CN102001939B - Method for preparing succinate - Google Patents
Method for preparing succinate Download PDFInfo
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- CN102001939B CN102001939B CN 201010524041 CN201010524041A CN102001939B CN 102001939 B CN102001939 B CN 102001939B CN 201010524041 CN201010524041 CN 201010524041 CN 201010524041 A CN201010524041 A CN 201010524041A CN 102001939 B CN102001939 B CN 102001939B
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- dicarboxylic ester
- acid dicarboxylic
- succinic acid
- preparation
- ester
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Abstract
The invention discloses a method for preparing succinate. The method comprises the following steps of: mixing hydrogen and maleic acid ester, and performing hydrogenation with a fixed bed reactor filled with a hydrogenation catalyst to obtain the succinate; and partially circulating the generated succinate, mixing with the maleic acid ester to obtain raw materials, and feeding a product subjected to hydrogenation into a gas-liquid separator to obtain succinate with content of over 99.6 percent, wherein the separated hydrogen can be recycled. The method has the advantages that: raw materials are diluted in a reaction product circulation mode, so that temperature runaway caused by hydrogenation heat release can be effectively avoided, by-products of the reaction is very few, and the service life of the catalyst is prolonged and the stability of the catalyst is improved.
Description
Technical field
The invention belongs to a kind of method for preparing the Succinic Acid dicarboxylic ester, specially refer to a kind of method of being produced the Succinic Acid dicarboxylic ester by toxilic acid dicarboxylic ester hydrogenation.
Technical background
The Succinic Acid dicarboxylic ester is important synthetic perfume, foodstuff additive, organic solvent, also is the synthetic intermediate of organic synthesis and medicine, is widely used in industries such as food, spices, daily-use chemical industry, medicine, coating, rubber, plastics.Especially in recent years, because environmental consciousness strengthens, the environmental protection series products is subjected to people's favor, be the environment-friendly type coating of solvent and be the pigment (as quinacridine ketone pigment) of intermediate preparation with it with the Succinic Acid dicarboxylic ester, will have vast market prospect, this will drive the demand of Succinic Acid dicarboxylic ester.
The preparation method of Succinic Acid dicarboxylic ester mainly is with Succinic Acid and corresponding C at present
1-C
5Alcohol is raw material, obtains with the sulphuric acid catalysis esterification.But because the vitriol oil has strong oxidizing property, this technology side reaction is many, and product color is deepened, and yield is low, the aftertreatment complexity, and equipment corrosion is serious, and the by product serious environment pollution.Therefore, Many researchers has been developed the production process that diverse ways improves the Succinic Acid dicarboxylic ester, and research mainly concentrates on solid catalysts such as adopting solid acid, acidic ion exchange resin, molecular sieve and substitutes sulfuric acid.For example, to disclose a kind of solid super-strong acid, heteropolyacid and storng-acid cation exchange resin of adopting be the method that solid catalyst prepares diethyl succinate to patent CN101323566A.
CN101747189A, CN101745396A has announced with the technology of alkyl maleate hydrogenation preparing succinic acid dialkyl ester and catalyzer, but it is directly with the dialkyl maleate raw material, diluent free, and alkyl maleate hydrogenation is a strong exothermal reaction, be easy to cause temperature runaway, and its used copper zinc catalyst is subjected to thermal shock resistance properties poor, especially for this class strong exothermal reaction of carbon-carbon double bond hydrogenation, the poor stability of catalyzer is relatively poor, life-span is short, be easy to inactivation, and copper-based catalysts is as the most frequently used carbonyl hydrogen catalyzer, be easy to generate 1, the 4-butyleneglycol, gamma-butyrolactone, by products such as tetrahydrofuran (THF), hydrogenated products need separate purification just can obtain qualified product.
Summary of the invention
The purpose of this invention is to provide a kind of good stability, the life-span is short long, and what by product was few is the method for raw material hydrogenation preparing Succinic Acid dicarboxylic ester with the toxilic acid dicarboxylic ester,
Preparation method of the present invention comprises the steps:
Hydrogen is mixed with the toxilic acid dicarboxylic ester, generate the Succinic Acid dicarboxylic ester by the fixed-bed reactor hydrogenation reaction that hydrogenation catalyst is housed, the Succinic Acid dicarboxylic ester that generates partly circulated be mixed into raw material with the toxilic acid dicarboxylic ester, product behind the hydrogenation is behind gas-liquid separator, be the Succinic Acid dicarboxylic ester of content more than 99.6%, hydrogen recycles after separating.
Xun Huan Succinic Acid dicarboxylic ester and toxilic acid dicarboxylic ester volume ratio are 0.5～4: 1 as mentioned above, preferred 1: 1～2: 1.
Aforesaid hydrogenation catalyst is nickel-base hydrogenation catalyst, as Ni/Al
2O
3, Ni/SiO
2, Ni/AC etc., preferred Ni/Al
2O
3, Ni/AC, nickel content is 5wt%～30wt%.Also can add auxiliary agents such as a small amount of K, Ca, Mg, Mn, Ba, Cu.As the disclosed Ni/Al of CN1644656A
2O
3Catalyzer, wherein NiO content is 10wt%-30wt%; The disclosed Ni catalyzer of CN 101757917A, wherein NiO is 5wt%～30wt%, auxiliary agent content is 0.1wt%～4.0wt% etc.
Aforesaid hydrogenation reaction temperature is 50～200 ℃, preferred 60～150 ℃; Pressure is 0.1～5MPa, preferred 0.5～1MPa;
Aforesaid hydrogen and toxilic acid dicarboxylic ester mol ratio are 20～500, preferred 30～200; The volume space velocity of toxilic acid dicarboxylic ester is 0.2～5h
-1, preferred 0.5～1h
-1Aforesaid toxilic acid dicarboxylic ester is C
1-C
5Carboxylicesters, as dimethyl maleate, ethyl maleate, toxilic acid dibutyl ester or toxilic acid diisopropyl alcohol ester etc.
Preparation method of the present invention has the following advantages:
1. adopt the mode of reaction product circulation to dilute raw material, can avoid the hydrogenation heat release to cause temperature runaway effectively.
Byproduct of reaction seldom, and thinner this as reaction product, product need not can obtain the very high product of purity through distillation or complex separations step such as rectifying.
3. employing nickel-base catalyst can effectively improve catalyzer work-ing life, and catalyzer has very high activity and selectivity.
Description of drawings
Fig. 1 is process flow sheet of the present invention
Embodiment
Further specify the present invention with following embodiment, but invention is not limited.
Embodiment 1:
5%Ni-0.05%K is equipped with in the dimethyl maleate feeding
2O/Al
2O
3Fixed-bed reactor in, reaction pressure is 5MPa, 50 ℃ of temperature, air speed 0.2h
-1, hydrogen and toxilic acid dicarboxylic ester mol ratio mol ratio 20, the dimethyl succinate of circulation and dimethyl maleate volume ratio are 0.5: 1, through the 1000h stability experiment, the result is as shown in Table 1.
Embodiment 2:
15%Ni-8%MnO is equipped with in the ethyl maleate feeding
2/ SiO
2Fixed-bed reactor in, reaction pressure is 0.1MPa, 200 ℃ of temperature, air speed 5h
-1, hydrogen and toxilic acid dicarboxylic ester mol ratio 500, the diethyl succinate of circulation and ethyl maleate volume ratio are 4: 1, through the 1000h stability experiment, the result is as shown in Table 1.
Embodiment 3:
The isopropyl maleate feeding is equipped with in the fixed-bed reactor of 30%Ni-2%MgO/AC, and reaction pressure is 1MPa, 120 ℃ of temperature, air speed 0.5h
-1, hydrogen and toxilic acid dicarboxylic ester mol ratio 50, the diisopropyl ester amber acid of circulation and isopropyl maleate volume ratio are 1: 1, through the 1000h stability experiment, the result is as shown in Table 1.
Embodiment 4:
The dibutyl maleinate feeding is equipped with in the fixed-bed reactor of 10%Ni/AC, and reaction pressure is 2MPa, 80 ℃ of temperature, air speed 1h
-1, hydrogen and toxilic acid dicarboxylic ester mol ratio 200, the dibutyl succinate of circulation and dibutyl maleinate volume ratio are 2: 1, through the 1000h stability experiment, the result is as shown in Table 1.
Table one reaction conditions and result
Claims (10)
1. the preparation method of a Succinic Acid dicarboxylic ester is characterized in that may further comprise the steps:
Hydrogen is mixed with the toxilic acid dicarboxylic ester, generate the Succinic Acid dicarboxylic ester by the fixed-bed reactor hydrogenation reaction that hydrogenation catalyst is housed, the Succinic Acid dicarboxylic ester that generates partly circulated be mixed into raw material with the toxilic acid dicarboxylic ester, product behind the hydrogenation is behind gas-liquid separator, be the Succinic Acid dicarboxylic ester of content more than 99.6%, hydrogen recycles after separating;
Described hydrogenation catalyst is Ni/Al
2O
3, Ni/SiO
2Or Ni/AC, nickel content is 5wt%～30wt%.
2. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 1 is characterized in that the Succinic Acid dicarboxylic ester of described circulation and toxilic acid dicarboxylic ester volume ratio are 0.5～4: 1.
3. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 2 is characterized in that described Succinic Acid dicarboxylic ester and toxilic acid dicarboxylic ester volume ratio are 1: 1～2: 1.
4. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 1 is characterized in that described nickel-base hydrogenation catalyst adds a small amount of K, Ca, Mg, Mn, Ba or Cu auxiliary agent.
5. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 1 is characterized in that described hydrogenation reaction temperature is 50～200 ℃, and pressure is 0.1～5MPa, and the volume space velocity of toxilic acid dicarboxylic ester is 0.2～5h
-1
6. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 5 is characterized in that described hydrogenation reaction temperature is 60～150 ℃; Pressure is 0.5～1Mpa, and the volume space velocity of toxilic acid dicarboxylic ester is 0.5～1h
-1
7. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 1 is characterized in that described hydrogen and toxilic acid dicarboxylic ester mol ratio are 20～500.
8. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 7 is characterized in that described hydrogen and toxilic acid dicarboxylic ester mol ratio are 30～200.
9. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 1 is characterized in that described toxilic acid dicarboxylic ester is C
1-C
5Carboxylicesters.
10. the preparation method of a kind of Succinic Acid dicarboxylic ester as claimed in claim 1 is characterized in that described C
1-C
5Carboxylicesters be dimethyl maleate, ethyl maleate, toxilic acid dibutyl ester or toxilic acid diisopropyl alcohol ester.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010524041 CN102001939B (en) | 2010-10-26 | 2010-10-26 | Method for preparing succinate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010524041 CN102001939B (en) | 2010-10-26 | 2010-10-26 | Method for preparing succinate |
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|---|---|
| CN102001939A CN102001939A (en) | 2011-04-06 |
| CN102001939B true CN102001939B (en) | 2013-08-14 |
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|---|---|---|---|
| CN 201010524041 Active CN102001939B (en) | 2010-10-26 | 2010-10-26 | Method for preparing succinate |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163761B (en) * | 2014-08-06 | 2016-04-13 | 中建安装工程有限公司 | A kind of method of rectified purified dimethyl succinate |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU419512A1 (en) * | 1972-11-04 | 1974-03-15 | Г. С. Гсворк , Газар Ереванский завод химических реактивов | METHOD OF OBTAINING COMPLEX ETHERS OF YANT.LRNO ACID |
| US3830830A (en) * | 1972-02-29 | 1974-08-20 | Eastman Kodak Co | Production of dialkyl esters of succinic acid |
| EP0728731A1 (en) * | 1995-02-22 | 1996-08-28 | Bayer Ag | Process for the preparation of dialkyl esters of succinic acid |
| CN1890230A (en) * | 2003-12-16 | 2007-01-03 | 戴维加工技术有限公司 | Process for the production of ethers |
| CN101747189A (en) * | 2008-12-03 | 2010-06-23 | 中国科学院大连化学物理研究所 | Method for preparing succinic acid dialkyl ester by maleic acid dialkyl ester hydrogenation |
| CN101745396A (en) * | 2008-12-03 | 2010-06-23 | 中国科学院大连化学物理研究所 | Catalyst for preparing succinic acid dialkyl ester and preparation method thereof |
-
2010
- 2010-10-26 CN CN 201010524041 patent/CN102001939B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3830830A (en) * | 1972-02-29 | 1974-08-20 | Eastman Kodak Co | Production of dialkyl esters of succinic acid |
| SU419512A1 (en) * | 1972-11-04 | 1974-03-15 | Г. С. Гсворк , Газар Ереванский завод химических реактивов | METHOD OF OBTAINING COMPLEX ETHERS OF YANT.LRNO ACID |
| EP0728731A1 (en) * | 1995-02-22 | 1996-08-28 | Bayer Ag | Process for the preparation of dialkyl esters of succinic acid |
| CN1890230A (en) * | 2003-12-16 | 2007-01-03 | 戴维加工技术有限公司 | Process for the production of ethers |
| CN101747189A (en) * | 2008-12-03 | 2010-06-23 | 中国科学院大连化学物理研究所 | Method for preparing succinic acid dialkyl ester by maleic acid dialkyl ester hydrogenation |
| CN101745396A (en) * | 2008-12-03 | 2010-06-23 | 中国科学院大连化学物理研究所 | Catalyst for preparing succinic acid dialkyl ester and preparation method thereof |
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