CN102070448A - Method for preparing dimethyl succinate - Google Patents
Method for preparing dimethyl succinate Download PDFInfo
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- CN102070448A CN102070448A CN201110042296XA CN201110042296A CN102070448A CN 102070448 A CN102070448 A CN 102070448A CN 201110042296X A CN201110042296X A CN 201110042296XA CN 201110042296 A CN201110042296 A CN 201110042296A CN 102070448 A CN102070448 A CN 102070448A
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- dimethyl succinate
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- tower
- esterification
- hydrogenation
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Abstract
The invention discloses a method for preparing dimethyl succinate. The method comprises two reaction processes of esterification and hydrogenation and the reaction processes are as follows: (1) after pre-esterification reaction, maleic anhydride-methanol solution enters a catalytic distillation tower from the upper rectifying section of the tower, methanol enters the tower from the lower stripping section of the catalytic distillation tower, the reaction section is filled with solid acid catalyst, the two material flows perform countercurrent contact on the surface of the catalyst to perform esterification reaction and synthetize dimethyl maleate; and (2) dimethyl maleate and hydrogen are placed in a fixed bed reactor to perform hydrogenation reaction and generate the dimethyl succinate product in the presence of hydrogenation catalyst under a certain reaction condition. The method of the invention has the advantages of high raw material conversion rate and good product selectivity; and the process flow is simple, the energy consumption is low, no pollution can be caused and the scale production of dimethyl succinate can be realized.
Description
Technical field
The present invention relates to a kind of method for preparing dimethyl succinate, relate in particular to a kind of by the method for cis-butenedioic anhydride through esterification, hydrogenation preparing dimethyl succinate.
Background technology
Dimethyl succinate (also claiming Succinic acid dimethylester) is a kind of colourless or weak yellow liquid (room temperature), is widely used in environment protection type high-boiling-point solvent.Dimethyl succinate also is a kind of important chemical intermediate, is widely used in industries such as food, spices, medicine, coating, rubber, plastics, is used for synthetic photostabilizer, high-grade paint, sterilant, medicine intermediate.
Traditional dimethyl succinate Technology is that Succinic Acid and methyl alcohol interrupter method catalytic esterification are synthetic, and catalyzer is used the vitriol oil always.Because vitriol oil etching apparatus, have oxidisability, side reaction is many, product is not easily separated and shortcoming such as contaminate environment, and throughput is lower, can not satisfy the requirement of current green chemical industry.In addition, the existing esterification technique speed of response of Succinic Acid and methyl alcohol that adopts is slow, and reaction is difficult to carry out thoroughly, makes the refining difficulty of product separation.
CN101824627 discloses a kind of preparation method of dimethyl succinate, cis-butenedioic anhydride and methyl alcohol adopt electrolytic reduction that dimethyl maleate is changed into dimethyl succinate at the synthetic dimethyl maleate of tank reactor discontinuous ground catalytic esterification then under sulfuric acid or hydrochloric acid effect.Cis-butenedioic anhydride is as the raw material of producing Succinic Acid, and its catalytic esterification with methyl alcohol is easier, more thorough than the esterification of Succinic Acid and methyl alcohol.But this method uses liquid acid easily to cause equipment corrosion in esterification process, catalyzer and product need carry out separating for several times and product loss bigger, not only energy consumption height, and contaminate environment; In addition, current efficiency and feed stock conversion are not high in the dimethyl maleate electrolytic reduction synthesis of dimethyl succinate, and whole process energy consumption, material consumption are all bigger, and floor space is unfavorable for large-scale production greatly.
Summary of the invention
At the deficiencies in the prior art, a kind of technical process is fairly simple, feed stock conversion is high and the method for the low mass-producing continuous production of energy consumption dimethyl succinate but the invention provides.
The present invention is achieved through the following technical solutions: a kind of method for preparing dimethyl succinate, it is characterized in that: comprise esterification, two reaction process of hydrogenation: (1) cis-butenedioic anhydride-methanol solution enters in the tower through the upper rectifying section from catalytic distillation tower behind the pre-esterification reactor, and methyl alcohol enters in the tower from the bottom stripping section of catalytic distillation tower, solid acid catalyst is housed in the conversion zone, two kinds of logistics are in the catalyst surface counter current contact, through the synthetic dimethyl maleate of esterification; (2) under hydrogenation catalyst and reaction conditions, dimethyl maleate becomes the dimethyl succinate product with hydrogen hydrogenation reaction in fixed-bed reactor.
The pre-esterification reactor of described cis-butenedioic anhydride-methanol solution carries out in fixed-bed reactor.Catalyzer is a solid acid catalyst, and reaction conditions is: 60～90 ℃ of temperature, and pressure 0.2～0.8MPa, methyl alcohol and cis-butenedioic anhydride mol ratio are 2～6, the cis-butenedioic anhydride air speed is 0.5～1.0h
-1Behind pre-esterification reactor, still have a small amount of cis-butenedioic anhydride unconverted, the dimethyl maleate selectivity remains further to be improved simultaneously, contains a large amount of monomethyl maleates in the product.
Described catalytic distillation tower comprises a tower still, a stripping section, a conversion zone, a rectifying section and a trim the top of column condenser, filling solid acid catalyst in the conversion zone.Wherein, solid acid catalyst is a storng-acid cation exchange resin.Resin catalyst needs to carry out pre-treatment according to means known in the art before use.
The operational condition of described catalytic distillation tower is: pressure 0.1～0.4MPa, and 65～80 ℃ of tower top temperatures, 70～110 ℃ of conversion zone middle part temperature, 80～120 ℃ of tower still temperature, methyl alcohol and monomethyl maleate mol ratio are 1.2～4, the residence time is 80～140 minutes.Owing to adopt the catalytic distillation mode, can in time remove resultant dimethyl maleate and water, make monomethyl maleate reach the degree of depth and transform, also make that unreacted cis-butenedioic anhydride reacts completely in the pre-esterification reactor device simultaneously.
Described hydrogenation catalyst is a loaded catalyst, adopts conventional dipping method preparation.The catalyst activity component is one or more among group VIII metal Fe, Co, Ni, Pd, Pt, Ru, Rh, the Ir, and the content of active ingredient total amount in catalyzer is 0.2～10% (wt), and carrier is Al
2O
3, SiO
2, TiO
2, ZrO
2, in the activated carbon (C) one or more.Wherein, the catalyst activity component is preferably Pd, and content is 0.4～2.0% (wt).
Described hydrogenation reaction processing condition are: reaction pressure 0.1～5MPa, preferred 2～3MPa; 60～200 ℃ of temperature, preferred 120～160 ℃; Ester charging air speed 0.2～3.0h
-1, preferred 0.5～1.5h
-1Hydrogen ester mol ratio 2～100, preferred 10～40.
In the inventive method, operational condition is applicable to the situation of dimethyl succinate preparation, and present method also is applicable to the preparation situation of other succinic acid dialkyl ester in fact.
The present invention has following advantage: (1) adopts solid acid catalyst and catalytic distillation technology, has simplified separating technology, and the entire reaction flow process is simple, energy consumption is low, pollution-free; (2) in cis-butenedioic anhydride catalytic esterification section, cis-butenedioic anhydride transformation efficiency 100%, the dimethyl maleate selectivity is greater than 99%; (3) in dimethyl maleate catalytic hydrogenation reaction section, the selectivity of the transformation efficiency of dimethyl maleate and product dimethyl succinate is all greater than 99.8%; (4) successive esterification, hydrogenation process make the production of dimethyl succinate realize serialization, mass-producing.
Embodiment
Further specify the inventive method and effect below by embodiment, but be not limited only to embodiment.
Embodiment 1～5
According to the inventive method, use acid resin catalyst, cooperate appropriate processing condition, be that raw material carries out the synthetic dimethyl maleate of catalytic esterification with cis-butenedioic anhydride and methyl alcohol, actual conditions and reaction result see Table 1.
Table 1Cis-butenedioic anhydride and methyl alcohol catalytic esterification synthesize the dimethyl maleate result
As known from Table 1, in cis-butenedioic anhydride catalytic esterification section, cis-butenedioic anhydride transformation efficiency 100%, the dimethyl maleate selectivity is greater than 99%.
Embodiment 6～12
According to the inventive method, make spent hydroprocessing catalyst (catalyzer is formed by weight), cooperate appropriate processing condition, be catalytic material hydrogenation synthesis of dimethyl succinate with the dimethyl maleate, actual conditions and reaction result see Table 2.
Table 2Dimethyl maleate shortening synthesis of dimethyl succinate result
As known from Table 2, in dimethyl maleate catalytic hydrogenation reaction section, the selectivity of the transformation efficiency of dimethyl maleate and product dimethyl succinate is all greater than 99.8%.
Claims (8)
1. a cis-butenedioic anhydride prepares the method for dimethyl succinate, it is characterized in that: comprise two reaction process of esterification and hydrogenation: (1) cis-butenedioic anhydride-methanol solution enters in the tower through the upper rectifying section from catalytic distillation tower behind the pre-esterification reactor, and methyl alcohol enters in the tower from the bottom stripping section of catalytic distillation tower, a kind of solid acid catalyst is housed in the conversion zone, two kinds of logistics are in the catalyst surface counter current contact, through the synthetic dimethyl maleate of esterification; (2) under hydrogenation catalyst and reaction conditions, dimethyl maleate becomes the dimethyl succinate product with hydrogen hydrogenation reaction in fixed-bed reactor.
2. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: described pre-esterification reactor carries out in fixed-bed reactor, catalyzer is a solid acid catalyst, reaction conditions is: 60～90 ℃ of temperature, pressure 0.2～0.8MPa, methyl alcohol and cis-butenedioic anhydride mol ratio are 2～6, and the cis-butenedioic anhydride air speed is 0.5～1.0h
-1
3. according to claim 1, the 2 described methods that prepare dimethyl succinate, it is characterized in that: described solid acid catalyst is an acidic cation-exchange resin.
4. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: the operational condition of described catalytic distillation tower is: pressure 0.1～0.4MPa, 65～80 ℃ of tower top temperatures, 70～110 ℃ of conversion zone middle part temperature, 80～120 ℃ of tower still temperature, methyl alcohol and monomethyl maleate mol ratio are 1.2～4, and the residence time is 80～140 minutes.
5. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: the active ingredient of described hydrogenation catalyst is one or more in the group VIII metal, and the content of active ingredient total amount in catalyzer is 0.2～10% (wt), and carrier is Al
2O
3, SiO
2, TiO
2, ZrO
2, in the activated carbon one or more.
6. according to the described method for preparing dimethyl succinate of claim 5, it is characterized in that: described VIII family metal is Pd, and content is 0.4～2.0% (wt).
7. according to the described method for preparing dimethyl succinate of claim 1, it is characterized in that: described hydrogenation reaction processing condition are: pressure 0.1～5MPa; 60～200 ℃ of temperature; Ester charging air speed 0.2～3.0h
-1Hydrogen ester mol ratio 2～100.
8. according to the described method for preparing dimethyl succinate of claim 7, it is characterized in that: described hydrogenation reaction processing condition are: pressure 2～3MPa; 120～160 ℃ of temperature; Ester charging air speed 0.5～1.5h
-1Hydrogen ester mol ratio 10～40.
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| CN201110042296XA CN102070448B (en) | 2011-02-22 | 2011-02-22 | Method for preparing dimethyl succinate |
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|---|---|---|---|
| CN201110042296XA CN102070448B (en) | 2011-02-22 | 2011-02-22 | Method for preparing dimethyl succinate |
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| CN102070448B CN102070448B (en) | 2013-04-03 |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863335A (en) * | 2012-10-15 | 2013-01-09 | 中国科学院长春应用化学研究所 | Preparation method of diethyl succinate |
| CN103342638A (en) * | 2013-07-31 | 2013-10-09 | 山东兰典生物科技股份有限公司 | Preparation method of dibutyl succinate |
| CN103464153A (en) * | 2013-09-27 | 2013-12-25 | 凯瑞化工股份有限公司 | Method for preparing hydrogenation catalyst for producing dimethyl succinate |
| CN103611546A (en) * | 2013-12-12 | 2014-03-05 | 中国科学院新疆理化技术研究所 | Bimetal catalyst for synthesizing butanedioic-acid dialkyl ester and preparation method thereof |
| CN103657693A (en) * | 2013-12-12 | 2014-03-26 | 王金明 | Dimethyl maleate hydrogenating catalyst and preparation method thereof |
| CN104193619A (en) * | 2014-08-06 | 2014-12-10 | 宁波浙铁江宁化工有限公司 | Technique for hydrogenation production of dimethyl succinate by using intermediate product of 1,4-butanediol device |
| GB2523617A (en) * | 2013-10-14 | 2015-09-02 | Johnson Matthey Davy Technologies Ltd | Process |
| CN105566112A (en) * | 2016-02-29 | 2016-05-11 | 彩客科技（北京）有限公司 | Continuous hydrogenation reaction method of organic intermediates and reactor thereof |
| CN107473966A (en) * | 2017-08-29 | 2017-12-15 | 南京雪郎化工科技有限公司 | A kind of production method of dimethyl maleate |
| CN110563933A (en) * | 2019-09-16 | 2019-12-13 | 宁波窦氏化学科技有限公司 | Preparation method of ultrahigh molecular weight PBS |
| CN112175752A (en) * | 2020-08-21 | 2021-01-05 | 希玛石油制品（镇江）有限公司 | Universal environment-friendly normal-temperature water-based cleaning agent and preparation method thereof |
| CN112961058A (en) * | 2021-02-08 | 2021-06-15 | 宁波窦氏化学科技有限公司 | Process method for preparing glycol maleate |
| CN113200853A (en) * | 2021-05-19 | 2021-08-03 | 宁波窦氏化学科技有限公司 | Process method for preparing butanediol succinate |
| CN113461523A (en) * | 2021-07-06 | 2021-10-01 | 彩客化学(沧州)有限公司 | Preparation method and equipment of dimethyl succinate |
| WO2022190141A1 (en) | 2021-03-12 | 2022-09-15 | Conser S.P.A. | Process for the co-production of dialkyl succinate and 1,4-butanediol by hydrogenating dialkyl maleate in two stages. |
| CN115536528A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Production process of dimethyl maleate |
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| EP0190424A2 (en) * | 1985-02-01 | 1986-08-13 | Chemie Linz Gesellschaft m.b.H. | Process for the preparation of pure dialkyl succinates |
| CN101314564A (en) * | 2007-06-01 | 2008-12-03 | 上海焦化有限公司 | Preparation of maleic acid di-methyl ester |
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| EP0190424A2 (en) * | 1985-02-01 | 1986-08-13 | Chemie Linz Gesellschaft m.b.H. | Process for the preparation of pure dialkyl succinates |
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Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863335B (en) * | 2012-10-15 | 2014-10-22 | 中国科学院长春应用化学研究所 | Preparation method of diethyl succinate |
| CN102863335A (en) * | 2012-10-15 | 2013-01-09 | 中国科学院长春应用化学研究所 | Preparation method of diethyl succinate |
| CN103342638A (en) * | 2013-07-31 | 2013-10-09 | 山东兰典生物科技股份有限公司 | Preparation method of dibutyl succinate |
| CN103342638B (en) * | 2013-07-31 | 2015-01-14 | 山东兰典生物科技股份有限公司 | Preparation method of dibutyl succinate |
| CN103464153A (en) * | 2013-09-27 | 2013-12-25 | 凯瑞化工股份有限公司 | Method for preparing hydrogenation catalyst for producing dimethyl succinate |
| CN103464153B (en) * | 2013-09-27 | 2015-01-07 | 凯瑞化工股份有限公司 | Hydrogenation catalyst for producing dimethyl succinate and method for preparing hydrogenation catalyst for producing dimethyl succinate |
| GB2523617A (en) * | 2013-10-14 | 2015-09-02 | Johnson Matthey Davy Technologies Ltd | Process |
| US9776947B2 (en) | 2013-10-14 | 2017-10-03 | Johnson Matthey Davy Technologies Limited | Process for the production of dialkyl succinate from maleic anyhdride |
| GB2523617B (en) * | 2013-10-14 | 2016-04-27 | Johnson Matthey Davy Technologies Ltd | A process for the production of dialkyl succinate |
| CN103611546A (en) * | 2013-12-12 | 2014-03-05 | 中国科学院新疆理化技术研究所 | Bimetal catalyst for synthesizing butanedioic-acid dialkyl ester and preparation method thereof |
| CN103657693B (en) * | 2013-12-12 | 2015-05-27 | 王金明 | Dimethyl maleate hydrogenating catalyst and preparation method thereof |
| CN103611546B (en) * | 2013-12-12 | 2016-03-16 | 中国科学院新疆理化技术研究所 | Bimetallic catalyst of a kind of synthesizing succinic acid dialkyl and preparation method thereof |
| CN103657693A (en) * | 2013-12-12 | 2014-03-26 | 王金明 | Dimethyl maleate hydrogenating catalyst and preparation method thereof |
| CN104193619A (en) * | 2014-08-06 | 2014-12-10 | 宁波浙铁江宁化工有限公司 | Technique for hydrogenation production of dimethyl succinate by using intermediate product of 1,4-butanediol device |
| CN105566112A (en) * | 2016-02-29 | 2016-05-11 | 彩客科技（北京）有限公司 | Continuous hydrogenation reaction method of organic intermediates and reactor thereof |
| CN107473966A (en) * | 2017-08-29 | 2017-12-15 | 南京雪郎化工科技有限公司 | A kind of production method of dimethyl maleate |
| CN110563933A (en) * | 2019-09-16 | 2019-12-13 | 宁波窦氏化学科技有限公司 | Preparation method of ultrahigh molecular weight PBS |
| CN110563933B (en) * | 2019-09-16 | 2022-03-11 | 宁波窦氏化学科技有限公司 | Preparation method of ultrahigh molecular weight PBS |
| CN112175752A (en) * | 2020-08-21 | 2021-01-05 | 希玛石油制品（镇江）有限公司 | Universal environment-friendly normal-temperature water-based cleaning agent and preparation method thereof |
| CN112961058A (en) * | 2021-02-08 | 2021-06-15 | 宁波窦氏化学科技有限公司 | Process method for preparing glycol maleate |
| WO2022166540A1 (en) * | 2021-02-08 | 2022-08-11 | 窦和瑞 | Process method for preparing glycol maleate |
| WO2022190141A1 (en) | 2021-03-12 | 2022-09-15 | Conser S.P.A. | Process for the co-production of dialkyl succinate and 1,4-butanediol by hydrogenating dialkyl maleate in two stages. |
| CN113200853A (en) * | 2021-05-19 | 2021-08-03 | 宁波窦氏化学科技有限公司 | Process method for preparing butanediol succinate |
| CN115536528A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Production process of dimethyl maleate |
| CN113461523A (en) * | 2021-07-06 | 2021-10-01 | 彩客化学(沧州)有限公司 | Preparation method and equipment of dimethyl succinate |
| CN113461523B (en) * | 2021-07-06 | 2024-05-03 | 河北彩客新材料科技股份有限公司 | Preparation method and equipment of dimethyl succinate |
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