75wt%; Described Primary Catalysts is elemental metals or metallic compound, described elemental metals to be selected from the periodic table of elements one or two or more kinds mixture in VIII metal, and described metallic compound is selected from one or two or more kinds mixture in the halogenide of VIII metal in the periodic table of elements, oxide compound or oxysalt; Described promotor is substituted benzenesulfonic acid.This invention simplifies the preparation process of vinyl acetate between to for plastic, reduce the preparation cost of vinyl acetate between to for plastic, the yield more than 10% ~ 30% of vinyl acetate between to for plastic can be improved.
Description
Technical field
The present invention relates to the preparation method of a kind of vinyl-acetic ester (having another name called vinyl acetate or vinyl acetate between to for plastic), specifically, relate to a kind of method being prepared vinyl acetate between to for plastic by dme and synthetic gas (carbon monoxide and hydrogen) through catalyzed reaction.
Background technology
Vinyl-acetic ester (having another name called vinyl acetate or vinyl acetate between to for plastic) is a kind of Organic Chemicals having widespread use and be worth.The products such as Vinyl Acetate Copolymer (PVAc), polyvinyl alcohol (PVA), vinyl acetate between to for plastic/ethylene copolymer (VAE) and vinylchlorid/acetate ethylene copolymer (PVCA) are prepared as can be used for.
Traditional method preparing vinyl acetate between to for plastic is mainly ethylene process, natural gas act and acetylene method.Because ethene and natural gas source lack, acetylene method is again because the shortcoming of its high energy consumption is restricted day by day.Therefore, explore one and do not rely on crude oil and new synthesis route based on coal has important economic implications.
EP0566371A2 provides one and prepares ethylidene diacetate (ethylidenediacetate, EDDA) preparation method's (EDDA can be used for preparing vinyl acetate between to for plastic), catalyst system wherein used basic composition is the elemental metals or its compound, methyl iodide and lithium iodide (or also comprising lithium acetate) that comprise in periodic table of elements VIII, the selectivity of the transformation efficiency of dme and ethylidene diacetate (EDDA) is all higher.But EDDA also needs, through a step eliminative reaction, just can obtain vinyl acetate between to for plastic.
EP0048174B1 discloses a kind of method preparing vinyl acetate between to for plastic, and the defect that the method exists is: the selectivity of vinyl acetate between to for plastic is low; Solvent selects aceticanhydride or ethylidene diacetate, product cost high.
Given this, a kind of method succinctly preparing vinyl acetate between to for plastic is efficiently provided, becomes the technical issues that need to address of the present invention.
Summary of the invention
The object of the invention is, provides a kind of with dme (CH
3oCH
3, english abbreviation: DME) with synthetic gas (carbon monoxide and hydrogen) be raw material, obtain the preparation method of vinyl acetate between to for plastic through a step catalyzed reaction.
The method preparing vinyl acetate between to for plastic of the present invention, its key step is: under catalyzer existence condition, is reacted, obtain target compound (vinyl acetate between to for plastic) by dme and synthetic gas (mixed gas be made up of hydrogen and CO (carbon monoxide converter) gas);
Wherein: described catalyzer is primarily of Primary Catalysts, promotor and methyl iodide composition, and in the gross weight of described catalyzer for 100wt%, Primary Catalysts accounts for 1wt% ~ 25wt%, and promotor accounts for 5wt% ~ 35wt%, and methyl iodide accounts for 40wt% ~ 75wt%;
Described Primary Catalysts is elemental metals or metallic compound, described elemental metals to be selected from the periodic table of elements one or two or more kinds (containing two kinds) mixture in VIII metal, and described metallic compound is selected from one or two or more kinds (containing two kinds) mixture in halogen (F, Cl, Br or I) compound of VIII metal in the periodic table of elements, oxide compound or oxysalt;
Described promotor is for by compound shown in formula I:
In formula I, R is H or C
1~ C
3alkyl.
This invention simplifies the preparation process of vinyl acetate between to for plastic, reduce the preparation cost of vinyl acetate between to for plastic, the yield more than 10% ~ 30% of vinyl acetate between to for plastic can be improved.
Embodiment
In an optimal technical scheme of the present invention, described catalyzer is made up of Primary Catalysts, promotor, Lithium Acetate or lithium iodide, methyl iodide and palladium;
In the gross weight of described catalyzer for 100wt%, Primary Catalysts accounts for 2.5wt% ~ 15wt%, promotor accounts for 10wt% ~ 25wt%, Lithium Acetate or lithium iodide account for 7wt% ~ 25wt% (preferred mass content is 12wt% ~ 20wt%), methyl iodide accounts for 50wt% ~ 70wt%, and palladium accounts for 1wt% ~ 3wt% (preferred mass content is 1wt% ~ 2wt%).
In another optimal technical scheme of the present invention, said Primary Catalysts is halogen (F, Cl, Br or I) compound of metal rhodium (Rh) or metal rhodium, oxide compound or oxysalt; Preferred Primary Catalysts is halogen (F, Cl, Br or I) compound of metal rhodium; Best Primary Catalysts is iodate rhodium (RhI3).
In another optimal technical scheme of the present invention, described promotor is for by compound shown in formula I, and wherein, R is H or methyl;
Preferred promotor is Phenylsulfonic acid or tosic acid.
Catalyzer of the present invention is obtained by the method that key step is following:
By Primary Catalysts (preferred rhodium triiodid), promotor (preferred tosic acid or Phenylsulfonic acid), Lithium Acetate or lithium iodide, the mixing of methyl iodide palladium, obtain mixture (this mixture is the present invention and states catalyzer).
The method preparing vinyl acetate between to for plastic of the present invention, comprises the steps:
(1) catalyzer obtained by aforesaid method is moved into one with in the successive reaction still of temperature regulating device and whipping appts, in this successive reaction still, pass into CO (carbon monoxide converter) gas, pressure be 0.8MPa ~ 1.3MPa, the state of temperature 50 C ~ 80 DEG C keeps 10 hours ~ 120 hours (activation of catalyzer);
(2) by dme (DME) and synthetic gas (CO+H
2) pass into and be above-mentionedly equipped with in the successive reaction still of activated catalyzer that (successive reaction still is equipped with solvent, as acetic acid etc.), in 140 DEG C ~ 200 DEG C, pressure is that 2.5MPa ~ 6MPa state keeps 1 hour ~ 8 hours, obtains target compound (vinyl acetate between to for plastic);
Wherein: in described synthetic gas, the mol ratio of hydrogen and carbon monoxide controls to be 1: (1 ~ 5) is advisable; DME, H
2be control with the mol ratio of CO be 2: 1: 4; The mass ratio of solvent and described catalyzer is (3 ~ 500): 1, and preferred mass ratio is (5 ~ 20): 1.
Below by embodiment, the present invention is further elaborated, and its object only understands content of the present invention in better.Therefore, the cited case does not limit the scope of the invention.
Embodiment 1
By 0.10g rhodium triiodid, 0.50g Lithium Acetate, 0.05g palladium, the continuous stirred tank reactor that a volume is 0.2L put into by 1.80g methyl iodide, 0.30g Phenylsulfonic acid and 14.00g acetic acid, passes into CO stir-activating after 24 hours, passes into 2.30g dme and CO: H
2the gas mixture of=2: 1, in temperature of reaction 180 DEG C, reaction pressure 4.0MPa, stirring velocity is under 600r/min condition, reacts after 10 hours, and the sample gas chromatographic analysis still liquid that takes a morsel forms, and adopts fid detector, capillary column model: HP-5.Reaction result is as follows: dimethyl ether conversion rate 90.20%, ritalin selectivity 10.24%, vinyl acetate between to for plastic selectivity 40.23%, the selectivity 8.18% of aceticanhydride, ethylidene diacetate selectivity 41.35%.
Embodiment 2
By 0.10g rhodium triiodid, 0.50g Lithium Acetate, 0.05g palladium, the continuous stirred tank reactor that a volume is 0.2L put into by the catalyzer that 1.80g methyl iodide, 0.32g tosic acid and 14.00g acetic acid are made into, pass into CO stir-activating after 24 hours, pass into 2.30g dme and CO: H
2the gas mixture of=2: 1, in temperature of reaction 175 DEG C, reaction pressure 5.0MPa, stirring velocity is under 600r/min condition, reacts after 10 hours, and the sample gas chromatographic analysis still liquid that takes a morsel forms, and adopts fid detector, capillary column model: HP-5.Reaction result is as follows: dimethyl ether conversion rate 91.30%, ritalin selectivity 13.23%, vinyl acetate between to for plastic selectivity 51.34%, the selectivity 7.51% of aceticanhydride, ethylidene diacetate selectivity 27.92%.
Claims (9)
1. prepare the method for vinyl acetate between to for plastic for one kind, it is characterized in that, the key step of described method is: dme and synthetic gas are passed into and be equipped with in the successive reaction still of activated catalyzer and solvent, in 140 DEG C ~ 200 DEG C, pressure is that 2.5MPa ~ 6MPa state keeps 1 hour ~ 8 hours, obtains target compound;
Wherein: in dme, synthetic gas, in hydrogen and synthetic gas, the mol ratio of carbon monoxide is 2: 1: 4; The mass ratio of solvent and described catalyzer is (3 ~ 500): 1;
Described catalyzer is primarily of Primary Catalysts, promotor and methyl iodide composition, and in the gross weight of described catalyzer for 100wt%, Primary Catalysts accounts for 1wt% ~ 25wt%, and promotor accounts for 5wt% ~ 35wt%, and methyl iodide accounts for 40wt% ~ 75wt%;
Described Primary Catalysts is elemental metals or metallic compound, described elemental metals to be selected from the periodic table of elements one or two or more kinds mixture in VIII metal, and described metallic compound is selected from one or two or more kinds mixture in the halogenide of VIII metal in the periodic table of elements, oxide compound or oxysalt;
Described promotor is for by compound shown in formula I:
In formula I, R is H or C
1~ C
3alkyl.
2. the method for claim 1, is characterized in that, wherein said catalyzer is made up of Primary Catalysts, promotor, Lithium Acetate or lithium iodide, methyl iodide and palladium;
In the gross weight of described catalyzer for 100wt%, Primary Catalysts accounts for 2.5wt% ~ 15wt%, and promotor accounts for 10wt% ~ 25wt%, and Lithium Acetate or lithium iodide account for 7wt% ~ 25wt%, and methyl iodide accounts for 50wt% ~ 70wt%, and palladium accounts for 1wt% ~ 3wt%.
3. method as claimed in claim 2, it is characterized in that, wherein said catalyzer is made up of Primary Catalysts, promotor, Lithium Acetate or lithium iodide, methyl iodide and palladium;
In the gross weight of described catalyzer for 100wt%, Primary Catalysts accounts for 2.5wt% ~ 15wt%, and promotor accounts for 10wt% ~ 25wt%, and Lithium Acetate or lithium iodide account for 12wt% ~ 20wt%, and methyl iodide accounts for 50wt% ~ 70wt%, and palladium accounts for 1wt% ~ 2wt%.
4. the method as described in claim 1,2 or 3, is characterized in that, wherein said Primary Catalysts is the halogenide of metal rhodium or metal rhodium, oxide compound or oxysalt.
5. method as claimed in claim 4, it is characterized in that, wherein said Primary Catalysts is the halogenide of metal rhodium.
6. method as claimed in claim 5, it is characterized in that, wherein said Primary Catalysts is iodate rhodium.
7. the method as described in claim 1,2 or 3, is characterized in that, wherein said promotor is for by compound shown in formula I, and wherein, R is H or methyl.
8. method as claimed in claim 7, it is characterized in that, wherein said promotor is Phenylsulfonic acid or tosic acid.
9. as the method in claims 1 to 3 as described in any one, it is characterized in that, wherein said deactivated catalyst is by following method activation:
Catalyzer in claims 1 to 3 described in any one is moved into one with in the successive reaction still of temperature regulating device and whipping appts, in this successive reaction still, pass into CO (carbon monoxide converter) gas, pressure be 0.8MPa ~ 1.3MPa, the state of temperature 50 C ~ 80 DEG C keeps 10 hours ~ 120 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210355557.8A CN103664588B (en) | 2012-09-19 | 2012-09-19 | The preparation method of vinyl acetate between to for plastic |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210355557.8A CN103664588B (en) | 2012-09-19 | 2012-09-19 | The preparation method of vinyl acetate between to for plastic |
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|---|---|
| CN103664588A CN103664588A (en) | 2014-03-26 |
| CN103664588B true CN103664588B (en) | 2016-01-20 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0108539B1 (en) * | 1982-10-30 | 1986-08-27 | BP Chemicals Limited | Preparation of esters |
| EP0566371A2 (en) * | 1992-04-15 | 1993-10-20 | Air Products And Chemicals, Inc. | Process for converting dimethyl ether to ethylidene diacetate |
| CN101245003A (en) * | 2008-03-06 | 2008-08-20 | 华东理工大学 | Process for producing vinyl acetate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58157746A (en) * | 1982-03-16 | 1983-09-19 | Mitsubishi Gas Chem Co Inc | Production of vinyl acetate |
-
2012
- 2012-09-19 CN CN201210355557.8A patent/CN103664588B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0108539B1 (en) * | 1982-10-30 | 1986-08-27 | BP Chemicals Limited | Preparation of esters |
| EP0566371A2 (en) * | 1992-04-15 | 1993-10-20 | Air Products And Chemicals, Inc. | Process for converting dimethyl ether to ethylidene diacetate |
| CN101245003A (en) * | 2008-03-06 | 2008-08-20 | 华东理工大学 | Process for producing vinyl acetate |
Non-Patent Citations (1)
| Title |
|---|
| 双醋酸亚乙酯裂解制醋酸乙烯的研究;李俊岭等，;《上海化工》;201201;第37卷(第1期);P11-14 * |
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