CN108047022A - A kind of method for preparing succinic acid - Google Patents
A kind of method for preparing succinic acid Download PDFInfo
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- CN108047022A CN108047022A CN201711318800.8A CN201711318800A CN108047022A CN 108047022 A CN108047022 A CN 108047022A CN 201711318800 A CN201711318800 A CN 201711318800A CN 108047022 A CN108047022 A CN 108047022A
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- succinic acid
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- sodium succinate
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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
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- Oil, Petroleum & Natural Gas (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method for preparing succinic acid, step is：(1) sodium succinate zymotic fluid is subjected to cross-flow filtration by the microfiltration membranes that aperture is 0.1~0.5um, removes thalline and the larger impurity particle of particle；(2) solution that step (1) obtains is subjected to cross-flow filtration by the NF membrane that molecular cut off is 500~2000, removes protein and pigment, obtain clarification sodium succinate solution；(3) by bipolar membrane electrodialysis, succinic acid solution and sodium hydroxide solution containing a small amount of sodium succinate are respectively obtained；(4) the succinic acid solution containing a small amount of sodium succinate is removed remaining sodium ion, obtains pure succinic acid solution by hydrogen type strong acid type cation exchange resin；(5) evaporate, crystallization obtains succinic acid crystal.It connects between each step of method of the present invention close, feed liquid cycles under conditions of closed always, and technological process is short, and step is simple, low for equipment requirements, and product purity is high.
Description
Technical field
The present invention relates to biological chemical fields, and in particular to a kind of method for preparing succinic acid.
Background technology
Succinic acid (succinic acid) is a kind of important C4 platform chemicals, be widely used in medicine, pesticide, dyestuff, fragrance,
Paint, food, plastics and photographic material industry.It is 1,4-butanediol, tetrahydrofuran, gamma-butyrolacton, PBT resin, N- methyl pyrroles
The basic material of the important bulk chemical such as pyrrolidone, adipic acid and specialty chemicals.Main the having of the synthetic method of succinic acid
Method and microbe fermentation method.Chemical method mainly have paraffin oxidation, the cyaniding hydrolysis of methyl chloroacetate, cyclenes ozone oxidation,
The electrolysis of maleic anhydride or fumaric catalytic hydrogenation and maleic acid.Succinic acid meeting is produced in chemical synthesis
It causes largely to pollute, and the raw material of chemical synthesis is non-renewable petrochemicals, is subject to its extensive use
Limitation.The raw material of producing succinic acid by microbial fermentation is renewable resource such as corn pulp, sugarcane, glucose etc., in addition, fermentation
CO2 is absorbed in engineering, from environmentally friendly and resource utilization, fermentation method production succinic acid is that one kind is emerging, has very much development to dive
The friendly process of power.The preferable level of microbial fermentation is that the content of succinic acid in zymotic fluid is 50g/L or so at present.So hair
Contained ingredient also mainly includes thalline, graininess nutrient media components, solubility large biological molecule, small except succinic acid in addition in zymotic fluid
Molecular organic and organic acid (formic acid, acetic acid) etc..Therefore the post processing and purification of succinic acid are prepared for microbial fermentation solution
Research be of great significance.The method of purification for preparing succinic acid using microbial fermentation mainly has calcium salt method, ammonia salt method, solvent
Extraction, conventional electroosmose process, membrane separation process.United States Patent (USP) US5143833, US5168055 disclose calcium salt extraction succinic acid
Method, calcium hydroxide is added in into zymotic fluid, the precipitation of calcium succinate is generated, is acidified after filtering, remove calcium sulfate after obtain
Succinic acid solution, but the yield of the above method is relatively low, there are substantial amounts of calcium sulfate discarded object is generated in extraction process, soda acid disappears
The defects of consumption is big, and energy consumption is big.United States Patent (USP) US5958744 discloses a kind of method of ammonia salt extraction succinic acid, first uses hydrogen-oxygen
The pH for changing sodium adjusting zymotic fluid is more than 6.5, then adds ammonium hydrogen sulfate, is crystallized, is purified finally by methanol.Ammonium salt process
Route is long, need to use substantial amounts of solvent, and crystallization condition is not easy to grasp, and step is more numerous, and difficulty is big, and operating cost is high, post processing into
This height.United States Patent (USP) US503415, which is disclosed after conventional electrodialysis, to be removed most of salt through desalination electrodialysis again to obtain purity higher
Succinic acid solution.But electroosmose process route is long, high energy consumption, processing foreign ion has significant limitation, cannot such as handle
Divalent ion, operating difficulties big to equipment investment.Lee SY(Proess Biochem,2006,41:1461-1465), Wang great
For (colleges and universities' chemical engineering journal, 1994,8 (2)；143.The method extraction succinic acid with solvent is reported, but in the mistake of extraction
The a large amount of expensive organic solvents of Cheng Zhongxu consumption, cause cost for purification higher, while the toxicity of residual solvent is to food-grade and doctor
The quality of medicine grade product has harmful effect, which is also not suitable for the zymotic fluid system of high-strength ionic strength.Chinese patent
CN1887843 discloses a kind of using micro-filtrate membrane filtration, and then with ultrafiltration membrance filter, then with activated carbon decolorizing, concentration, crystallization comes
The method for extracting succinic acid, but succinate cannot be converted into succinic acid by this method, be finally also acidified with acid, and can be led
It causes to introduce substantial amounts of salt in solution, as a result can cause that refined product is more difficult, and yield is relatively low.Chinese patent CN101348428A
A kind of method with yin, yang resin purification succinic acid, but the meeting during ion exchange are disclosed with CN101348429A
Consume substantial amounts of water so that evaporation cost is higher, adds energy consumption cost, and regenerated process can generate substantial amounts of waste water.
It is high for salt content in zymotic fluid simultaneously, cause resin stain serious, regeneration is difficult, and resin life shortens.Said extracted method
Middle have that post processing cost for purification is high, and costly, process route is long for agents useful for same material, and method is excessively complicated, and energy consumption is big
Problem is unfavorable for the large-scale production of fermentation method production succinic acid.
The content of the invention
In order to solve the problems in the prior art, the present invention provides a kind of method for preparing succinic acid.
Realize the object of the invention technical solution be：
(1) steel-making, coker offgas collect the CO purified2, the sodium succinate zymotic fluid of Production by Microorganism Fermentation will be passed through
In operating pressure it is 0.1-0.15MPa by the microfiltration membranes that aperture is 0.1~0.5um, operation temperature is 10~30 DEG C of condition
Lower carry out cross-flow filtration, 15~25 times of cycles of concentration, leaching requirement are the 10~50% of fermentating liquid volume, remove thalline and particle compared with
Big impurity particle；
(2) by the solution that step (1) obtains by the NF membrane that molecular cut off is 500~2000 pressure be 1~
5MPa, temperature carry out cross-flow filtration, 20~40 times of cycles of concentration under conditions of being 20~60 DEG C, leaching requirement is fermentating liquid volume
10~30%, remaining protein and pigment in zymotic fluid are removed, obtains clarification sodium succinate solution；
(3) sodium succinate solution is clarified under conditions of 5~40 DEG C by bipolar membrane electrodialysis by described, respectively obtain and contain
The succinic acid solution and sodium hydroxide solution of a small amount of sodium succinate；
(4) the succinic acid solution containing a small amount of sodium succinate is removed by hydrogen type strong acid type cation exchange resin
Remaining sodium ion, obtains pure succinic acid solution；
(5) the pure succinic acid solution decompression is evaporated, decrease temperature crystalline obtains white succinic acid crystal.The Hydrogen
The model of strongly acidic cation-exchange is preferably 001*4,001*7,001*8,001*10, D001 or SQD-65.
Beneficial effects of the present invention are：The method of the present invention eliminates traditional decolorization, avoids activated carbon to fourth
The absorption of diacid, reduces operating procedure；Also avoid it is traditional be adjusted with acid-base pair pH value, while cause secondary in system
The sodium hydroxide of production is recycled, and reduces production cost.It connects between each step of the present invention close, feed liquid is always close
It is cycled under conditions of closing, entire technical conditions are mild, do not add any organic solvent and other organic compounds, technique stream
Journey is short, and step is simple, not high to equipment requirement, and last product purity is high, reaches 99.4% through HPLC analyses succinic acid content.
Other indexs meet USP30 standards.
Specific embodiment
Further technology explanation is carried out to technical scheme below.Explanation is the solution to present inventive concept below
It releases, is not used in and limits the scope of the invention.
Embodiment 1
(1) by the sodium succinate zymotic fluid of the 20L 50g/L containing succinic acid produced by microbial fermentation through the micro- of 0.3um
Filter membrane is 0.12MPa in operating pressure, and operation temperature carries out cross-flow filtration, 19 times of cycles of concentration, wash water under conditions of being 30 DEG C
It measures as 4L, removing thalline and granule foreign；
(2) solution for obtaining step (1) is 2MPa in operating pressure by the NF membrane that molecular cut off is 500, temperature
It spends to carry out cross-flow filtration, 35 times of cycles of concentration under conditions of 40 DEG C, wash water water is 2L, removes remaining albumen in zymotic fluid
Matter and pigment obtain clarification sodium succinate solution；
(3) sodium succinate solution will be clarified under conditions of 25 DEG C by bipolar membrane electrodialysis, respectively obtained containing a small amount of fourth
The succinic acid solution and sodium hydroxide solution of diacid sodium, sodium hydroxide solution recycling；
(4) the succinic acid solution containing a small amount of sodium succinate is handed over by model 001*4 hydrogen type strong acids type cation
Resin is changed, remaining sodium ion is removed, obtains pure succinic acid solution；
(5) by the pure succinic acid solution in 60 DEG C of reduction vaporization, decrease temperature crystalline after succinic acid concentration is more than 20%
White succinic acid crystal is obtained, is filtered, drying obtains the succinic acid finished product of 895g whites, yield 89.5%.
Embodiment 2
The method that succinic acid is extracted from zymotic fluid, includes the following steps：
(1) it is by aperture by the sodium succinate zymotic fluid of the 20L 50g/L containing succinic acid produced by microbial fermentation
The microfiltration membranes of 0.2um are 0.12MPa in operating pressure, and operation temperature carries out cross-flow filtration, cycles of concentration under conditions of being 15 DEG C
20 times, leaching requirement is the 10% of fermentating liquid volume, removes thalline and the larger impurity particle of particle；
(2) solution for obtaining step (1) is 3MPa in pressure by the NF membrane that molecular cut off is 1000, and temperature is
Cross-flow filtration, 30 times of cycles of concentration are carried out under conditions of 40 DEG C, leaching requirement is the 20% of fermentating liquid volume, is removed residual in zymotic fluid
The protein and pigment stayed obtains clarification sodium succinate solution；
(3) sodium succinate solution is clarified under conditions of 30 DEG C by bipolar membrane electrodialysis by described, respectively obtain containing few
Measure the succinic acid solution and sodium hydroxide solution of sodium succinate；
(4) the succinic acid solution containing a small amount of sodium succinate is handed over by model 001*7 hydrogen type strong acids type cation
Resin is changed, remaining sodium ion is removed, obtains pure succinic acid solution；
(5) by the pure succinic acid solution in 60 DEG C of reduction vaporization, decrease temperature crystalline after succinic acid concentration is more than 20%
White succinic acid crystal is obtained, is filtered, drying obtains the succinic acid finished product of 880g whites, yield 88.0%.
Embodiment 3
The method that succinic acid is extracted from zymotic fluid, includes the following steps：
(1) it is by aperture by the sodium succinate zymotic fluid of the 20L 50g/L containing succinic acid produced by microbial fermentation
The microfiltration membranes of 0.1um are 0.15MPa in operating pressure, and operation temperature carries out cross-flow filtration, cycles of concentration under conditions of being 30 DEG C
15 times, leaching requirement is the 50% of fermentating liquid volume, removes thalline and the larger impurity particle of particle；
(2) solution for obtaining step (1) is 2MPa in pressure by the NF membrane that molecular cut off is 800, and temperature is
Cross-flow filtration, 20 times of cycles of concentration are carried out under conditions of 30 DEG C, leaching requirement is the 20% of fermentating liquid volume, is removed residual in zymotic fluid
The protein and pigment stayed obtains clarification sodium succinate solution；
(3) sodium succinate solution is clarified under conditions of 25 DEG C by bipolar membrane electrodialysis by described, respectively obtain containing few
Measure the succinic acid solution and sodium hydroxide solution of sodium succinate；
(4) the succinic acid solution containing a small amount of sodium succinate is passed through into model 001*8 hydrogen type strong acid type cation exchanges
Resin removes remaining sodium ion, obtains pure succinic acid solution；
(5) by the pure succinic acid solution in 60 DEG C of reduction vaporization, decrease temperature crystalline after succinic acid concentration is more than 20%
White succinic acid crystal is obtained, is filtered, drying obtains the succinic acid finished product of 890g whites, yield 89.0%.
Embodiment 4
The method that succinic acid is extracted from zymotic fluid, includes the following steps：
(1) it is by aperture by the sodium succinate zymotic fluid of the 20L 50g/L containing succinic acid produced by microbial fermentation
The microfiltration membranes of 0.5um are 0.1MPa in operating pressure, and operation temperature carries out cross-flow filtration, cycles of concentration 25 under conditions of being 10 DEG C
Times, leaching requirement is the 20% of fermentating liquid volume, removes thalline and the larger impurity particle of particle；
(2) solution for obtaining step (1) is 1MPa in pressure by the NF membrane that molecular cut off is 500, and temperature is
Cross-flow filtration, 20 times of cycles of concentration are carried out under conditions of 20 DEG C, leaching requirement is the 10% of fermentating liquid volume, is removed residual in zymotic fluid
The protein and pigment stayed obtains clarification sodium succinate solution；
(3) sodium succinate solution is clarified under conditions of 30 DEG C by bipolar membrane electrodialysis by described, respectively obtain containing few
Measure the succinic acid solution and sodium hydroxide solution of sodium succinate；
(4) the succinic acid solution containing a small amount of sodium succinate is handed over by model 001*10 hydrogen type strong acids type cation
Resin is changed, remaining sodium ion is removed, obtains pure succinic acid solution；
(5) by the pure succinic acid solution in 60 DEG C of reduction vaporization, decrease temperature crystalline after succinic acid concentration is more than 20%
White succinic acid crystal is obtained, is filtered, drying obtains the succinic acid finished product of 875g whites, yield 87.5%.
Embodiment 5
The method that succinic acid is extracted from zymotic fluid, includes the following steps：
(1) it is by aperture by the sodium succinate zymotic fluid of the 20L 50g/L containing succinic acid produced by microbial fermentation
The microfiltration membranes of 0.3um are 0.12MPa in operating pressure, and operation temperature carries out cross-flow filtration, cycles of concentration under conditions of being 20 DEG C
20 times, leaching requirement is the 30% of fermentating liquid volume, removes thalline and the larger impurity particle of particle；
(2) solution for obtaining step (1) is 5MPa in pressure by the NF membrane that molecular cut off is 2000, and temperature is
Cross-flow filtration, 40 times of cycles of concentration are carried out under conditions of 60 DEG C, leaching requirement is the 30% of fermentating liquid volume, is removed residual in zymotic fluid
The protein and pigment stayed obtains clarification sodium succinate solution；
(3) sodium succinate solution is clarified under conditions of 5 DEG C by bipolar membrane electrodialysis by described, respectively obtain containing a small amount of
The succinic acid solution and sodium hydroxide solution of sodium succinate；
(4) the succinic acid solution containing a small amount of sodium succinate is passed through into model D001 hydrogen type strong acid type cation exchanges
Resin removes remaining sodium ion, obtains pure succinic acid solution；
(5) by the pure succinic acid solution in 60 DEG C of reduction vaporization, decrease temperature crystalline after succinic acid concentration is more than 20%
White succinic acid crystal is obtained, is filtered, drying obtains the succinic acid finished product of 895g whites, yield 89.5%.
Embodiment 6
The method that succinic acid is extracted from zymotic fluid, includes the following steps：
(1) it is by aperture by the sodium succinate zymotic fluid of the 20L 50g/L containing succinic acid produced by microbial fermentation
The microfiltration membranes of 0.2um are 0.13MPa in operating pressure, and operation temperature carries out cross-flow filtration, cycles of concentration under conditions of being 15 DEG C
22 times, leaching requirement is the 20% of fermentating liquid volume, removes thalline and the larger impurity particle of particle；
(2) solution for obtaining step (1) is 4MPa in pressure by the NF membrane that molecular cut off is 1000, and temperature is
Cross-flow filtration, 30 times of cycles of concentration are carried out under conditions of 50 DEG C, leaching requirement is the 20% of fermentating liquid volume, is removed residual in zymotic fluid
The protein and pigment stayed obtains clarification sodium succinate solution；
(3) sodium succinate solution is clarified under conditions of 40 DEG C by bipolar membrane electrodialysis by described, respectively obtain containing few
Measure the succinic acid solution and sodium hydroxide solution of sodium succinate；
(4) the succinic acid solution containing a small amount of sodium succinate is handed over by model SQD-65 hydrogen type strong acids type cation
Resin is changed, remaining sodium ion is removed, obtains pure succinic acid solution；
(5) by the pure succinic acid solution in 60 DEG C of reduction vaporization, decrease temperature crystalline after succinic acid concentration is more than 20%
White succinic acid crystal is obtained, is filtered, drying obtains the succinic acid finished product of 885g whites, yield 88.5%.
The method of the present invention eliminates traditional decolorization, avoids absorption of the activated carbon to succinic acid, reduces behaviour
Make step；Also avoid it is traditional be adjusted with acid-base pair pH value, while so that the sodium hydroxide of by-product is returned in system
It receives and utilizes, reduce production cost.It connects between each step of the present invention close, feed liquid cycles under conditions of closed always, whole
A technical conditions are mild, do not add any organic solvent and other organic compounds, and technological process is short, and step is simple, right
Equipment requirement is not high, and last product purity is high, reaches 99.4% through HPLC analyses succinic acid content.Other indexs meet
USP30 standards.
Above-described embodiment is only the specific embodiment of the invention, but is not limited to embodiment, all not depart from structure of the present invention
In the case of think of, equivalent modification and the prior art addition done according to the application are accordingly to be regarded as the technology of the present invention scope.
Claims (2)
1. the method for succinic acid is prepared a kind of, it is characterized in that including the following steps：(1) CO of gas sampling purifying is made steel2, will be logical
The sodium succinate zymotic fluid for crossing Production by Microorganism Fermentation is in operating pressure by the microfiltration membranes that aperture is 0.1~0.5um
0.1-0.15MPa, operation temperature carry out cross-flow filtration, 15~25 times of cycles of concentration under conditions of being 10~30 DEG C, and leaching requirement is
The 10~50% of fermentating liquid volume remove thalline and the larger impurity particle of particle；(2) solution that step (1) obtains is passed through
The NF membrane that molecular cut off is 500~2000 is 1~5MPa in pressure, and temperature carries out cross-flow under conditions of being 20~60 DEG C
Filter, 20~40 times of cycles of concentration, leaching requirement are the 10~30% of fermentating liquid volume, remove remaining protein and color in zymotic fluid
Element obtains clarification sodium succinate solution；(3) the clarification sodium succinate solution is passed through into Bipolar Membrane under conditions of 5~40 DEG C
Electrodialysis respectively obtains succinic acid solution and sodium hydroxide solution containing a small amount of sodium succinate；(4) described a small amount of succinic acid will be contained
The succinic acid solution of sodium removes remaining sodium ion, obtains pure succinic acid by hydrogen type strong acid type cation exchange resin
Solution；(5) the pure succinic acid solution decompression is evaporated, decrease temperature crystalline obtains white succinic acid crystal.
2. a kind of method for preparing succinic acid according to claim 1, it is characterized in that hydrogen type strong acid type cation is handed over
Change model 001*4,001*7,001*8,001*10, D001 or SQD-65 of resin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393378A (en) * | 2020-04-13 | 2020-07-10 | 浙江迪萧环保科技有限公司 | Method for extracting sulfadimethoxine from sulfadimethoxine sodium alkali liquor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887843A (en) * | 2006-07-18 | 2007-01-03 | 南京工业大学 | Method for separating and extracting succinic acid from anaerobic fermentation broth |
| CN101811953A (en) * | 2009-02-23 | 2010-08-25 | 凯能高科技工程（上海）有限公司 | Method for extracting succinic acid from fermentation broth |
| CN103420826A (en) * | 2012-05-15 | 2013-12-04 | 常茂生物化学工程股份有限公司 | Method for extracting succinic acid from fermentation broth |
-
2017
- 2017-12-12 CN CN201711318800.8A patent/CN108047022A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887843A (en) * | 2006-07-18 | 2007-01-03 | 南京工业大学 | Method for separating and extracting succinic acid from anaerobic fermentation broth |
| CN101811953A (en) * | 2009-02-23 | 2010-08-25 | 凯能高科技工程（上海）有限公司 | Method for extracting succinic acid from fermentation broth |
| CN103420826A (en) * | 2012-05-15 | 2013-12-04 | 常茂生物化学工程股份有限公司 | Method for extracting succinic acid from fermentation broth |
Non-Patent Citations (1)
| Title |
|---|
| NHUAN P. NGHIEM, ET AL.: "Succinic Acid: Technology Development and Commercialization", 《FERMENTATION》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393378A (en) * | 2020-04-13 | 2020-07-10 | 浙江迪萧环保科技有限公司 | Method for extracting sulfadimethoxine from sulfadimethoxine sodium alkali liquor |
| CN111393378B (en) * | 2020-04-13 | 2024-03-29 | 浙江迪萧科技有限公司 | Method for extracting sulfamonomethoxine from sulfamonomethoxine sodium alkali liquor |
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