CN1205178C - Process for extracting glutamine from fermentation broth - Google Patents
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Abstract
本发明涉及一种从发酵液中提取谷氨酰胺的工艺方法，属于药用和保健用氨基酸制备技术领域。本方法是先对谷氨酰胺发酵液进行预处理，除去菌体和部分蛋白质、色素及多糖，控制预处理后发酵液的pH值，通过电渗析设备去除其中的无机盐，重新调节料液pH值，并通入处理好的OH型阴离子交换柱，杂质与树脂发生交换被吸附，谷氨酰胺流过离子交换柱得到分离，流出液先脱色、真空浓缩，然后等电结晶，粗晶体通过有机溶剂洗涤，干燥即可。利用本发明的工艺提取发酵液中谷氨酰胺，可以明显减少交换树脂的用量，有效避免谷氨酰胺在强碱和强酸环境中的转化问题，大大降低生产成本，谷氨酰胺的总提取收率达到70%左右，适用于工业生产。The invention relates to a process for extracting glutamine from fermentation liquid, belonging to the technical field of amino acid preparation for medicine and health care. This method is to pretreat the glutamine fermentation liquid first, remove bacteria and some proteins, pigments and polysaccharides, control the pH value of the fermented liquid after pretreatment, remove the inorganic salts in it through electrodialysis equipment, and re-adjust the pH of the feed liquid Value, and pass into the treated OH type anion exchange column, the impurities are exchanged with the resin and adsorbed, glutamine flows through the ion exchange column to be separated, the effluent is first decolorized, vacuum concentrated, and then isoelectric crystallization, the crude crystal is passed through the organic Solvent wash and dry. Utilizing the process of the present invention to extract glutamine in the fermentation broth can significantly reduce the amount of exchange resin, effectively avoid the conversion problem of glutamine in strong alkali and strong acid environment, greatly reduce the production cost, and the total extraction yield of glutamine reaches About 70%, suitable for industrial production.
Description
Technical field
The present invention relates to a kind of processing method of from fermented liquid, extracting glutamine, belong to amino acid preparing technical field medicinal and for health care.
Background technology
L-glutaminate (Gln) is the γ-Carboxylamide thing of L-L-glutamic acid (Glu), is 20 kinds and constitutes one of proteinic primary amino acid.Its chemical molecular formula is H
2NCOCH
2CH
2CH (NH
2) COOH, molecular weight 146.15, decomposition temperature 184-185 ℃, iso-electric point 5.65 belongs to neutral amino acids.Medical discovery shows that glutamine is the essential amino acid of a kind of condition in recent years, plays a part very importantly in biological metabolism, will cause multiple disease during shortage.
The major country of production of fermentative Production glutamine is Japan and Korea S.It is estimated that the annual production of existing whole world glutamine has reached about 4000 tons, and shows a rising trend.The technical study of fermentative Production glutamine is in the existing recent two decades history of China, but at present owing to also there is not sophisticated downstream separation technology, still none tame enterprise adopts fermentation method scale operation glutamine.Both at home and abroad the separation and Extraction glutamine all adopts negative and positive twin columns ion exchange method basically, just difference to some extent on the combination of resin choice, zwitterion post and concrete operations mode.Domestic report (ion-exchange and absorption, 1998,14 (2), 97～103) in 1998 adopts twin columns method stepwise elution, and the laboratory yield can reach 56.6%.The early 1990s foreign patent (Miyazawa et al.Method for purifying L-glutamine, Int.Cl.C07C 227/00, United States Patent 4,966,994 Filed:July.11,1989 Date ofPatent:Oct.30,1990.) yield in the laboratory reaches more than 70% by fermented liquid coarse crystallization and ion-exchange process combined.Negative and positive twin columns separating technology is because the exchange resin consumption is huge, and wash-out and regeneration acid and alkali consumption are too many, causes serious environmental to pollute, and glutamine changes into L-glutamic acid easily at highly basic and strong acid environment in addition, causes yield very low; Coarse crystallization technology then consumes energy bigger.
Summary of the invention
For solving the problem that existing ion exchange method exists, the purpose of this invention is to provide a kind of yield and purity height, low, the low processing method of from fermented liquid, extracting glutamine that reaches environmental protection of power consumption of product cost.
A kind of processing method of from fermented liquid, extracting glutamine that the present invention proposes, it is characterized in that: described processing method is earlier glutamine ferment liquid to be carried out pre-treatment, remove thalline and partial protein, pigment and polysaccharide, the pH value of control pretreatment secondary fermentation liquid, by electrodialysis appts removal inorganic salt wherein, readjust pH value feed liquid, and feed the OH type anion-exchange column handle well, exchange takes place and is adsorbed in impurity and resin, and glutamine flows through ion exchange column and obtains separating, and effluent liquid is decolouring earlier, vacuum concentration, isoelectric point crystallization then, coarse crystal is by organic solvent washing, and drying gets final product, and its processing step is:
(1) flocculation and ultrafiltration coupling pre-treatment fermented liquid: glutamine ferment liquid is adjusted to pH3.0-7.0, slowly stir down and add polymeric flocculant to fermented liquid, final quality concentration is 500-1500ppm, stir fast then, remove by filter solid phase, use the deionized water wash solid phase, collect supernatant liquor and washing water, merge the back ultrafiltration, the molecular weight cut-off of ultra-filtration membrane is 5000-50000, and it is standby to see through liquid;
(2) electrodialytic desalting: see through liquid and regulate pH4-7, enter the electrodialysis unit desalination, the red-tape operati voltage and current is when current density drops to 10-30mA/cm
2The time, stopping electrodialysis, the collection feed liquid is standby;
(3) TREATMENT OF ION EXCHANGE RESINS: deacidite is handled back dress post according to a conventional method, changes into behind the OH type standby then;
(4) impurity is removed in ion-exchange: with the feed adjustment pH4.0-6.0 of step (2) gained, and feed the ion exchange column that step (3) is handled well, the pH value of monitoring stream fluid is determined the moment that feed liquid begins and stops collecting, and guarantees that L-glutamic acid and other impurity do not penetrate resin;
(5) feed liquid decolouring: in above-mentioned effluent liquid, add gac, stir, filter;
(6) vacuum concentration of feed liquid: the feed liquid vacuum concentration after will decolouring;
(7) concentrated solution crystallization: regulate the concentrated solution pH value after decolouring, decrease temperature crystalline filters, and collects crystal;
(8) the primary crystallization mother liquor concentrates according to step (6) earlier, carries out crystallization according to step (7) then, and the crystal of crystal and step (7) collection is merged;
(9) glutamine crystal washing: add organic solvent according to 1-3 ratio doubly in coarse crystal, the after-filtration that stirs is collected crystal;
(10) glutamine crystal drying:, promptly get the glutamine finished product after the cooling with step (9) gained crystal drying.
In above-mentioned processing method, described fermented liquid is a glutamine ferment liquid, removes outside thalline, foreign protein and the residual sugar, the content of glutamine must be higher than 30g/l, L-glutamic acid content must be lower than 10g/l, and ammonium sulfate and ammonium chloride total amount 60g/l also have other salt of carbamate additives for low phosphorus hydrochlorate; The pH value of the described fermented liquid of step (1) is with mineral acid example hydrochloric acid, sulfuric acid and phosphoric acid, any adjusting in organic acid such as acetate, acetic acid and the lactic acid; The described polymeric flocculant of step (1) is any in anionic, cationic, non-ionic polyacrylamide and the chitosan; It is mineral acid example hydrochloric acid, sulfuric acid and phosphoric acid that step (2) is regulated the used acid of material liquid pH, and any in organic acid such as acetate, acetic acid and the lactic acid, used alkali are any in sodium hydroxide, ammoniacal liquor, the yellow soda ash; The used anionite-exchange resin of step (3) is any among D296, D261, D290,201 * 4,201 * 7, D301, D380, D314, the D392; The described organic solvent of step (9) is a dehydrated alcohol, 95% ethanol and methyl alcohol, any in acetone and the butanone.
Because the present invention has adopted electrodialytic desalting and single anion-exchange column to extract glutamine in the fermented liquid except that the technology that impurity such as L-glutamic acid are coupled, can obviously reduce the consumption of exchange resin, avoided the transition problem of glutamine in highly basic and strong acid environment effectively, reduced production cost widely, total extract yield of glutamine reaches about 70%, and quality product meets Japanese Pharmacopoeia.Also making industrially becomes possibility by the fermentative Production glutamine.
Embodiment
The present invention carries out pre-treatment to glutamine ferment liquid earlier, removes most thalline and partial protein, pigment and polysaccharide.The pH value of pretreatment secondary fermentation liquid is controlled within the specific limits, by electrodialysis appts removal inorganic salt wherein, mainly is ammonium sulfate, ammonium chloride and phosphoric acid salt material.Feed liquid readjusts the pH value then, and feeds the OH type anion-exchange column of handling well with suitable flow velocity, and impurity such as L-glutamic acid are because with resin exchange having taken place is adsorbed, and most glutamine then flow through ion exchange column, thereby obtain separating.Effluent liquid is decolouring, vacuum concentration, isoelectric point crystallization then earlier.Coarse crystal is by organic solvent washing, and drying can obtain finished product.
First key point of described processing method is the pre-treatment of fermented liquid, by suitable pretreatment mode, comprise flocculation, ultrafiltration or traditional centrifuging process, remove whole thalline and part foreign protein, polysaccharide, reduce the viscosity of fermented liquid, the obstruction of the film when not only fundamentally having avoided electrodialysis operation and pollution, and be convenient to the mother liquor recrystallization one time, be easy to improve the yield of whole technology.
The control of material liquid pH when second key point of described processing method is electrodialysis.By adding suitable soda acid, and control the electrodialytic operating time well, this process just can be removed the inorganic salt of the overwhelming majority, and product glutamine loss simultaneously seldom.
The adjusting of material liquid pH when selection that the 3rd key point of described processing method is ion exchange resin and ion-exchange.By selecting suitable resin, and guarantee that material liquid pH in certain limit, just can remove impurity such as whole L-glutamic acid, separated and make most glutamine pass ion exchange column.Its processing step is:
1, flocculation and ultrafiltration coupling pre-treatment fermented liquid: glutamine ferment liquid is adjusted to pH3.0-6.0,25 ℃ of temperature, slowly stir down and add polymeric flocculant to fermented liquid, final quality concentration is 500-1500ppm, stirs fast then 10-30 minute, leaves standstill 30-60 minute, remove by filter solid phase, with 2-4 times of deionized water wash solid phase, collect supernatant liquor and washing water, merge the back ultrafiltration.The molecular weight cut-off of ultra-filtration membrane is 5000-50000.It is standby to see through liquid.
2, electrodialytic desalting: see through liquid and regulate pH4-7, enter the electrodialysis unit desalination.Electrodialysis appts is by how in parallel or be composed in series to anode membrane, cavity block and/or Bipolar Membrane, and pole plate is stainless steel or titanium, and the red-tape operati voltage and current is kept feed temperature 10-40 ℃.When current density drops to 10-30mA/cm
2The time, stopping electrodialysis, the collection feed liquid is standby.
3, TREATMENT OF ION EXCHANGE RESINS: deacidite is handled back dress post according to a conventional method, changes into behind the OH type standby then.
4, impurity such as L-glutamic acid are removed in ion-exchange: with the feed adjustment pH4.0-6.0 of step (2) gained, feed the ion exchange column that step (3) is handled well with 1.0-4.0BV/ hour flow velocity.The pH value of monitoring stream fluid is determined the moment that feed liquid begins and stops collecting, and guarantees that L-glutamic acid and other impurity do not penetrate resin.
5, feed liquid decolouring: in above-mentioned effluent liquid, add granular gradually or powdery pharmaceutical level gac in the ratio of 0.5-2%, 30 ℃ were stirred 20-60 minute down, filter.
6, the vacuum concentration of feed liquid: the feed liquid after will decolouring is 60-120g/l at 40-70 ℃ of following vacuum concentration to glutamine content.
7, concentrated solution crystallization: the concentrated solution after will decolouring is adjusted to pH4-6, lowers the temperature with 2-4 ℃/hour speed then.1-4 hour growing the grain of insulation about 10 ℃ whenever falls in temperature, continues then to reduce to 3-5 ℃ with same speed cooling until feed temperature, keeps 8-12 hour growing the grain under this temperature, filters, and collects crystal.
8, the primary crystallization mother liquor concentrates according to step (6) earlier, carries out crystallization according to step (7) then, and the crystal of crystal and step (7) collection is merged.
9, glutamine crystal washing: in coarse crystal, add organic solvent according to 1-3 ratio doubly, stirred 1-2 hour down, filter and collect crystal at 30-50 ℃.
10, glutamine crystal drying: with step (9) gained crystal 40-50 ℃ dry 3-6 hour down, then 80 ℃ dry 1-2 hour, promptly get the glutamine finished product after the cooling.
Described fermented liquid is a glutamine ferment liquid, removes outside thalline, foreign protein and the residual sugar, and the content of glutamine must be higher than 30g/l, and L-glutamic acid content must be lower than 10g/l, about ammonium sulfate and ammonium chloride total amount 60g/l, also has other salts such as carbamate additives for low phosphorus hydrochlorate.
The pH value of the described fermented liquid of step 1 is that organic acid is regulated as one of acetate, acetic acid and lactic acid with mineral acid example hydrochloric acid, sulfuric acid and phosphoric acid.
The described polymeric flocculant of step 1 is one of anionic, cationic, non-ionic polyacrylamide and chitosan.
The described ultrafiltration apparatus of step 1 is one of tubular membrane, flat sheet membrane, rolled film and hollow-fibre membrane.
The anode membrane that the described electrodialysis appts of step 2 uses, cavity block can be in parallel, also can connect.
It is mineral acid example hydrochloric acid, sulfuric acid and phosphoric acid that step 2 is regulated the used acid of material liquid pH, and one of organic acid such as acetate, acetic acid and lactic acid, used alkali are one of sodium hydroxide, ammoniacal liquor, yellow soda ash.
The used anionite-exchange resin of step 3 is one of D296, D261, D290,201 * 4,201 * 7, D301, D380, D314, D392.
The described organic solvent of step 9 is alcohols such as dehydrated alcohol, ethanol and methyl alcohol or ketone such as one of acetone and butanone of 95%.
The present invention is further elaborated below in conjunction with example.
Embodiment 1:
The main component of glutamine ferment liquid is: glutamine 35g/l, and L-glutamic acid 8g/l, ammonium sulfate 50g/l, ammonium chloride 10g/l, other inorganic salt are a small amount of, pH6.7, fermentating liquid volume 5L.
The 5g cationic-type polyacrylamide is made flocculation agent, joins in the fermented liquid under slowly stirring, and stirs fast then 10 minutes, leaves standstill 30 minutes, filters.With 500ml washed with de-ionized water solid phase.Supernatant liquor and washing water merging back are carried out ultrafiltration by tubular membrane component, and the ultra-filtration membrane molecular weight cut-off is 6000.Regulating fermented liquid pH with 2M sulfuric acid is 6, carries out electrodialysis, and electrodialyzer is made up of two anode membranes and a cavity block.In this process, be stabilized in about 6 about 30 ℃ of controlled temperature with 2M sulfuric acid and 2M sodium hydroxide control fermented liquid pH.When electric current is reduced to 20mA/cm
2The time, stop electrodialysis.Be 5.0 with above-mentioned acid-alkali accommodation pH then, feed the D380 anion-exchange column of handling well with 3BV/ hour flow velocity, the post bed volume is 1 liter.Monitoring stream fluid pH value is not less than 5, guarantees that impurity such as L-glutamic acid do not penetrate resin.Collect effluent liquid, add powdered carbon 30g, slowly stir 20 minutes after-filtration twice.With the destainer vacuum concentration to 1/5 of original volume.The pH value of regulating concentrated solution with hydrochloric acid is 5.6, and according to 2 ℃/hour speed cooling, every cooling is incubated 3 hours for 10 ℃, reduce to 5 ℃ after, be incubated crystallization in 10 hours.Filter, collect crystal.Mother liquor concentrates under these conditions again, crystallization, and secondary crystal and a crystal are merged.The amount of pressing 1ml/g in crystal adds dehydrated alcohol, and 35 ℃ are stirred 1 hour after-filtration down, 0 ℃ of crystal 5 dry 5 hours down, and 80 ℃ of dryings 2 hours promptly get the glutamine finished product after the cooling.The yield 68.5% of this process glutamine, purity 98.8%.
Embodiment 2:
The main component of glutamine ferment liquid is: glutamine 32g/l, and L-glutamic acid 7g/l, ammonium sulfate 50g/l, ammonium chloride 6g/l, other inorganic salt are a small amount of, pH6.6, fermentating liquid volume 5L.
The 6g chitosan as flocculant joins in the fermented liquid under slowly stirring, and stirs fast then 15 minutes, leaves standstill 30 minutes, filters.With 500ml washed with de-ionized water solid phase.Supernatant liquor and washing water merging back are carried out ultrafiltration by the flat membrane ultrafiltration device, and the ultra-filtration membrane molecular weight cut-off is 10000.Regulating fermented liquid pH with 2M hydrochloric acid is 5, carries out electrodialysis, and electrodialyzer is made up of two anode membranes and a cavity block.In this process, be stabilized in about 5 about 35 ℃ of controlled temperature with 2M hydrochloric acid and 20% ammoniacal liquor control fermented liquid pH.When electric current is reduced to 25mA/cm
2The time, stop electrodialysis.Be 4.5 with above-mentioned acid-alkali accommodation pH then, feed 201 * 7 anion-exchange columns of handling well with 1.5BV/ hour flow velocity, the post bed volume is 1 liter.Monitoring stream fluid pH value is not less than 5, guarantees that impurity such as L-glutamic acid do not penetrate resin.Collect effluent liquid, add granular carbon 25g, slowly stir 30 minutes after-filtration twice.With the destainer vacuum concentration to 1/4 of original volume.The pH value of regulating concentrated solution with hydrochloric acid is 5.6, and according to 3 ℃/hour speed cooling, every cooling is incubated 4 hours for 10 ℃, reduce to 5 ℃ after, be incubated crystallization in 10 hours.Filter, collect crystal.Mother liquor concentrates under these conditions again, crystallization, and secondary crystal and a crystal are merged.The amount of press 1ml/g again in the crystal after merging adds methyl alcohol, and 30 ℃ are stirred 1.5 hours after-filtration down, and 5 ℃ of crystal 4s are drying 3 hours down, and 80 ℃ of dryings 2 hours promptly get the glutamine finished product after the cooling.The yield 67.6% of this process glutamine, purity 99.3%.
Embodiment 3:
The main component of glutamine ferment liquid is: glutamine 38g/l, and L-glutamic acid 10g/l, ammonium sulfate 40g/l, ammonium chloride 20g/l, other inorganic salt are a small amount of, pH6.7, fermentating liquid volume 5L.
The 7g non-ionic polyacrylamide is made flocculation agent, joins in the fermented liquid under slowly stirring, and stirs fast then 15 minutes, leaves standstill 30 minutes, filters.With 500ml washed with de-ionized water solid phase.Supernatant liquor and washing water are merged the back by the hollow fiber membrane device ultrafiltration, and the ultra-filtration membrane molecular weight cut-off is 30000.Regulating fermented liquid pH with 2M nitric acid is 6.5, carries out electrodialysis, and electrodialyzer is made up of two anode membranes and a cavity block.In this process, be stabilized in about 6.5 about 25 ℃ of controlled temperature with 2M sulfuric acid and 2M sodium hydroxide control fermented liquid pH.When electric current is reduced to 15mA/cm
2The time, stop electrodialysis.Be 5.5 with above-mentioned acid-alkali accommodation pH then, feed the D330 anion-exchange column of handling well with 2BV/ hour flow velocity, the post bed volume is 1 liter.Monitoring stream fluid pH value is not less than 5.5, guarantees that impurity such as L-glutamic acid do not penetrate resin.Collect effluent liquid, add powdered carbon 28g, slowly stir 20 minutes after-filtration twice.With the destainer vacuum concentration to 1/4 of original volume.The pH value of regulating concentrated solution with hydrochloric acid is 5.6, and according to 3 ℃/hour speed cooling, every cooling is incubated 3 hours for 10 ℃, reduce to 4 ℃ after, be incubated crystallization in 12 hours.Filter, collect crystal.Mother liquor concentrates under these conditions again, crystallization, and secondary crystal and a crystal are merged.Amount by 1ml/g in coarse crystal adds 95% ethanol, and 30 ℃ are stirred down 1 hour after-filtration, 5 ℃ of crystal 5s dry 4 hours down, and 80 ℃ of dryings 2 hours promptly get the glutamine finished product after the cooling.The yield 70.8% of this process glutamine, purity 99.0%.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293848B (en) * | 2007-04-27 | 2012-05-09 | 福建省麦丹生物集团有限公司 | A kind of glutamic acid extraction process |
| CN101659691B (en) * | 2009-09-28 | 2011-08-17 | 绍兴民生医药有限公司 | Industrial process for producing glutamine dipeptide |
| CN102924321B (en) * | 2012-11-30 | 2015-12-09 | 通辽梅花生物科技有限公司 | A kind of method extracting glutamine from fermented liquid |
| CN103232362B (en) * | 2013-04-26 | 2014-07-02 | 新疆阜丰生物科技有限公司 | Process for extracting L-glutamine |
| CN103467333B (en) * | 2013-09-09 | 2015-04-08 | 东辰控股集团有限公司 | Method for purifying L-glutamine from fermentation liquid through two-step crystallization |
| CN103445229B (en) * | 2013-09-09 | 2014-12-17 | 南京农业大学 | A method for simultaneously effectively removing laver protein and laver polysaccharide from laver extract |
| CN104557729B (en) * | 2014-12-11 | 2017-02-22 | 山东福田科技集团有限公司 | Tetrahydropyrimidine extraction process |
| CN106107242A (en) * | 2016-07-29 | 2016-11-16 | 舟山市瑞丰生物技术有限公司 | A kind of nonreactive aquatic immune reinforcing agent |
| CN106434781B (en) * | 2016-08-31 | 2019-11-15 | 新疆阜丰生物科技有限公司 | A kind of L-Glutamine fermentation method process for cleanly preparing |
| CN108285913B (en) * | 2017-12-09 | 2020-12-29 | 新疆阜丰生物科技有限公司 | Process for preparing and extracting L-glutamine |
| CN110003039A (en) * | 2019-03-28 | 2019-07-12 | 新泰市佳禾生物科技有限公司 | The isolation and purification method of altheine in a kind of conversion fluid |
| CN110372527B (en) * | 2019-08-13 | 2020-10-09 | 江南大学 | A kind of method for recovering glutamic acid from glutamic acid concentrated isoelectric mother liquor |
| CN111187178B (en) * | 2020-01-13 | 2023-06-23 | 廊坊梅花生物技术开发有限公司 | Preparation method of glutamine crystals |
| CN112552373B (en) * | 2020-12-08 | 2022-11-29 | 河北一品制药股份有限公司 | Industrial preparation method of glycyl-L-tyrosine |
| CN112694413A (en) * | 2021-03-24 | 2021-04-23 | 鲁东大学 | Method for extracting L-homoserine from fermentation liquor |
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