CN107473954A - A kind of greenization production method of succinic acid - Google Patents
A kind of greenization production method of succinic acid Download PDFInfo
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- CN107473954A CN107473954A CN201710755622.9A CN201710755622A CN107473954A CN 107473954 A CN107473954 A CN 107473954A CN 201710755622 A CN201710755622 A CN 201710755622A CN 107473954 A CN107473954 A CN 107473954A
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- succinic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/043—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
- C07C51/087—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides by hydrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Crystallography & Structural Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of greenization production method of succinic acid, it is specifically in the fixed-bed tube reactor equipped with catalyst, by one or more of any combination in the cis-butenedioic anhydride aqueous solution, aqueous maleic acid, the fumaric acid aqueous solution and the method for hydrogen progress catalytic hydrogenation reaction production succinic acid.Using ordered mesoporous material be carrier-supported precious metal as hydrogenation catalyst, can effectively avoid hydration reaction from generating DL malic acid, catalytic hydrogenation is selectively reached 100%, raw material is fully converted to succinic acid, product purity reaches more than 99.5%, while catalyst activity is high, reusable multiple.Centrifuge mother liquor, which can return to, after aqueous solution crystallisation by cooling after hydrogenation continues on for preparation hydrogenating materials, three-waste free discharge, and the scale continuous production of succinic acid can be realized using fixed-bed tube reactor catalytic hydrogenation reaction.
Description
Technical field
The invention provides a kind of greenization production method of succinic acid, is specifically in the fixed bed equipped with catalyst
In tubular reactor, by the one or more of any combination and hydrogen in the cis-butenedioic anhydride aqueous solution, aqueous maleic acid, the fumaric acid aqueous solution
The method that gas carries out catalytic hydrogenation reaction production succinic acid, is related to succinic acid production field.
Background technology
Succinic acid is the scientific name of butanedioic acid, is white crystalline body, molecular formula C4H6O4, 185 DEG C of fusing point, relative density
1.572, the solubility under normal temperature in water is about 8g.Succinic acid is a kind of important Organic Chemicals and intermediate, extensively
Applied to fields such as surfactant, ion chelating agent, food additives and medical industries.Using succinic acid and 1,4- butanediols as
The poly butylene succinate that raw material polycondensation obtains（PBS）It is a kind of complete biodegradable plastics, its mechanical property and heat-resisting
Excellent performance, it is cost-effective, have broad application prospects.
The preparation of succinic acid mainly includes biological fermentation process and chemical method.Biological fermentation process is sent out using bacterium or microorganism
Ferment prepares succinic acid, because this method has the defects of low production efficiency, production cost are expensive and seriously polluted, is difficult to realize work
Industry metaplasia is produced.Chemical method mainly includes paraffin oxidation style, electrolysis and catalytic hydrogenation method.Wherein, paraffin oxidation style technics comparing
Maturation, but product yield and purity is not high, and pollution problem be present；Electrolysis current efficiency be present and conversion ratio is low, electrode is rotten
The problems such as erosion is serious, electrolytic cell maintenance difficult, cost of investment are high, floor space is big, limits the large-scale production of succinic acid；Urge
Changing hydrogenation method has high conversion rate, product purity height, advantages of environment protection, is widest succinic acid synthesis industrial at present
Method.
Nonaqueous phase method and Aqueous phase are mainly included using cis-butenedioic anhydride preparing butanedioic acid under catalytic hydrogenation.
Nonaqueous phase method be cis-butenedioic anhydride organic solvent or it is solvent-free it is lower succinic anhydride is made through catalytic hydrogenation, succinic anhydride passes through again
Succinic acid made from hydrolysis.Catalytic hydrogenation is carried out using organic solvent, reaction needs desolventizing after terminating, heated without solvent
Under the conditions of cis-butenedioic anhydride liquefaction hydrogenation, cis-butenedioic anhydride viscosity is big, and the succinic anhydride fusing point of generation is up to 120 DEG C, is not easy to separate with catalyst, together
When easily cause line clogging discharging it is difficult the problems such as.
Aqueous phase is to be catalyzed cis-butenedioic anhydride aqueous phase Hydrogenation using loaded catalyst for succinic acid under certain reaction condition.It is suitable
Acid anhydride is hydrolyzed to maleic acid first, and maleic acid is isomerized to the more stable richness with transconfiguration under certain condition
Horse acid；Under catalyst action, intermediate maleic acid and fumaric acid are hydrogenated and are reduced to succinic acid, while with hydration
The generation of accessory substance DL-malic acid.
Subject matter existing for Aqueous phase catalytic hydrogenation process is as follows：
1. the catalyst used at present such as selectivity such as Pd/C, Pt/C, Raney's nickel is not high, catalytic hydrogenation and hydration reaction are entered simultaneously
OK, accessory substance DL-malic acid can be generated；
Cause to be catalyzed 2. metal active constituent such as Fe, Co, Ni in some loaded catalysts can be dissolved in acidic aqueous solution
Agent, which is lost in, to be reduced catalytic activity while influences product quality；
3. reaction temperature is low, accessory substance malic acid is few, but reacts slow, while succinic acid solubility is smaller, easily separates out and blocks pipe
Road；
4. reaction temperature is high, reaction is fast, but accessory substance malic acid is more, and yield is relatively low.
The content of the invention
The present invention is in view of the above-mentioned problems, provide that a kind of flow is simple, cost energy consumption is low, can serialization large-scale production
The greenization method of fixed-bed catalytic hydrogenation production succinic acid.
A kind of the technical scheme is that greenization production method of succinic acid, it is characterised in that：Comprise the following steps：
1. the hydrogenating materials that concentration is 10~50wt% are with hydrogen in the fixed bed reactors equipped with particulate supported type catalyst
Interior carry out catalytic hydrogenation reaction；
2. being centrifuged after hydrogenation resulting material crystallisation by cooling, earth tide product and centrifuge mother liquor are obtained, damp product dry to obtain succinic acid product；
It is used to prepare hydrogenating materials 3. centrifuge mother liquor returns to preceding road.
The hydrogenating materials are that the one or more in the cis-butenedioic anhydride aqueous solution, aqueous maleic acid, the fumaric acid aqueous solution are any
Combination.
The noble metal active component of the particulate supported type catalyst is the one or more in Pd, Pt, Ru, Rh, living
The content of property component is 3.0~10.0wt%；The carrier of the catalyst be CMK-3 mesoporous carbons, Y-MCM-41 mesopore molecular sieves,
One kind in the ordered mesoporous materials such as the mesoporous resin of M41S mesopore silicon oxides, FDU-15.
The catalytic hydrogenation reaction condition is：40~100 DEG C of inlet temperature is reacted, reacts 70~160 DEG C of outlet temperature,
React 0. 5~5.0MPa of hydrogen dividing potential drop, 0. 5 ~ 3.0h of volume space velocity -1, hydracid mol ratio 2~10:1.
Advantages of the present invention：
1. use fixed-bed tube reactor catalytic hydrogenation, it is possible to achieve the serialization and large-scale production of succinic acid；
2. using ordered mesoporous material be carrier-supported precious metal as hydrogenation catalyst, can effectively avoid hydration reaction from generating DL-
Malic acid, catalytic hydrogenation is set selectively to reach 100%, raw material is fully converted to succinic acid, while catalyst activity is high, repeats
Use more than 20 times；
Continue on for preparing hydrogenating materials 3. centrifuge mother liquor can return to after the aqueous solution crystallisation by cooling after hydrogenation；
4. three-waste free discharge, it is the greenization production technology of succinic acid.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment 1
By n (Al2O3):n(SiO2):n(Na2O):n(H2O)=1:10:10:180 alumina silica hydrogel is stirred vigorously at 98 DEG C
10h, obtain the hydrogel of the secondary building units of zeolite containing Y.Hydrogel is added to 25% cetyl trimethylammonium bromide
（CTAB）In solution, 3h is stirred, adjusts PH=10.Crystallization 3 days at 110 DEG C in crystallizing kettle, filtration washing are dried, and are forged at 550 DEG C
5h is burnt, obtains silica alumina ratio 10:1 Y-MCM-41 mesopore molecular sieve carriers.The water that carrier adds 25 times of amounts is well mixed, and adds one
Quantitative Pd (NH3)4Cl2The aqueous solution, it is 0.05 to make Pd and carrier quality ratio:1.Filtration washing is dried after stirring at normal temperature 24h, is risen
Temperature calcines 2h to 450 DEG C.Add extrusion after binding agent and obtain the mesoporous molecular sieve carried types of Pd- Y-MCM-41 of graininess 5% and urge
Agent.
Catalytic hydrogenation preparation is wherein carried out in fixed bed pipe reaction using the mesoporous molecular sieve carried type catalyst of 5% Pd-
Succinic acid.Hydrogenating materials are the 40wt% cis-butenedioic anhydride aqueous solution, and reaction condition is：It is 50 DEG C to react inlet temperature, and outlet temperature is
100 DEG C, reaction hydrogen dividing potential drop is 1.0MPa, volume space velocity 1.0h -1, hydracid mol ratio 3:1.Material reaction terminates crystallisation by cooling, from
Heart filtering drying obtains succinic acid.Feed stock conversion is 99.5%, succinic acid selectivity 100%, succinic acid product content 99.7%.
Embodiment 2
By silica alumina ratio 10:The water that 1 Y-MCM-41 mesopore molecular sieves carrier adds 25 times of amounts is well mixed, and adds a certain amount of Pt
(NH3)4Cl2The aqueous solution, it is 0.05 to make Pt and carrier quality ratio:1.Filtration washing is dried after stirring at normal temperature 24h, is warming up to 450 DEG C
Calcine 2h.Extrusion obtains the mesoporous molecular sieve carried type catalyst of Pt- Y-MCM-41 of graininess 5% after adding binding agent.
Catalytic hydrogenation preparation is wherein carried out in fixed bed pipe reaction using the mesoporous molecular sieve carried type catalyst of 5% Pt-
Succinic acid.Hydrogenating materials be 35wt% downstream（Water absorbs gained water after the tentatively cooling of mixed gas containing cis-butenedioic anhydride obtained by benzene oxidatoin method
Solution）, main component is maleic acid and a small amount of fumaric acid.Reaction condition is：It is 70 DEG C to react inlet temperature, and outlet temperature is
130 DEG C, reaction hydrogen dividing potential drop is 2.0MPa, volume space velocity 2.0h -1, hydracid mol ratio 2:1.Material reaction terminates crystallisation by cooling, from
Heart filtering drying obtains succinic acid.Feed stock conversion is 99.9%, succinic acid selectivity 100%, succinic acid product content 99.9%.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
For personnel it should be appreciated that the present invention is not limited to the above embodiments, that described in above-described embodiment and specification is only the present invention
Preference, be not intended to limit the present invention, without departing from the spirit and scope of the present invention, the present invention also have it is various
Changes and improvements, these changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by institute
Attached claims and its equivalent thereof.
Claims (5)
- A kind of 1. greenization production method of succinic acid, it is characterised in that：Comprise the following steps：1. the hydrogenating materials that concentration is 10~50wt% are with hydrogen in the fixed bed reactors equipped with particulate supported type catalyst Interior carry out catalytic hydrogenation reaction；2. being centrifuged after hydrogenation resulting material crystallisation by cooling, earth tide product and centrifuge mother liquor are obtained, damp product dry to obtain succinic acid product；It is used to prepare hydrogenating materials 3. centrifuge mother liquor returns to preceding road.
- A kind of 2. greenization production method of succinic acid according to claim 1, it is characterised in that：The hydrogenating materials are One or more of any combination in the cis-butenedioic anhydride aqueous solution, aqueous maleic acid, the fumaric acid aqueous solution.
- A kind of 3. greenization production method of succinic acid according to claim 1, it is characterised in that：The particulate supported The noble metal active component of type catalyst is the one or more in Pd, Pt, Ru, Rh, the content of active component for 3.0~ 10.0wt%。
- A kind of 4. greenization production method of succinic acid according to claim 1, it is characterised in that：The particulate supported The carrier of type catalyst is CMK-3 mesoporous carbons, Y-MCM-41 mesopore molecular sieves, M41S mesopore silicon oxides, the mesoporous resins of FDU-15 Deng one kind in ordered mesoporous material.
- A kind of 5. greenization production method of succinic acid according to claim 1, it is characterised in that：The catalytic hydrogenation is anti- The condition is answered to be：40~100 DEG C of inlet temperature of reaction, 70~160 DEG C of outlet temperature of reaction, reaction hydrogen dividing potential drop 0. 5~ 5.0MPa, 0. 5 ~ 3.0h of volume space velocity -1, hydracid mol ratio 2~10:1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111330581A (en) * | 2020-03-10 | 2020-06-26 | 中国科学院山西煤炭化学研究所 | Acid-resistant hydrogenation catalyst, and preparation method and application thereof |
| CN111689845A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by maleic anhydride aqueous phase hydrogenation |
| CN111689846A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by aqueous phase hydrogenation |
| CN112479862A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Low-cost method for synthesizing succinic acid by continuous aqueous phase catalytic hydrogenation |
| CN112806492A (en) * | 2021-02-04 | 2021-05-18 | 成都大帝汉克生物科技有限公司 | Compound acidifier for improving digestion capacity of piglet feed and piglet feed obtained by same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935375A (en) * | 2006-10-19 | 2007-03-28 | 复旦大学 | Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation |
| CN101844976A (en) * | 2010-04-27 | 2010-09-29 | 湖南长岭石化科技开发有限公司 | Method for preparing butanedioic acid under catalytic hydrogenation |
| KR20120035760A (en) * | 2010-10-06 | 2012-04-16 | 서울대학교산학협력단 | PALLADIUM-ALUMINA COMPLEX CATALYST FOR PRODUCTION OF γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID, PREPARATION METHOD THEREOF AND PRODUCTION METHOD FOR γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID USING SAID CATALYST |
| CN104874416A (en) * | 2015-05-13 | 2015-09-02 | 山西大学 | Catalyst for hydrogenating maleic anhydride to prepare succinic anhydride and preparation method of catalyst |
| CN105597742A (en) * | 2016-01-07 | 2016-05-25 | 上海华谊（集团）公司 | Catalyst and method of reaction for preparing butanedioic anhydride from maleic anhydride through liquid phase hydrogenation |
| CN105833863A (en) * | 2015-01-13 | 2016-08-10 | 广东工业大学 | Catalyst for preparing succinic anhydride from maleic anhydride through low-temperature hydrogenation and preparation method and application of catalyst |
-
2017
- 2017-08-29 CN CN201710755622.9A patent/CN107473954A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935375A (en) * | 2006-10-19 | 2007-03-28 | 复旦大学 | Method for preparing catalyst for preparing 1,4-cis-butanediol by dimethyl maleate hydrogenation |
| CN101844976A (en) * | 2010-04-27 | 2010-09-29 | 湖南长岭石化科技开发有限公司 | Method for preparing butanedioic acid under catalytic hydrogenation |
| KR20120035760A (en) * | 2010-10-06 | 2012-04-16 | 서울대학교산학협력단 | PALLADIUM-ALUMINA COMPLEX CATALYST FOR PRODUCTION OF γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID, PREPARATION METHOD THEREOF AND PRODUCTION METHOD FOR γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID USING SAID CATALYST |
| CN105833863A (en) * | 2015-01-13 | 2016-08-10 | 广东工业大学 | Catalyst for preparing succinic anhydride from maleic anhydride through low-temperature hydrogenation and preparation method and application of catalyst |
| CN104874416A (en) * | 2015-05-13 | 2015-09-02 | 山西大学 | Catalyst for hydrogenating maleic anhydride to prepare succinic anhydride and preparation method of catalyst |
| CN105597742A (en) * | 2016-01-07 | 2016-05-25 | 上海华谊（集团）公司 | Catalyst and method of reaction for preparing butanedioic anhydride from maleic anhydride through liquid phase hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| 上海市经济团体联合会 上海市化学化工学会 编著: "《节能减排新途径与新技术》", 31 May 2010, 华东理工大学出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112479862A (en) * | 2019-09-11 | 2021-03-12 | 王宏涛 | Low-cost method for synthesizing succinic acid by continuous aqueous phase catalytic hydrogenation |
| CN111330581A (en) * | 2020-03-10 | 2020-06-26 | 中国科学院山西煤炭化学研究所 | Acid-resistant hydrogenation catalyst, and preparation method and application thereof |
| CN111689845A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by maleic anhydride aqueous phase hydrogenation |
| CN111689846A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by aqueous phase hydrogenation |
| CN111689845B (en) * | 2020-03-18 | 2021-07-30 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by maleic anhydride aqueous phase hydrogenation |
| CN112806492A (en) * | 2021-02-04 | 2021-05-18 | 成都大帝汉克生物科技有限公司 | Compound acidifier for improving digestion capacity of piglet feed and piglet feed obtained by same |
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Application publication date: 20171215 |