CN104876817B - A kind of method that use succinic acid fermentation liquor extracts succinic acid - Google Patents

A kind of method that use succinic acid fermentation liquor extracts succinic acid Download PDF

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CN104876817B
CN104876817B CN201510196882.8A CN201510196882A CN104876817B CN 104876817 B CN104876817 B CN 104876817B CN 201510196882 A CN201510196882 A CN 201510196882A CN 104876817 B CN104876817 B CN 104876817B
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succinic acid
solution
transferred
fermentation
magnesium
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CN104876817A (en
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吕涛
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SHANDONG FEIYANG CHEMICAL CO., LTD.
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Farsighted Bio Tech Ltd That Makes Country Prosperous Is Won In Zhenjiang
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Abstract

The present invention relates to a kind of method that use succinic acid fermentation liquor extracts succinic acid, its extracting method is(1)The preparation of succinic acid fermentation liquor(2)Succinate is converted into the ammonium of succinic acid two acidification succinic acid fermentation liquor again using ammonia(3)The extraction of succinic acid(4)Introduce magnesium salts Ammonia Process and bipolar membrane electrodialysis reclaims soda acid technique, recycle evaporation water, ammonia, magnesium carbonate suspension, hydrochloric acid;During by the ammonium of succinic acid two intermediate product realize during clean manufacturing, while having used resins exchange that the ammonium of succinic acid two is converted into succinic acid during avoiding traditional handicraft, cause the problem of quantity of wastewater effluent is big, and process difficulty is reduced, it is the process for cleanly preparing of a closure.

Description

A kind of method that use succinic acid fermentation liquor extracts succinic acid
Technical field
Succinic acid fermentation liquor is used the present invention relates to one kind, by the method for the ammonium procedure extraction succinic acid of succinic acid two.This Invention belongs to technical field of biochemical industry.
Background technology
Succinic acid(succinic acid)Also known as butanedioic acid, it is widely present in organism, is that a kind of important binary has Machine carboxylic acid, is also the important metabolite of microorganism tricarboxylic acid cycle glycolytic pathway.At present, succinic acid can pass through microorganism Fermentation is prepared.
During microbial fermentation prepares succinic acid, according to the species of microorganism and the difference of zymotechnique, generate The process of many different rear extractions.
The process isolated and purified is exactly to remove insoluble impurities, and succinate is converted into free succinic acid, and by its Concentration brings up to required process.A kind of route is short, cost is low, separation-extraction technology pollution-free, easy to operate is for work Industry fermentation production of succinic acid is very crucial.
The process isolated and purified is exactly to remove insoluble impurities, and succinate is converted into free succinic acid, and by its Concentration brings up to required process.A kind of route is short, cost is low, separation-extraction technology pollution-free, easy to operate is for work Industry fermentation production of succinic acid is very crucial.
Several extraction processes studied at present have liquid-liquid extraction method, calcium salt perfectly crystallization process, ammonium sulfate cracking partition method and Membrane separation process etc..
Liquid-liquid extraction method be in chemical industry one kind work well, widely used method, but used in extraction process A large amount of organic solvents, the toxic effect of residual solvent its medicine food industry application.
Calcium salt method need to consume a large amount of sulfuric acid, calcium oxide or calcium hydroxide, and can not recycle.
Embrane method extraction efficiency is high, but during easily block, flow is unstable.
US5168055 discloses one kind and does not consume a large amount of reagents, and production and the purifying fourth two of a large amount of accessory substances are not produced yet Accessory substance ammonium sulfate in the technique of acid, production process, which can be realized, to be recycled, so as to form the clean manufacturing mistake of a closure Journey, succinic acid crystal is unique product, but this crystallization process operating condition is harsher, and difficulty is larger.
CN101665428 provides a kind of method for extracting succinic acid, has used ammonia, ammonium carbonate or ammonium hydrogen carbonate by fourth Diacid salt is converted into the ammonium of succinic acid two, reuses cationic ion-exchange resin and is converted into succinic acid;Wherein cation regenerant exchanges tree The cleaning fluid of fat prepares ammonium salt as fertilizer application, reuse magnesium precipitate thing to fermentation system.It the method use resins exchange Traditional handicraft process, causes quantity of wastewater effluent big, and reclaim can as chemical fertilizer ammonium salt when need the water of cleaning being all evaporated, Cost recovery is high.Whole flow process fails to realize closure, it is impossible to the salts substances and hydrochloric acid used in removal process, causes auxiliary material Waste and problem of environmental pollution.This method is unsuitable for industrialization production requirements.
The content of the invention
It is an object of the invention to overcome defect of the prior art there is provided a kind of using succinic acid fermentation liquor extraction fourth two The method of acid.
The present invention is achieved by the following technical programs.
A kind of method that use succinic acid fermentation liquor extracts succinic acid, its extracting method is as follows:
(1)The preparation of succinic acid fermentation liquor
1. Actinobacillus succinogenes are cultivated using seed culture medium in fermentation cauldron, the group of the seed culture medium It is calculated as into composition by mass concentration:Peptone 5g/L, corn steep liquor 20g/L, glucose 20g/L, potassium dihydrogen phosphate 1.5g/L, phosphorus Sour disodium hydrogen 1.5g/L, yeast extract 5g/L, deionized water are prepared, and need the volume per minute of carbon dioxide to be passed through in the fermentation cauldron Measure the fermenter volume for 0.1% ~ 0.5%, during stream plus magnesium carbonate mass concentration be 20% magnesium carbonate suspension, maintain body It is pH stable in 6.0-7.0;
2. the Actinobacillus succinogenes Jing Guo seed culture medium culture are moved into fermentation medium, carried out in fermentation cauldron Succinic acid fermentation liquor is cultivated to obtain, the constituent of the fermentation medium is calculated as by mass concentration:Peptone 5g/L, corn steep liquor 10g/L, glucose 100g/L, potassium dihydrogen phosphate 2.5g/L, disodium hydrogen phosphate 2.5g/L, yeast extract 5g/L, sodium acetate 5g/L, Configured with deionized water, the fermentation tank that the volume intake per minute that carbon dioxide is needed in the fermentation cauldron is 0.1% ~ 0.5% Product, during stream plus magnesium carbonate mass concentration be 20% magnesium carbonate suspension, maintenance system pH stable is in 6.0-7.0;Now The main comprise material of succinic acid fermentation liquor is succinic acid magnesium and the culture medium residue of fermentation process;
(2)The processing of succinic acid fermentation liquor
1. succinic acid fermentation liquor is filtered into obtain clear liquid by being pumped into ceramic film component;
2. clear liquid is transferred in the ammonium conversion tank of succinic acid two, ammonia enters from conversion pot bottom, anti-after pH value to 10 ~ 10.2 It should finish, stop ammonia and enter, react to obtain conversion fluid;
3. conversion fluid is subjected to secondary filter, the separation ammonium of succinic acid two and magnesium hydroxide by being pumped into ceramic film component Solid, obtains clear liquid and magnesium hydroxide suspension containing the ammonium of succinic acid two, and magnesium hydroxide suspension mass concentration reaches 20%;
4. the clear liquid containing the ammonium of succinic acid two is transferred in acidifying kettle, the hydrochloric acid conditioning solution pH value for adding 5% is 2, generation Succinic acid and ammonium chloride mixed solution;
(3)The extraction of succinic acid
1. step will be passed through(2)4. the mixed solution after handling is by being pumped into evaporating column, and vapor is from steaming in solution The outflow of tower top is sent out, it is 25% ~ 30% that solution concentration, which is concentrated into succinic acid content, obtains concentrate;
2. concentrate is transferred to crystallizing tank, speed of agitator is 20 ~ 30rpm, and control temperature is reduced to after 8 ~ 10 DEG C, stops 4 Hour, crystallization is finished;
3. step will be passed through(3)2. the solution after handling is transferred to centrifuge, centrifuges to obtain succinic acid crystal product and crystallization mother Liquid;
(4)The recovery and utilization of accessory substance
1. the recovery and utilization of water are evaporated:Step will be passed through(3)1. the vapor flowed out reclaims evaporation water through subcooler, For arbitrarily needing water step;
2. the recovery and utilization of ammonia:By step(3)3. the crystalline mother solution and step reclaimed(2)3. the magnesium hydroxide reclaimed Suspension solution mixing is transferred to the reaction of ammonia generation tank, and it is 120 ~ 130 DEG C control temperature, 1.5 ~ 2kg/cm2 of pressure, pH value for 9 ~ 10, the ammonia of generation is transferred to step(2)2. utilize, crystalline mother solution must react phase after completion of the reaction with magnesium hydroxide suspension solution, Reaction is mutually the magnesium chloride solution of mass concentration 20 ~ 25%;
3. the recovery and utilization of magnesium carbonate suspension:Sodium hydroxide solution is loaded raw after injector, absorbing carbon dioxide Sodium carbonate is produced, sodium carbonate is transferred in bipolar membrane electrodialysis equipment;Step will be passed through(4)2. reaction is mutually transferred to magnesium carbonate generation Tank, magnesium carbonate suspension and sodium chloride solution that generation magnesium carbonate mass concentration is 20%, magnesium carbonate suspension are mixed with sodium carbonate It is transferred to step(1)2. utilize, sodium chloride solution reclaims generation hydrochloric acid by bipolar membrane electrodialysis equipment;
4. the recovery and utilization of hydrochloric acid:Recycling step(4)3. the hydrochloric acid generated in bipolar membrane electrodialysis equipment, is transferred to step (2)4. utilize.
A kind of method that use succinic acid fermentation liquor extracts succinic acid, wherein, succinic acid magnesium in the succinic acid fermentation liquor Mass percentage content be 8% ~ 12%.
Beneficial effects of the present invention are:
Use Actinobacillus succinogenes(Actinobacillus succinogenes)The anaerobic fermentations of CGMCC 1593 are carried out The preparation of succinic acid is a kind of very reliable efficient method.PH adjusting agent in using magnesium carbonate as fermentation process, then send out Main comprise material is succinic acid magnesium and the culture medium residue of fermentation process in zymotic fluid.
Process for cleanly preparing during being advantageously implemented in extraction process by the intermediate product of the ammonium of succinic acid two, suitably Involved other chemicals during change, reduce process difficulty, you can reach the requirement of industrialized production, and during The ammonium of succinic acid two is converted into by succinic acid using acidization, it is to avoid used resins exchange during traditional handicraft, caused dirt The problem of water discharge capacity is big.
If it was found that, during introduce the technique that magnesium salts Ammonia Process and bipolar membrane electrodialysis reclaim soda acid, make Process reaches the cleaning procedure of closure, while process difficulty is reduced, for example, the step of avoiding pyrolytic ammonium hydrogen sulfate Deng.Whole technical process, generates succinic acid crystal product, evaporation water, ammonia, magnesium carbonate suspension, hydrochloric acid it is all recyclable with Utilize, without the generation of other accessory substances.
It should be noted that due to microbial fermentation feature, there is a small amount of acetic acid generation in zymotic fluid, therefore acetic acid can be During accumulate, but this have no effect on this patent proposition technical process and method.
Embodiment
Embodiment one
A kind of method that use succinic acid fermentation liquor extracts succinic acid, its extracting method is as follows:
(1)The preparation of succinic acid fermentation liquor
1. peptone 5kg, corn steep liquor 20kg, glucose 20kg, potassium dihydrogen phosphate 1.5kg, disodium hydrogen phosphate are weighed 1.5kg, yeast extract 5kg, deionized water 947kg are configured to the seed culture medium that gross mass is 1000kg, are used in fermentation cauldron Seed culture medium is cultivated Actinobacillus succinogenes, and the volume intake per minute that carbon dioxide is needed in the fermentation cauldron is 10L, during stream plus magnesium carbonate mass concentration be 20% magnesium carbonate suspension, maintenance system pH stable is in 6.0-7.0;
2. peptone 50kg, corn steep liquor 100kg, glucose 1000kg, potassium dihydrogen phosphate 25kg, disodium hydrogen phosphate are weighed 25kg, yeast extract 50kg, sodium acetate 50kg, deionized water 8700kg are configured to the fermentation medium that gross mass is 10000kg, will Actinobacillus succinogenes by seed culture medium culture are moved into fermentation medium, and ferment to obtain succinic acid fermentation liquor, now fourth The main comprise material of diacid zymotic fluid is succinic acid magnesium and the culture medium residue of fermentation process, the quality percentage of succinic acid magnesium Specific concentration is 10%, needed in the fermentation cauldron carbon dioxide volume intake per minute be 10L, during stream plus carbonic acid it is magnesia The magnesium carbonate suspension that concentration is 20% is measured, maintenance system pH stable is in 6.0-7.0;
(2)The processing of succinic acid fermentation liquor
1. succinic acid fermentation liquor is filtered into obtain clear liquid by being pumped into ceramic film component;
2. clear liquid is transferred in the ammonium conversion tank of succinic acid two, ammonia enters from conversion pot bottom, has been reacted after pH value to 10 Finish, stop ammonia and enter, react to obtain conversion fluid;
3. conversion fluid is subjected to secondary filter, the separation ammonium of succinic acid two and magnesium hydroxide by being pumped into ceramic film component Solid, obtains clear liquid and magnesium hydroxide suspension containing the ammonium of succinic acid two, and magnesium hydroxide suspension mass concentration reaches 20%;
4. the clear liquid containing the ammonium of succinic acid two is transferred in acidifying kettle, adds 10 tons of 5% hydrochloric acid, mixing generation succinic acid 845kg and ammonium chloride 739kg mixed solution;
(3)The extraction of succinic acid
1. step will be passed through(2)4. the mixed solution after handling is by being pumped into evaporating column, and vapor is from steaming in solution The outflow of tower top is sent out, it is 25% that solution concentration, which is concentrated into succinic acid content, obtains concentrate;
2. concentrate is transferred to crystallizing tank, speed of agitator is 30rpm, control temperature is reduced to after 10 DEG C, is stopped 4 hours, Crystallization is finished;
3. step will be passed through(3)2. the solution after handling is transferred to centrifuge, centrifuges to obtain succinic acid crystal product 709kg and knot Brilliant mother liquor 2266kg;
(4)The recovery and utilization of accessory substance
1. the recovery and utilization of water are evaporated:Step will be passed through(3)1. the vapor flowed out reclaims evaporation water through subcooler, Water step is needed available for any;
2. the recovery and utilization of ammonia:By step(3)3. the crystalline mother solution and step reclaimed(2)3. the magnesium hydroxide reclaimed Suspension solution mixing is transferred to the reaction of ammonia generation tank, and it is 120 ~ 130 DEG C control temperature, 1.5 ~ 2kg/cm2 of pressure, pH value for 9 ~ 10, the ammonia of generation can be transferred to step(2)2. utilize, crystalline mother solution must react phase after completion of the reaction with magnesium hydroxide suspension solution 3324kg, reaction is mutually the magnesium chloride solution of mass concentration 20%;
3. the recovery and utilization of magnesium carbonate suspension:Sodium hydroxide solution is loaded raw after injector, absorbing carbon dioxide Sodium carbonate is produced, sodium carbonate is transferred in bipolar membrane electrodialysis equipment;Step will be passed through(4)2. reaction is mutually transferred to magnesium carbonate generation Tank, magnesium carbonate suspension 2957kg and sodium chloride solution that generation magnesium carbonate mass concentration is 20%, magnesium carbonate are mixed with sodium carbonate Suspension is transferred to step(1)2. utilize, sodium chloride solution reclaims generation hydrochloric acid by bipolar membrane electrodialysis equipment;
4. the recovery and utilization of hydrochloric acid:Recycling step(4)3. the hydrochloric acid generated in bipolar membrane electrodialysis equipment, is transferred to step (2)4. utilize.
As can be seen from the above-described embodiment, the clean manufacturing work during being realized by the intermediate product of the ammonium of succinic acid two Skill, while having used resins exchange that the ammonium of succinic acid two is converted into succinic acid during avoiding traditional handicraft, causes sewage to arrange High-volume big the problem of, and during introduce the technique that magnesium salts Ammonia Process and bipolar membrane electrodialysis reclaim soda acid, reach process The cleaning procedure of closure, while reducing process difficulty;Whole technical process generates succinic acid crystal product, evaporation water, ammonia Gas, magnesium carbonate suspension, hydrochloric acid are all recyclable with utilizing, without the generation of other accessory substances.
Here description of the invention and application be illustrative, be not wishing to limit the scope of the invention to above-described embodiment In, therefore, the present invention is not limited by the present embodiment, and the technical scheme that any use equivalence replacement is obtained is in present invention protection In the range of.

Claims (2)

1. a kind of method that use succinic acid fermentation liquor extracts succinic acid, it is characterized in that, its extracting method is as follows:
(1)The preparation of succinic acid fermentation liquor
1. Actinobacillus succinogenes are cultivated using seed culture medium in fermentation cauldron, the composition of the seed culture medium into Divide and be calculated as by mass concentration:Peptone 5g/L, corn steep liquor 20g/L, glucose 20g/L, potassium dihydrogen phosphate 1.5g/L, phosphoric acid hydrogen Disodium 1.5g/L, yeast extract 5g/L, deionized water are prepared, and the volume intake per minute that carbon dioxide is needed in the fermentation cauldron is 0.1% ~ 0.5% fermenter volume, during stream plus magnesium carbonate mass concentration be 20% magnesium carbonate suspension, maintenance system pH Value stabilization is in 6.0-7.0;
2. the Actinobacillus succinogenes Jing Guo seed culture medium culture are moved into fermentation medium, cultivated in fermentation cauldron Succinic acid fermentation liquor is obtained, the constituent of the fermentation medium is calculated as by mass concentration:Peptone 5g/L, corn steep liquor 10g/L, Glucose 100g/L, potassium dihydrogen phosphate 2.5g/L, disodium hydrogen phosphate 2.5g/L, yeast extract 5g/L, sodium acetate 5g/L, spend from The fermenter volume that the volume intake per minute of carbon dioxide is 0.1% ~ 0.5%, process are needed in sub- water configuration, the fermentation cauldron Middle stream plus the magnesium carbonate suspension that magnesium carbonate mass concentration is 20%, maintenance system pH stable is in 6.0-7.0;Now succinic acid The main comprise material of zymotic fluid is succinic acid magnesium and the culture medium residue of fermentation process;
(2)The processing of succinic acid fermentation liquor
1. succinic acid fermentation liquor is filtered into obtain clear liquid by being pumped into ceramic film component;
2. clear liquid is transferred in the ammonium conversion tank of succinic acid two, ammonia enters from conversion pot bottom, has been reacted after pH value to 10 ~ 10.2 Finish, stop ammonia and enter, react to obtain conversion fluid;
3. conversion fluid is subjected to secondary filter by being pumped into ceramic film component, the separation ammonium of succinic acid two and magnesium hydroxide are solid Body, obtains clear liquid and magnesium hydroxide suspension containing the ammonium of succinic acid two, and magnesium hydroxide suspension mass concentration reaches 20%;
4. the clear liquid containing the ammonium of succinic acid two is transferred in acidifying kettle, the hydrochloric acid conditioning solution pH value for adding 5% is 2, generates fourth two Acid and ammonium chloride mixed solution;
(3)The extraction of succinic acid
1. step will be passed through(2)4. the mixed solution after handling is by being pumped into evaporating column, and vapor is from evaporating column in solution Top is flowed out, and it is 25% ~ 30% that solution concentration, which is concentrated into succinic acid content, obtains concentrate;
2. concentrate is transferred to crystallizing tank, speed of agitator is 20 ~ 30rpm, and control temperature is reduced to after 8 ~ 10 DEG C, stopped 4 hours, Crystallization is finished;
3. step will be passed through(3)2. the solution after handling is transferred to centrifuge, centrifuges to obtain succinic acid crystal product and crystalline mother solution;
(4)The recovery and utilization of accessory substance
1. the recovery and utilization of water are evaporated:Step will be passed through(3)1. the vapor flowed out reclaims evaporation water through subcooler, is used for Arbitrarily need water step;
2. the recovery and utilization of ammonia:By step(3)3. the crystalline mother solution and step reclaimed(2)3. the magnesium hydroxide reclaimed is suspended Solution mixing is transferred to the reaction of ammonia generation tank, and it is 120 ~ 130 DEG C, 1.5 ~ 2kg/cm of pressure to control temperature2, pH value is 9 ~ 10, raw Into ammonia be transferred to step(2)2. utilize, crystalline mother solution must react phase after completion of the reaction with magnesium hydroxide suspension solution, react phase For the magnesium chloride solution of mass concentration 20 ~ 25%;
3. the recovery and utilization of magnesium carbonate suspension:Carbon is produced after sodium hydroxide solution is loaded into injector, absorbing carbon dioxide Sour sodium, sodium carbonate is transferred in bipolar membrane electrodialysis equipment;Step will be passed through(4)2. reaction is mutually transferred to magnesium carbonate generation tank, with Magnesium carbonate suspension and sodium chloride solution that sodium carbonate mixing generation magnesium carbonate mass concentration is 20%, magnesium carbonate suspension are transferred to Step(1)2. utilize, sodium chloride solution reclaims generation hydrochloric acid by bipolar membrane electrodialysis equipment;
4. the recovery and utilization of hydrochloric acid:Recycling step(4)3. the hydrochloric acid generated in bipolar membrane electrodialysis equipment, is transferred to step(2) 4. utilize.
2. the method that a kind of use succinic acid fermentation liquor as claimed in claim 1 extracts succinic acid, it is characterized in that the fourth two The mass percentage content of succinic acid magnesium is 8% ~ 12% in acid fermentation liquid.
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CN105566096B (en) * 2015-12-18 2018-11-16 江西科技师范大学 A kind of technique isolating and purifying succinic acid from microbial fermentation solution
CN110373432A (en) * 2018-04-12 2019-10-25 中国科学院过程工程研究所 It is a kind of using synthesis gas as the system and its processing method of raw material coproduction succinic acid and alcohols
CN114540433B (en) * 2022-02-17 2023-07-25 山东飞扬化工有限公司 Technological method for producing succinic acid and purification method thereof

Citations (5)

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US5168055A (en) * 1986-06-11 1992-12-01 Rathin Datta Fermentation and purification process for succinic acid
CN101348428A (en) * 2008-09-05 2009-01-21 江南大学 Method for extracting amber acid in fermentation liquor by anion resin adsorption
CN101748161A (en) * 2010-01-19 2010-06-23 南京工业大学 Succinic acid purification process through anaerobic fermentation
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
CN103524327A (en) * 2013-10-16 2014-01-22 江阴奥瑞诺生物技术有限公司 Method for extracting succinic acid from succinic acid fermentation liquor by using electrodialysis method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5168055A (en) * 1986-06-11 1992-12-01 Rathin Datta Fermentation and purification process for succinic acid
CN101348428A (en) * 2008-09-05 2009-01-21 江南大学 Method for extracting amber acid in fermentation liquor by anion resin adsorption
CN101748161A (en) * 2010-01-19 2010-06-23 南京工业大学 Succinic acid purification process through anaerobic fermentation
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
CN103524327A (en) * 2013-10-16 2014-01-22 江阴奥瑞诺生物技术有限公司 Method for extracting succinic acid from succinic acid fermentation liquor by using electrodialysis method

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