CN1172797A - Method for preparing methacrylic acid methyl ester and ethyl ester and ethyl ester - Google Patents
Method for preparing methacrylic acid methyl ester and ethyl ester and ethyl ester Download PDFInfo
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- CN1172797A CN1172797A CN 96111119 CN96111119A CN1172797A CN 1172797 A CN1172797 A CN 1172797A CN 96111119 CN96111119 CN 96111119 CN 96111119 A CN96111119 A CN 96111119A CN 1172797 A CN1172797 A CN 1172797A
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Abstract
A catalystic distillation process for preparing perspex and ethyl methylacrylate features use of strong-acidic macroreticular cation exchange resin as catalyst, feeding raw materials from bottom, the ratio of length to diameter for reactor being greater than 10 and reaction temp of 80-100 deg. C. The resultant of esterification reaction is discharged from reactor in the form of azeotrope vapour to unbalance the reaction, resulting in continuous reaction. The transform rate of methylcrylic acid and the selectivity of resultant ester all are more than 99.5%. Water-carrying agent is not needed.
Description
The present invention relates to the method for a kind of production methyl methacrylate (MMA) and Jia Jibingxisuanyizhi (EMA).Specifically, it is catalyzer that the present invention adopts storng-acid cation exchange resin, under the situation of not solubilizing agent or azeotropic agent, with the method for catalytic distillation methacrylic acid (MAA) and methyl alcohol (MeOH) or ethanol (EtOH) is reacted, and generates MMA or EMA.
The demand of MMA and EMA is in continuous rising, and Application Areas is also in continuous expansion; Its traditional manufacture method has liquid phase method, liquid-solid phase method, the gentle liquid-solid trichotomy of gas solid method etc.In these methods, transformation efficiency of great majority is lower, thereby need carry out recirculation operation, has increased running cost.In clear 55-122740 of Ri Tekai and the clear 58-159442 of Ri Tekai, disclosing with ion exchange resin is the method for catalyzer continuous production methacrylic ester.The disclosed method of the clear 58-159442 of Ri Tekai need adopt two-stage reaction, uses two reactors, will add lower boiling organic inert solvent in the system and make azeotropic agent, moves right to impel chemical equilibrium, reaches higher transformation efficiency.Like this, its postprocessing working procedures relative complex.And point out its " resultant flows out from reactor with gas-liquid phase admixture " in the disclosed method of the clear 55-122740 of Ri Tekai, " temperature of reaction is high more favourable more, and the general temperature range that adopts is 80～200 ℃ ".The temperature that adopts among the embodiment of the disclosure special permission preparation MMA is 100～110 ℃, and adopts dimethylbenzene to make solvent (dimethylbenzene can play the azeotropic agent effect, but makes the aftertreatment complexity).Because its temperature of reaction is higher, be unfavorable for prolonging the life-span of ion-exchange resin catalyst, also need more heat to come the preheating reaction system simultaneously.
Purpose of the present invention just provide a kind of can do not add any solvent, than under the low reaction temperatures, high conversion makes the method for MMA, EMA.
According to the present invention, esterification is carried out under the condition of catalytic distillation, the temperature of reaction system is controlled in the temperature range a little more than ester water azeotrope boiling point, the product of esterification shifts out reactor rapidly with the formula of azeotrope steam, break original balance, make it to move towards the direction that generates ester.Thereby in the method for the invention, product flows out from reactor fast with gas phase state fully, and reaction can reach very high transformation efficiency once, there is no need to add organic inert solvent fully again and makes azeotropic agent and carry out recirculation operation.
In the present invention, MAA mixes by certain acid-alcohol ratio with alcohol, and with the mode of time charging underfeed from the catalytic distillation reactor.Reactor will be selected suitable length-to-diameter ratio, generally more than 10, can realize the effect of catalytic distillation with the cation exchange resin bed layer of protecting reactor.Specifically, in the present invention, the cation exchange resin catalyst bed obviously is divided into three districts in reaction system: Gu the bottom of bed is vapour-liquid-three-phase, but liquid phase is greater than gas phase; Gu the middle part of bed also is vapour-liquid-three-phase, but gas phase is greater than liquid phase; The top of bed then is vapour-solid phase.Like this, following, the middle part of bed are equivalent to catalytic section, and Zeo-karb plays catalysis MAA and alcohol reaction, and the top of bed is equivalent to distilling period, and its Zeo-karb plays filler effect.Esterification takes place with alcohol in MAA in catalytic section, generate ester and water, form ester-water and ester-pure azeotrope between ester and water and the excessive alcohol simultaneously, and under temperature of reaction formation azeotrope steam, the distilling period of upwards flowing through is with the form outflow reactor top of steam.Because product is shifted out reactor rapidly, has broken chemical equilibrium, makes balance move towards the product direction, MAA can react fully, and the selectivity of its transformation efficiency and generation ester all can reach more than 99.5%.
In the present invention, used Zeo-karb is the macropore strong acid cation exchange resin, and granularity is 0.3～1.5mm, and pore volume is 0.3～0.5ml/g, and exchange capacity is 4～5mmolH+/g, and specific surface area is 35～45m
2/ g, average pore radius is 200～600A, and degree of crosslinking is 8～30%, and during life-time service, sulfonic acid group does not come off under 100 ℃ temperature, has good thermotolerance and physical strength preferably.
The temperature of reactive system is vital for the present invention.The rising temperature of reaction, speed of response obviously increases.When the temperature of reactive system reached ester-water azeotrope critical temperature, this azeotrope became steam, and the reactor that speeds away makes that reaction continues to carry out to the product direction, and MAA reaches very high transformation efficiency.Thereby the temperature of reactor will be controlled in the scope a little more than the azeotrope critical temperature, and concrete temperature of reaction is wanted the selected pressure of viewing system and the raw material type that adopted and decide, generally in 80～100 ℃ scope.
In the present invention, the pressure of system can be normal pressure, also can be lower than slightly or a little higher than normal pressure, as long as make formed azeotrope critical temperature enough high, to guarantee enough fast speed of response and can not get final product other side effects of generation such as beds.The acid-alcohol ratio of raw material can be 2～5 (mol ratios), and preferable proportional range is between 2.5～3.5.Can add certain density Resorcinol in the reactive system and make stopper.
By adopting the method for catalytic distillation, the present invention can easily accomplish to make the selectivity of MAA transformation efficiency and ester all more than 99.5%, simultaneously need not add azeotropic agent, reduced last handling process, and the temperature of reactive system can maintain below 100 ℃, guarantee long-term, the runs steadily of ion-exchange resin catalyst energy that the energy of having saved preheating material again illustrates in greater detail the present invention by the following examples.Embodiment 1
Do reactor with the stainless steel tube that has chuck, and with feed preheater.Sleeve pipe in the chuck is the catalytic distillation reactor, its internal diameter is 25mm, the height of beds is 320mm, the catalyzer of packing into is a strongly acidic macroporous cation exchange resin, the mol ratio of MeOH and MAA is 3.0 in the raw material, and the Resorcinol of adding 300ppm is made stopper (MAA relatively).Raw material enters from the bottom of reactor, and liquid air speed is 0.5h
-1, the temperature of beds is 85 ℃, system pressure is a normal pressure.After the reaction, the transformation efficiency of MAA is 99.64%, and the selectivity of MMA is 99.80%.
Embodiment 2
Reactor, catalyzer are identical with embodiment 1, EtOH/MAA=3.0 (mol ratio), and add Resorcinol 300ppm (MAA relatively), 93 ℃ of temperature of reaction, liquid air speed 0.5h
-1, normal pressure.MAA transformation efficiency 99.5%, EMA selectivity 99.70%.
Embodiment 3
Reactor is identical with embodiment 1 with raw material, and reaction conditions is except that pressure, and other condition is also identical with embodiment 1.
When reacting system pressure (gauge pressure) is 0, when 20KPa, 35KPa, 40KPa and 60KPa, the MAA transformation efficiency is respectively 99.6%, 98.3%, 96%, 81% and 76%.
Embodiment 4
Except that MeOH/MAA than the difference, reactor is all identical with embodiment 1 with other condition.
When MeOH/MAA=2.0 (mol ratio), the MAA transformation efficiency is 94%.
Claims (6)
1. method of producing methyl methacrylate and ethyl ester, comprise with the strong-acid ion exchange resin being catalyzer, do not add organic inert solvent or azeotropic agent, it is characterized in that adopting the method for catalytic distillation, product ester and water that reaction generates are taken away from reactor with the form of its azeotrope steam.
2. the described method of claim 1 is characterized in that raw material adopts the mode of charging down to add in the reactor, and alcohol is 2～5 with the mol ratio of methacrylic acid in the raw material.
3, the described method of claim 1, the temperature maintenance that it is characterized in that reactive system is in 80～100 ℃ scope.
4. the described method of claim 1, the pressure that it is characterized in that reactive system is normal pressure or is lower than normal pressure slightly, or a little higher than normal pressure.
5. the described method of claim 1, the granularity that it is characterized in that used storng-acid cation exchange resin is 0.3～1.5mm, specific surface area is 35～45m
2/ g, pore volume are 0.3～0.5ml/g, and pore radius is 200～600A, and degree of crosslinking is 8～30%.
6. the described method of claim 1 is characterized in that length-to-diameter ratio reactor used in the catalytic distillation is greater than 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96111119A CN1069893C (en) | 1996-08-03 | 1996-08-03 | Method for preparing methacrylic acid methyl ester and ethyl ester and ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96111119A CN1069893C (en) | 1996-08-03 | 1996-08-03 | Method for preparing methacrylic acid methyl ester and ethyl ester and ethyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1172797A true CN1172797A (en) | 1998-02-11 |
| CN1069893C CN1069893C (en) | 2001-08-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96111119A Expired - Fee Related CN1069893C (en) | 1996-08-03 | 1996-08-03 | Method for preparing methacrylic acid methyl ester and ethyl ester and ethyl ester |
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| CN (1) | CN1069893C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1296341C (en) * | 2004-03-02 | 2007-01-24 | 三菱化学株式会社 | Process for producing (meth)acrylic acid |
| CN1305833C (en) * | 2001-10-05 | 2007-03-21 | 海尔特曼公司 | Method for producing a hydroxyacid esters |
| CN101006041B (en) * | 2004-08-18 | 2011-01-05 | 塞拉尼斯国际公司 | Acetic anhydride and acetate ester co-production |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2449811C2 (en) * | 1974-10-19 | 1983-01-05 | Hoechst Ag, 6000 Frankfurt | Process for the continuous production of dibutyl ether-free n-butyl acrylate |
| JPS5531046A (en) * | 1978-08-28 | 1980-03-05 | Mitsubishi Chem Ind Ltd | Preparation of acrylic or methacrylic ester |
| JPH0686406B2 (en) * | 1989-04-21 | 1994-11-02 | 株式会社日本触媒 | Method for producing acrylic ester |
-
1996
- 1996-08-03 CN CN96111119A patent/CN1069893C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305833C (en) * | 2001-10-05 | 2007-03-21 | 海尔特曼公司 | Method for producing a hydroxyacid esters |
| CN1296341C (en) * | 2004-03-02 | 2007-01-24 | 三菱化学株式会社 | Process for producing (meth)acrylic acid |
| CN101006041B (en) * | 2004-08-18 | 2011-01-05 | 塞拉尼斯国际公司 | Acetic anhydride and acetate ester co-production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1069893C (en) | 2001-08-22 |
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