CN106554279B - A method of extracting succinate from succinic acid fermentation liquor - Google Patents
A method of extracting succinate from succinic acid fermentation liquor Download PDFInfo
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- CN106554279B CN106554279B CN201510629799.5A CN201510629799A CN106554279B CN 106554279 B CN106554279 B CN 106554279B CN 201510629799 A CN201510629799 A CN 201510629799A CN 106554279 B CN106554279 B CN 106554279B
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- succinic acid
- succinate
- esterification
- fermentation liquor
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The method that the present invention relates to a kind of to extract succinate from succinic acid fermentation liquor: to succinic acid fermentation liquor using filter progress removing thallus and bulky grain suspended matter, filtered fluid is obtained；Concentrate is concentrated to give to filtered fluid；Concentrate is come into full contact under the action of an acid with alcohol, is esterified and is crystallized precipitation concerted reaction, obtains esterification crystallized mixed feed liquid；Crystal in removing esterification crystallized mixed feed liquid obtains de- crystal esterification clear liquid；Then rectifying to get.The subtractive process of succinic acid is omitted in the method for the present invention, can simultaneously be effectively remove the salt in fermentation liquid, with lower production cost, succinate product purity obtained is high, can be used for synthesizing light stabilizer, high-grade paint, fungicide, medicine intermediate or is hydrogenated to butanediol.
Description
Technical field
The method that the present invention relates to a kind of to extract succinate from succinic acid fermentation liquor, belongs to fine chemistry industry skill
Art field.
Background technique
Currently, the production of succinic acid mainly uses chemical method of the butane through maleic anhydride, this method is at high cost, seriously
Hinder the large-scale production of succinic acid.Compared with chemical method, using cheap reproducible resource as the anaerobic biological process of raw material
Production succinic acid has the characteristics that Atom economy is high, process is environmentally protective and can realize low-carbon emission reduction, receives the U.S., day
Originally, the extensive concern of the National Academies and industry such as South Korea and China.Since there are two active carboxylic acid groups for tool, succinic acid can
Important succinate is generated so that esterification occurs with alcohol, and then synthesizes light stabilizer, high-grade paint, fungicide, medicine
Intermediate is hydrogenated to butanediol.Synthetic method in relation to succinate has been disclosed in many documents.For example, Chinese
Patent of invention 201310120279.2 changes macropore styrene resin in such a way that chloro, alkali earth metal sulfate are modified
Property, modified resin has good heat-resistant stability and activity for succinate synthesis.Li Xiang etc. uses 3A molecule
Adsorption dewatering technology is sieved, is Material synthesis succinic acid two by catalyst, succinic acid and isopropanol of cation exchange resin NKC-9
Isopropyl ester (daily chemical industry, 546-549 pages of 10 phases of volume 44 in 2014).9 kinds of differences are prepared for Zhao using two-step method along grade
Lewis acidic ion liquid, and systematically investigated its catalytic performance to succinic acid and isopropanol esterification, obtained
Diisopropyl ester amber acid yield is reaction result (Journal of Chemical Industry and Engineering, 2 phase 561- of volume 65 in 2014 of 88.9% and esterification yield 92.7%
Page 569).Aqueous solution of such as the above succinate synthetic method reported in the literature with succinic acid or containing succinic acid is made
It for raw material, however obtains succinic acid sterling and needs cumbersome process, for biology base succinic acid.
The separation of biology base succinic acid mainly includes calcium salt method, electroosmose process, ammonium salt crystallization method, ion-exchange and film point
From method, these methods can be used alone or in combination to reach satisfactory separating-purifying effect.United States Patent (USP) US5168055
It reports and is directly added into calcium salt in fermentation liquid, form calcium succinate precipitating with succinic ion, then filtering precipitating, use
The method that the mode that sulfuric acid acidification, crystallization are precipitated obtains succinic acid product.US5143834, JP2283289 and JP2944157 are adopted
It is separated with electrolytic method and obtains succinic acid, the succinate solution of low concentration is specifically subjected to electrolysis, makes fourth two
The supersaturated solution and lye of acid.Wherein, the lye isolated may return to fermentation vat for neutralizing succinic acid, realize back
With.However, the electrolysis process initial investment and operating cost are higher, and are only suitable for being electrolysed the monovalent salt fermentation liquid of succinic acid,
To succinic acid divalent salts fermentation liquid and it is not suitable for.Yun Suk Huh etc. is using expensive trioctylamine-n-octyl alcohol solution complexometric extraction
Succinic acid, which may will affect the quality of succinic acid using the trioctylamine being more toxic, and recovered solvent makes again
Albumen therein, pigment (Process Biochemistry, 2006 volume 41 page 1461-1465) need to be removed before.
US5958744 is disclosed is added ammonium hydroxide and sulfuric acid adjusting pH value, subsequent progress coarse crystallization and recrystallizing methanol in fermentation liquid
The method for obtaining succinic acid.In the patent, the ammonium sulfate that ammonium hydroxide and sulfuric acid reaction generate thermally decomposes under 300 DEG C of hot conditions can
Ammonium hydroxide and sulfuric acid are recycled, but unfriendly to environment using toxic methanol in recrystallization process.US20090234160
The method that succinic acid is obtained from the succinate solution comprising alkali metal is reported, the technology utilization alkali metal sulfates and fourth
The different feature of diacid solubility with temperature variation tendency, is added sulfuric acid in alkali metal succinate solution, and high temperature crystallization is heavy
Partial alkaline-metal sulfate is isolated in shallow lake, and then low-temperature precipitation removes succinic acid crystal crude product, and last succinic acid crude product dissolution is lived
Property carbon decoloring, recrystallization and it is dry obtain succinic acid product, however, relatively complicated, the alkali metal sulphur of the step of being disclosed in the patent
Hydrochlorate may will affect the quality of succinic acid product.
Summary of the invention
The purpose of the present invention is the preparations for succinate in the prior art using succinic acid sterling as raw material, and biology
The problem of base succinic acid separation process complexity proposes a kind of method that succinate is extracted from succinic acid fermentation liquor.
Technical solution
A method of extracting succinate from succinic acid fermentation liquor, comprising the following steps:
(1) filtered fluid is obtained using filter progress removing thallus and bulky grain suspended matter to succinic acid fermentation liquor；
(2) concentrate is concentrated to give to filtered fluid；
(3) concentrate is come into full contact under the action of an acid with alcohol, is esterified and is crystallized precipitation concerted reaction, obtains ester
Change crystallized mixed feed liquid；
(4) crystal in removing esterification crystallized mixed feed liquid obtains de- crystal esterification clear liquid；
(5) de- crystal esterification clear liquid is obtained into succinate by the way of rectifying.
In step (1), the succinic acid fermentation liquor includes Escherichia coli, Actinobacillus in pH by the bacterial strain of succinic acid-producing
Value is fermenting and producing under 6~7.5, anaerobic condition, and succinic acid concentration in fermentation liquid is 36.0~90.0g/L.
In step (1), sodium salt fermentation liquid of the succinic acid fermentation liquor selected from succinic acid, the ammonium salt fermentation liquid of succinic acid,
The sylvite fermentation liquid of succinic acid, one of magnesium salts fermentation liquid or the calcium salt fermentation liquid of succinic acid of succinic acid.
In step (1), the filter progress is to be by 0.2 μm of microfiltration membranes and molecular cut off by succinic acid fermentation liquor
The ultrafiltration membrance filter of 5000 dalton.
In step (2), the filtered fluid concentration, which refers to for filtered fluid to be concentrated into, is calculated as 15- with succinic acid mass content
60%, 20-45% is preferably calculated as with succinic acid mass content.
In step (3), the alcohol includes the straight chain alcohol of C1-C16, the C1-C16 alcohol with branch, carbon atoms 3-16
Cycloalkyl alcohol and carbon atoms 3-16 aromatic radical alcohol, be chosen in particular from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol,
One of isobutanol or the tert-butyl alcohol.
In step (3), the succinate molar ratio in the alcohol and concentrate is 10:1-2:1, preferably 6:1-3:1.
In step (3), the acid in hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acidic materials containing sulfonic acid group one
Kind, preferably sulfuric acid.
In step (3), the esterification and crystallization collaboration evolution reaction temperature are 20-110 DEG C, preferably 50-98 DEG C.In order to protect
Card concentrate and alcohol come into full contact in the effect of acid, can be using stirring, ultrasound or baffled reactor mode, but are not limited only to
This.
In step (4), the method for the crystal in the removing esterification crystallized mixed feed liquid: it can be taken using staticly settling
The mode of clear liquid, or the mode of filtering, are preferably filtered.Crystal in the removing esterification crystallized mixed feed liquid includes chlorination
Sodium, sodium nitrate, sodium sulphate, sodium phosphate, sodium sulfonate, ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid hydrogen
Diammonium, ichthyodin, potassium chloride, potassium nitrate, potassium sulfate, potassium phosphate, potassium sulfonate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium phosphate, sulphur
Sour magnesium, calcium chloride, calcium nitrate, calcium sulfate, sulfoacid calcium.
In step (5), the operating pressure of the rectifying is 0.015-0.280MPa, preferably 0.02-0.15MPa.
Technical effect
It is different as raw material using succinic acid sterling and alcohol for synthesizing from traditional succinate, and the present invention is a kind of from succinic acid
The method that fermentation liquid directly obtains succinate, from succinic acid fermentation liquor directness, by filtering, concentration, esterification and essence
Evaporate and etc. succinate product can be obtained, the subtractive process of succinic acid is omitted, can simultaneously be effectively removing fermentation
Salt in liquid has lower production cost.The succinate product purity that the method for the present invention obtains is high, can be used for synthesizing
Light stabilizer, high-grade paint, fungicide, medicine intermediate are hydrogenated to butanediol.
Specific embodiment
The present invention is further explained in the light of specific embodiments.The concentration of succinic acid uses efficient liquid in the present invention
GC headspace analysis, succinate content use Agilent DB-FFAP chromatographic column gas chromatographic analysis.
Embodiment 1
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 12.0kg methanol, sulphur is added
Sour 2.5kg stirs 58 DEG C of reaction 30min, filters sulfur acid sodium sediment, obtains esterification clear liquid 19.0kg, smart at 0.05MPa
It evaporates to obtain the dimethyl succinate 5.2kg that purity is 99.2%.
Embodiment 2
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 17.0kg ethyl alcohol, sulphur is added
Sour 2.5kg stirs 58 DEG C of reaction 30min, filters sulfur acid sodium sediment, obtains esterification clear liquid 21.6kg, smart at 0.05MPa
It evaporates to obtain the diethyl succinate 6.2kg that purity is 99.3%.
Embodiment 3
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 23.0kg normal propyl alcohol, is added
Sulfuric acid 2.5kg stirs 60 DEG C of reaction 30min, filters sulfur acid sodium sediment, esterification clear liquid 27.2kg is obtained, at 0.03MPa
Rectifying obtains the succinic acid di-n-propyl ester 7.0kg that purity is 99.5%.
Embodiment 4
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 23.0kg n-butanol, is added
Sulfuric acid 2.5kg stirs 60 DEG C of reaction 30min, filters sulfur acid sodium sediment, esterification clear liquid 27.4kg is obtained, at 0.03MPa
Rectifying obtains the succinic acid di-n-butyl 8.1kg that purity is 99.4%.
Embodiment 5
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 23.0kg n-amyl alcohol, is added
Sulfuric acid 2.5kg stirs 60 DEG C of reaction 30min, filters sulfur acid sodium sediment, esterification clear liquid 26.8kg is obtained, at 0.03MPa
Rectifying obtains the two n-pentyl ester 8.0kg of succinic acid that purity is 99.6%.
Embodiment 6
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 28.0kg cyclohexanol, is added
Sulfuric acid 2.5kg stirs 70 DEG C of reaction 30min, filters sulfur acid sodium sediment, esterification clear liquid 31.1kg is obtained, at 0.05MPa
Rectifying obtains the succinic acid dicyclohexyl maleate 5.2kg that purity is 99.8%.
Embodiment 7
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 25.0kg benzyl alcohol, is added
Sulfuric acid 2.5kg stirs 50 DEG C of reaction 30min, filters sulfur acid sodium sediment, esterification clear liquid 28.7kg is obtained, at 0.05MPa
Rectifying obtains the succinic acid benzhydryl ester 4.2kg that purity is 99.6%.
Embodiment 8
The sodium salt fermentation liquid 100L that succinic acid concentration is 45.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 45.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 7.4L.Upper concentrate is mixed with 34.0kg laruyl alcohol, is added
Sulfuric acid 2.5kg stirs 58 DEG C of reaction 30min, filters sulfur acid sodium sediment, esterification clear liquid 37.4kg is obtained, at 0.05MPa
Rectifying obtains the succinic acid dilauryl 4.3kg that purity is 99.8%.
Embodiment 9
The ammonia salt fermentation liquid 100L that succinic acid concentration is 40.0g/L is taken to be by 0.2 μm of microfiltration membranes and molecular cut off
The ultrafiltration membrance filter removing thallus and bulky grain suspended matter of 5000 dalton, obtain ultrafiltrate 98L, concentration 39.3g/L, are concentrated
Ultrafiltrate to succinic acid mass concentration is 60%, obtains concentrate 6.2L.Upper concentrate is mixed with 17kg methanol, sulfuric acid is added
2.5kg stirs 58 DEG C of reaction 30min, filters liquid containing ammonium sulfate sediment, obtains esterification clear liquid 20.1kg, the rectifying at 0.05MPa
Obtain the succinic acid dilauryl 4.0kg that purity is 99.9%.
Claims (6)
1. a kind of method for extracting succinate from succinic acid fermentation liquor, which comprises the following steps:
(1) filtered fluid is obtained using filter progress removing thallus and bulky grain suspended matter to succinic acid fermentation liquor；
(2) concentrate is concentrated to give to filtered fluid；
(3) concentrate is come into full contact under the action of an acid with alcohol, is esterified and is crystallized precipitation concerted reaction, obtain esterification knot
Brilliant mixed liquor；
(4) crystal in removing esterification crystallized mixed feed liquid obtains de- crystal esterification clear liquid；
(5) de- crystal esterification clear liquid is obtained into succinate by the way of rectifying；
In step (1), the succinic acid fermentation liquor is fermented by the bacterial strain of succinic acid-producing in the case where pH value is 6~7.5, anaerobic condition
Production is made, and succinic acid concentration in fermentation liquid is 36.0~90.0g/L；
In step (1), the succinic acid fermentation liquor is selected from the sodium salt fermentation liquid of succinic acid, the ammonium salt fermentation liquid of succinic acid, fourth two
The sylvite fermentation liquid of acid, one of magnesium salts fermentation liquid or the calcium salt fermentation liquid of succinic acid of succinic acid；
In step (1), it by 0.2 μm of microfiltration membranes and molecular cut off is 5000 that the filter progress, which is by succinic acid fermentation liquor,
The ultrafiltration membrance filter of dalton；
In step (3), the succinate molar ratio in the alcohol and concentrate is 10:1-2:1；
In step (3), the esterification and crystallization collaboration evolution reaction temperature are 20-110 DEG C.
2. the method for succinate is extracted from succinic acid fermentation liquor as described in claim 1, which is characterized in that step
(2) in, the filtered fluid concentration, which refers to for filtered fluid to be concentrated into, is calculated as 15-60% with succinic acid mass content.
3. the method for succinate is extracted from succinic acid fermentation liquor as described in claim 1, which is characterized in that step
(3) in, the alcohol is selected from one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol or tert-butyl alcohol.
4. the method for succinate is extracted from succinic acid fermentation liquor as described in claim 1, which is characterized in that step
(3) in, the acid is selected from one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acidic materials containing sulfonic acid group.
5. the method for succinate is extracted from succinic acid fermentation liquor as described in claim 1, which is characterized in that step
(4) in, it is described removing esterification crystallized mixed feed liquid in crystal method are as follows: using staticly settle take supernatant by the way of or
The mode of filtering.
6. such as the method described in any one of claim 1 to 5 for extracting succinate from succinic acid fermentation liquor, feature exists
In in step (5), the operating pressure of the rectifying is 0.015-0.280MPa.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476989A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院过程工程研究所 | Succinic acid separating apparatus and method based on full membrane separation system |
| CN103343147A (en) * | 2013-07-31 | 2013-10-09 | 山东兰典生物科技股份有限公司 | Method for preparing dibutyl succinate from cassava raw materials |
| WO2015085185A1 (en) * | 2013-12-06 | 2015-06-11 | Myriant Corporation | A process for preparing succinate ester |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476989A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院过程工程研究所 | Succinic acid separating apparatus and method based on full membrane separation system |
| CN103343147A (en) * | 2013-07-31 | 2013-10-09 | 山东兰典生物科技股份有限公司 | Method for preparing dibutyl succinate from cassava raw materials |
| WO2015085185A1 (en) * | 2013-12-06 | 2015-06-11 | Myriant Corporation | A process for preparing succinate ester |
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