CN1361761A - Process for the preparation of methyl methacrylate - Google Patents
Process for the preparation of methyl methacrylate Download PDFInfo
- Publication number
- CN1361761A CN1361761A CN99816839.4A CN99816839A CN1361761A CN 1361761 A CN1361761 A CN 1361761A CN 99816839 A CN99816839 A CN 99816839A CN 1361761 A CN1361761 A CN 1361761A
- Authority
- CN
- China
- Prior art keywords
- methyl alcohol
- methacrylaldehyde
- methyl methacrylate
- reaction mixture
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for the preparation of methyl methacrylate, which comprises subjecting methacrolein and methanol to direct esterification to thereby obtain a reaction mixture containing at least methyl methacrylate and methanol, adding additional methacrolein as the entrainer to the reaction mixture, and distilling the resulting mixture to recover the methanol.
Description
The present invention relates to a kind of method for preparing methyl methacrylate, can from reaction mixture liquid, reclaim methyl alcohol according to this method by distillation, reaction mixture liquid is to be reacted by the direct esterification of methacrylaldehyde and methyl alcohol to obtain, it contains methyl methacrylate and methyl alcohol at least, and the methyl alcohol of recovery can be used as the raw material of direct esterification reaction.
Background technology
Concerning reclaim methyl alcohol from the reaction mixture liquid that contains methyl methacrylate and methyl alcohol by distillation, JP-B-1-47454 has proposed a kind of method, and it comprises goes into distillation tower with the stable hydrocarbon feeding that contains 6 to 8 carbon atoms, thereby carries out separation of methanol etc.
JP-A-57-9740 has proposed a kind of similar method, wherein work as the mixture liquid feeding that will contain methyl alcohol, water and methyl methacrylate and go into distillation tower, thereby during by distillation refining methacylic acid methyl esters, the stable hydrocarbon that will contain 6 to 7 carbon atoms places on the column plate that is higher than previous mixture liquid feed tray substantially, the result, stable hydrocarbon with basically all the methyl alcohol of amount distill out by cat head and separate by the phase separation jar, methyl alcohol is supplied to second column mutually with by recovery methyl alcohol at the bottom of the tower then.
In addition, JP-A-58-180457 discloses separation of methanol in such a way: in the presence of methyl methacrylate and water, can add with the entrainer that methyl alcohol forms azeotropic mixture and contain in the mixture of methyl alcohol, water and methyl methacrylate, carry out component distillation then, thereby obtain entrainer and methanol mixture by cat head, and when mixture forms two phase times, this two-phase can be separated from each other.In described JP-A,, other solvent such as Di Iso Propyl Ether, tetrahydrofuran (THF) and methylcarbonate have also been enumerated as suitable entrainer except listing hydrocarbon solvent such as normal hexane, octane, hexanaphthene, benzene and toluene.
And, JP-A-7-69948 discloses and can reclaim methyl alcohol in such a way: will obtain mixing liquid in hydrocarbon solvent and the water adding reaction mixture liquid, mixing liquid is separated into organic phase and aqueous methanol two-phase mutually, then by distillation by the aqueous methanol methyl alcohol that is separated.
Yet, according to these methods, in the still-process, add a large amount of hydrocarbon as entrainer implementing component distillation, the result, distillation needs a large amount of useful matteies.And, when attempting to react when preparing methyl methacrylate by the methyl alcohol that utilize to reclaim and methacrylaldehyde generation direct esterification, the entrainer that contains in must methyl alcohol by method Separation and Recovery such as distillation, extractions, this just makes that production process is pretty troublesome.
Except aforesaid method, also have by not using any entrainer distillation reaction mixture to reclaim the method for methyl alcohol.Yet according to these methods, the methyl alcohol of recovery contains the target product of a large amount of direct esterification reactions, i.e. methyl methacrylate, so such method is not efficiently.
Disclosure of an invention
Therefore, the purpose of this invention is to provide a kind of method for preparing methyl methacrylate, according to this method, can (obtain by reaction mixture liquid by distillation by the direct esterification of methacrylaldehyde and methyl alcohol reaction, it contains methyl methacrylate and methyl alcohol at least) the middle methyl alcohol that reclaims, the methyl alcohol that reclaims can be used as the material of direct esterification reaction, wherein when reclaiming methyl alcohol by distillation, do not use any hydrocarbon (should separating and remove afterwards) as entrainer to simplify production process, can reduce the content of methyl methacrylate in the methyl alcohol of recovery like this.
The contriver has carried out extensive studies, found that when reclaiming methyl alcohol by distillation can address the above problem as entrainer by adding extra methacrylaldehyde.Therefore, realized the present invention.
Here it is, the invention provides a kind of method for preparing methyl methacrylate, thereby it comprises the reaction mixture liquid that makes methacrylaldehyde and methyl alcohol generation direct esterification reaction be contained methyl methacrylate and methyl alcohol at least, in described reaction mixture, add extra methacrylaldehyde as entrainer, and distill resulting reaction mixture liquid to reclaim methyl alcohol.
Among the present invention, the methyl alcohol of recovery can be used as the raw material by direct esterification prepared in reaction methyl methacrylate.
Implement optimal mode of the present invention
Among the present invention, the method that the direct esterification reaction by methacrylaldehyde and methyl alcohol (being called for short " direct esterification reaction " here) prepares methyl methacrylate is not particularly limited, and can be gas phase or liquid phase reaction arbitrarily.How to implement this reaction and also be not particularly limited, can any mode continuous or intermittence implement reaction.For example, can provide in a continuous manner in liquid phase use palladium-based catalyst to implement the method for this reaction a kind of comprising here.
Though the reaction mixture liquid that obtains by the direct esterification reaction contains unreacted raw material and methyl methacrylate product usually, corresponding reaction mixture liquid is unreacting material and the methyl methacrylate product that contains methyl alcohol at least among the present invention.
The change in concentration of methyl alcohol and methyl methacrylate depends on reaction conditions etc. in the reaction mixture liquid.For example, when using palladium-based catalyst to implement this reaction in liquid phase, the concentration of methyl alcohol is generally 25 to 70% weight in the reaction mixture liquid, and wherein the concentration of methyl methacrylate is generally 20 to 60% weight.In addition, reaction mixture liquid contains unreacting material, methyl-formiate by product, water and other material of methacrylaldehyde usually.
When needs are removed low-boiling by-products such as methyl-formiate from reaction mixture liquid, before the distillation of reclaiming methyl alcohol, allow to add operation, implementation and operation in such a way for example: in advance the reaction mixture liquid feeding is gone into distillation tower, remove the low-boiling by-products that contains part methacrylaldehyde and methyl alcohol by the cat head distillation.
Among the present invention, from when reclaiming methyl alcohol the reaction mixture, in reaction mixture liquid, add extra methacrylaldehyde as entrainer by distillation.Be not particularly limited to the method that wherein adds extra methacrylaldehyde.For example, provide here to comprise respectively to carry the method for reaction mixture liquid and methacrylaldehyde and to comprise methacrylaldehyde is added in the reaction mixture liquid, be conveyed into the method for distillation tower then to the proper site of distillation tower.By distillation, methyl alcohol and methacrylaldehyde (it has azeotropic point with methyl alcohol) can be distillated by cat head.
The add-on that is used for the extra methacrylaldehyde of this purpose is preferably 20 to 200 weight parts, preferred especially 40 to 80 weight parts (methyl alcohol that contains in the reaction mixture liquid based on 100 weight parts).When the amount of methacrylaldehyde is less than 20 weight parts, may distill out a large amount of methyl methacrylates when reclaiming methyl alcohol, thereby make the recovery difficulty of methyl alcohol.When the amount of methacrylaldehyde during more than 200 parts of weight, the methacrylaldehyde of unnecessary amount loops back reactor, the result makes the ratio of methyl alcohol and methacrylaldehyde raw material restive in suitable scope, and perhaps auto-polymerization can take place methacrylaldehyde, thereby reaction is had adverse influence.
Among the present invention, the form that is used for the distillation tower of Methanol Recovery is not particularly limited, and is conventional as column plate type and filling type.Liquid in tower forms two phase times, uses decanting vessel separable and take away water.Though distillation condition is not particularly limited, preferably distilling pressure is normal pressure or decompression, and column bottom temperature is not higher than 120 ℃ to suppress polymerization.
Among the present invention, the methyl alcohol that reclaims by distillation contains methacrylaldehyde.The change in concentration of methyl alcohol and methacrylaldehyde depends on the reaction mixture liquid that is distilled, distillatory operational condition etc. in the methyl alcohol that reclaims.Methanol concentration is generally 30 to 70% weight, and the concentration of methacrylaldehyde is generally 20 to 70% weight.
The methyl alcohol of Hui Shouing can be used as the raw material by above-mentioned direct esterification prepared in reaction methyl methacrylate like this.When passing through the raw material of the direct esterification prepared in reaction methyl methacrylate in initial reaction device or another reactor, add methyl alcohol and methacrylaldehyde usually in right amount to regulate required material concentration or required add-on with its conduct.
With reference to following embodiment and Comparative Examples explanation the present invention.Weight by gas chromatographic analysis reaction mixture liquid and analogue is formed.
Embodiment 1
In being equipped with 4 liters of reactors of condenser and agitator, pack into the reaction liquid of 350g catalyzer (calcium carbonate catalyst that contains 5% weight palladium-1% weight lead-1% weight iron) and 700g methacrylaldehyde and 1280g methyl alcohol, reaction continues 4 hours under the pressure of 400kPaabs, 80 ℃ bath temperature, charge into air and nitrogen, synthesizing methylmethacrylate thus with the speed of 4.77Nl/min and 5.0Nl/min respectively simultaneously.Collect and the analytical reaction product, found that the transformation efficiency of methacrylaldehyde and the selectivity of methyl methacrylate are respectively 75.1% and 85.2%.
With collecting the distillation tower that the reaction mixture liquid feeding that obtains goes into to have 50 column plates like this, distill out low-boiling point material such as methyl-formiate by cat head.Like this after the distillation, find that reaction mixture liquid has the composition of the water of the methacrylaldehyde of the methyl alcohol of the methyl methacrylate that contains 32.1% weight, 51.1% weight, 8.8% weight and 6.4% weight.
Next, at tower top pressure is 80kPaabs, reflux ratio is to implement distillation at 2.0 o'clock, simultaneously described liquid is gone into to have the 25th column plate of the Oldershaw type distillation tower of 50 column plates with the 394.7g/h feeding, and methacrylaldehyde is gone into wherein the 24th column plate with the 105.3g/h feeding.The result, obtain containing the distillate of the methyl methacrylate of the methacrylaldehyde of methyl alcohol, 37.4% weight of 53.9% weight and 7.4% weight with 374.1g/h by the distillation cat head, by the liquid that obtains containing the methyl methacrylate of 78.8% weight and the water of 16.4% weight (in other words, not containing methacrylaldehyde and methyl alcohol substantially) at the bottom of the tower with 125.8g/h.The ratio of the partition rate of the methyl methacrylate in the distillate in methyl methacrylate and the liquid at the bottom of the tower is 0.28.Though the distillate that is obtained by cat head contains a spot of methyl methacrylate, it is no problem that distillate is still by the raw material that provides methyl alcohol and methacrylaldehyde to react as direct esterification.Comparative Examples 1
Implement distillation to reclaim methyl alcohol in the mode identical with embodiment 1, different is distillation tower not to be gone in the methacrylaldehyde feeding.The result, obtain containing the liquid of the methyl methacrylate of the methacrylaldehyde of methyl alcohol, 12.3% weight of 72.0% weight and 14.7% weight with 280.0g/h by the distillation cat head, by the liquid that obtains containing the methyl methacrylate of 74.7% weight and the water of 20.1% weight (in other words, not containing methacrylaldehyde and methyl alcohol substantially) at the bottom of the tower with 114.7g/h.Yet in the distillate in methyl methacrylate and the liquid at the bottom of the tower ratio of the partition rate of methyl methacrylate be 0.48, bigger than among the embodiment 1.
Industrial Applicability A
According to the present invention, can be by reactant mixture liquid (by methacrolein and methyl alcohol by distillation The direct esterification reaction obtains, and contains at least methyl methacrylate and methyl alcohol) the middle methyl alcohol that reclaims, When the methyl alcohol that reclaims is used as the raw material of direct esterification reaction, can simplify production process, and can reduce back The content of methyl methacrylate in the methyl alcohol of receiving is so that can make efficiently the target product methyl-prop The olefin(e) acid methyl esters.
Claims (2)
1, a kind of method for preparing methyl methacrylate, thereby it comprises the reaction mixture liquid that makes methacrylaldehyde and methyl alcohol generation direct esterification reaction be contained methyl methacrylate and methyl alcohol at least, in described reaction mixture liquid, add extra methacrylaldehyde as entrainer, and the reaction mixture liquid that distillation obtains is to reclaim methyl alcohol.
2, according to the process of claim 1 wherein that the methyl alcohol that reclaims is used as the raw material of described direct esterification reaction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02731998A JP3238894B2 (en) | 1998-02-09 | 1998-02-09 | Method for producing methyl methacrylate |
| PCT/JP1999/004268 WO2001010811A1 (en) | 1998-02-09 | 1999-08-06 | Process for the preparation of methyl methacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1361761A true CN1361761A (en) | 2002-07-31 |
| CN1155556C CN1155556C (en) | 2004-06-30 |
Family
ID=26365234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998168394A Expired - Lifetime CN1155556C (en) | 1998-02-09 | 1999-08-06 | Process for the preparation of methyl methacrylate |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3238894B2 (en) |
| CN (1) | CN1155556C (en) |
| WO (1) | WO2001010811A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111511468A (en) * | 2018-01-10 | 2020-08-07 | 陶氏环球技术有限责任公司 | Heterogeneous catalyst for the production of methyl methacrylate by oxidative esterification |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6680405B1 (en) | 1998-02-09 | 2004-01-20 | Mitsubishi Rayon Co., Ltd. | Process for the preparation of methyl methacrylate |
| JP3238894B2 (en) * | 1998-02-09 | 2001-12-17 | 三菱レイヨン株式会社 | Method for producing methyl methacrylate |
| WO2016069199A1 (en) * | 2014-10-31 | 2016-05-06 | Dow Global Technologies Llc | Process for in situ water removal from an oxidative esterification reaction using a coupled reactor-distillation system |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS579739A (en) * | 1980-06-20 | 1982-01-19 | Asahi Chem Ind Co Ltd | Purification of methyl methacrylate |
| DE3211901A1 (en) * | 1982-03-31 | 1983-10-13 | Basf Ag, 6700 Ludwigshafen | METHOD FOR SEPARATING METHANOL FROM WATER-CONTAINING MIXTURES OF METHYL METHACRYLATE AND METHANOL |
| JP3585989B2 (en) * | 1995-03-29 | 2004-11-10 | 大阪有機化学工業株式会社 | Separation method of methyl acrylate or methyl methacrylate and methanol |
| JP3880128B2 (en) * | 1997-05-08 | 2007-02-14 | 株式会社日本触媒 | Acrylic acid recovery method |
| JP3238894B2 (en) * | 1998-02-09 | 2001-12-17 | 三菱レイヨン株式会社 | Method for producing methyl methacrylate |
-
1998
- 1998-02-09 JP JP02731998A patent/JP3238894B2/en not_active Expired - Lifetime
-
1999
- 1999-08-06 CN CNB998168394A patent/CN1155556C/en not_active Expired - Lifetime
- 1999-08-06 WO PCT/JP1999/004268 patent/WO2001010811A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111511468A (en) * | 2018-01-10 | 2020-08-07 | 陶氏环球技术有限责任公司 | Heterogeneous catalyst for the production of methyl methacrylate by oxidative esterification |
| CN111511468B (en) * | 2018-01-10 | 2023-07-11 | 陶氏环球技术有限责任公司 | Heterogeneous catalyst for the production of methyl methacrylate by oxidative esterification |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1155556C (en) | 2004-06-30 |
| JP3238894B2 (en) | 2001-12-17 |
| WO2001010811A1 (en) | 2001-02-15 |
| JPH11228498A (en) | 1999-08-24 |
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| Date | Code | Title | Description |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Tokyo, Japan Patentee after: Mitsubishi Kasei Corporation Address before: Tokyo, Japan Patentee before: Mitsubishi Reiyon Co., Ltd. |
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| CP01 | Change in the name or title of a patent holder | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040630 |
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| CX01 | Expiry of patent term |