CN103224454A - Glutamic acid separating and extracting technology - Google Patents

Glutamic acid separating and extracting technology Download PDF

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CN103224454A
CN103224454A CN2013100858588A CN201310085858A CN103224454A CN 103224454 A CN103224454 A CN 103224454A CN 2013100858588 A CN2013100858588 A CN 2013100858588A CN 201310085858 A CN201310085858 A CN 201310085858A CN 103224454 A CN103224454 A CN 103224454A
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glutamic acid
acid
solution
ion exchange
mixing solutions
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CN103224454B (en
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唐永强
楼良旺
刘元涛
程文焕
张春宇
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INNER MONGLIA FUFENG BIOLOGICAL TECHNOLOGY Co Ltd
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Abstract

The invention discloses a glutamic acid separating and extracting technology. The technology is characterized in that glutamic acid in the isoelectric point liquid of glutamic acid is separated and extracted through adopting an ion exchange method, an acid solution not an alkali solution is directly used to elute for generation after the ion exchange resin adsorption of the glutamic acid, and an eluate obtained after the ion exchange returns to an isoelectric operation for glutamic acid extraction. Compared with traditional technologies, the technology disclosed in the invention has the advantages of saving of a large amount of an acid and an alkali, reduction of the production cost and the environmental pollution, and economic benefit improvement.

Description

A kind of separation-extraction technology of L-glutamic acid
Technical field
[0001] the invention belongs to the amino acid production technical field, be specifically related to a kind of separation-extraction technology of L-glutamic acid.
Background technology
L-glutamic acid is a kind of acidic amino acid.Molecule includes two carboxyls, and chemical name is the alpha-amino group pentanedioic acid.L-glutamic acid be in Suo Xun 1856 find, be clear crystal, delicate flavour is arranged, be slightly soluble in water, and be dissolved in hydrochloric acid soln, iso-electric point 3.22.Be present in a large number in the grain protein, content is also more in the animal brain.Account for critical role in the L-glutamic acid protein metabolism process in vivo, participate in the many important chemical reaction in animal, plant and the microorganism.Sodium Glutamate is commonly called as monosodium glutamate, is important tasty agents, and fragrance is had enhancement.Sodium Glutamate is widely used in food-flavoring comps, both can use separately, can and use with other amino acid etc. again.Be used in the food, the flavouring effect is arranged.Concentration is 0.2%-0.5% in food, and allowing intake (ADl) for each person every day is 0-120 microgram/kilograms (in L-glutamic acid).General consumption is 0.2-1.5 gram/kilograms in food-processing.
At present, the method for domestic main flow producer separation and Extraction L-glutamic acid has iso-electric point-ion exchange method.Iso-electric point-ion exchange method is that fermented liquid is after waiting electrical method separation and Extraction L-glutamic acid, again the iso-electric point mother liquor is exchanged absorption by ion exchange resin column, use the L-glutamic acid on the alkali lye wash-out resin then, collect high flow point, it is mixed with the next batch fermented liquid, extract L-glutamic acid with isoelectric point method again, this extraction process consumes higher sulfuric acid and liquefied ammonia.
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Summary of the invention
The objective of the invention is to solve bronsted lowry acids and bases bronsted lowry consumption problem of higher in iso-electric point-ion exchange method separation and Extraction L-glutamic acid technology, provide a kind of separating and extracting method of L-glutamic acid, with the purpose that reaches the resources conservation utilization and significantly reduce production costs.
For achieving the above object, the present invention improves realization on the basis of existing technology, its gordian technique is after utilizing isoelectric point crystallizing to separate out separation in L-glutamic acid in the fermented liquid, again with ion exchange column with the extracting glutamic acid in its mother liquor, its main points are at ion-exchange process, after the iso-electric point mother liquor exchanged absorption by ion exchange resin column, without the alkali lye wash-out, but carry out wash-out as eluent with the acid hydrolysis liquid or the acid solution of metacrystal mother liquor, the glutamic acid solution that wash-out goes out still contains the eluent of high level, this elutriant is returned electricity separation such as above-mentioned iso-electric point operation.Because without the alkali lye wash-out, so saved alkali; Because with acid solution wash-out regenerating resin post, contain the sour eluent of high level in the elutriant glutamic acid solution, but this sour eluent exactly is the required raw material of iso-electric point operation itself again, so saved acid again.
The invention provides a kind of separating and extracting method of L-glutamic acid, comprise the steps:
1) glutami acid fermentation liquor is collected trapped substance and filtered solution respectively through the micro-filtrate membrane filtration degerming; Then filtered solution is proceeded supermembrane and filtered, collect concentrated solution and L-glutamic acid scavenging solution; It is standby that above-mentioned trapped substance and concentrated solution are merged into mixing solutions;
2) pH that earlier regulates the L-glutamic acid scavenging solution with acid is to the L-glutamic acid iso-electric point, treat that electrolysiss such as L-glutamic acid in the solution go out after, obtain L-glutamic acid after filtration; Be divided into two parts of equal volume with separating mother liquor behind the L-glutamic acid; With a copy of it glutamic acid mother liquor pump in the ion exchange column that is filled with hydrogen type strong acid type resin cation (R.C.); In another part glutamic acid mother liquor, add acid, make pH<0.5 of solution, come the L-glutamic acid that adsorbs on the resin of the above-mentioned ion exchange column of wash-out as elutriant then; At last the L-glutamic acid elutriant is extracted L-glutamic acid with isoelectric point method;
3) in the mixing solutions of step 1), add Semen Maydis powder, bean dregs and vinasse, be stirred to pasty state while adding; Feed steam at last and be warming up to 105 ℃, distilled about 10 minutes; With after the distillment oven dry, pulverizing, add zinc sulfate and composite bacteria then, mix, obtain the powdery nutrient fodder; Composite bacteria is mixed by lactobacillus and the yeast mass ratio according to 1:1; Wherein, Semen Maydis powder, bean dregs and vinasse account for 5%, 2% and 1% of mixing solutions quality respectively, and zinc sulfate and composite bacteria account for the thousandth of mixing solutions quality respectively.
Preferably, microfiltration membrane is an inorganic ceramic film, and molecular weight cut-off is 2000MW, and the micro-filtration temperature is 40 ℃; The ultra-filtration membrane molecular weight cut-off is 300MW, and the ultrafiltration temperature is 40 ℃;
Preferably, described ion exchange column is filled with the 732# resin of Hydrogen.
Wherein, step 2) used sour available hydrochloric acid or sulfuric acid in, preferably sulfuric acid.
The separating and extracting method that the present invention adopts is on the basis that does not increase any investment in fixed assets, utilizes on the basis of existing equipment and technology and carries out the process modification innovation, and the advantage of comparing with existing L-glutamic acid separation-extraction technology has:
1, because without alkali lye wash-out ion exchange column, so saved a large amount of alkali, traditional technology, is produced L-glutamic acid per ton and can be saved the above liquefied ammonia of 150kg as wash-out alkali lye with ammonia soln, by producing 200000 tons of L-glutamic acid per year, this is annual cost-saved more than 9,000 ten thousand yuan as producer;
2, owing to,, thereby reduced sour consumption correspondingly also just no longer with the sour positively charged ion of from alkali lye, bringing into that goes wash-out to be adsorbed by ion exchange column without alkali lye wash-out ion exchange column;
3, adopt pickling to take off, the wash-out of Zeo-karb and regeneration step are finished simultaneously, simplified conventional from the skill of handing over; And the eluent that contains high level in the elutriant, the eluent of high level reduces the pH of solution, can increase the solubleness of L-glutamic acid, reduce the volume of electrician's preface L-glutamic acid elutriants such as returning, thereby the percent crystallization in massecuite of the L-glutamic acid of electrician's prefaces such as raising, total system circulates repeatedly, has both improved yield, has saved sour consumption again;
4, with sulfuric acid be example as eluent, produce L-glutamic acid per ton and can save the above sulfuric acid of 300kg, by producing 200000 tons of L-glutamic acid per year, this is annual cost-saved more than 24,000,000 yuan as producer;
5, since the high concentrated acid part that electrician's preface such as is used for earlier in the ion-exchange process dilution, the heat of emitting is utilized during by the L-glutamic acid wash-out, thereby has reduced the energy consumption that waits the cooling water of electrician's preface.
6, micro-filtration, ultrafiltration membrance filter process tropina, macromolecular polysaccharide etc. extract to receive greatly and improve, and have avoided this type of material that extracting glutamic acid is had a negative impact and extracted the back waste liquid being difficult to handle; Simultaneously, obtain nutritious animal feeding-stuff containing somatic protein, turned waste into wealth, increased economic benefit.
7, the technology of the present invention has realized the environmental protection of extracting glutamic acid process, almost do not have waste water and efflux, and the process water recycle, the feed liquid component makes full use of.
 
Embodiment
Below will adopt specific embodiment to come the present invention is further explained, but should not regard restriction as initiative spirit of the present invention.
Embodiment 1
A kind of separating and extracting method of L-glutamic acid comprises the steps:
1) glutami acid fermentation liquor is collected trapped substance and filtered solution respectively through the micro-filtrate membrane filtration degerming; Then filtered solution is proceeded supermembrane and filtered, collect concentrated solution and L-glutamic acid scavenging solution; It is standby that above-mentioned trapped substance and concentrated solution are merged into mixing solutions; Wherein, microfiltration membrane is an inorganic ceramic film, and molecular weight cut-off is 2000MW, and the micro-filtration temperature is 40 ℃; The ultra-filtration membrane molecular weight cut-off is 300MW, and the ultrafiltration temperature is 40 ℃;
2) pH that earlier regulates the L-glutamic acid scavenging solution with sulfuric acid is to the L-glutamic acid iso-electric point, treat that electrolysiss such as L-glutamic acid in the solution go out after, obtain L-glutamic acid after filtration; Be divided into two parts of equal volume with separating mother liquor behind the L-glutamic acid; With a copy of it glutamic acid mother liquor pump in the ion exchange column of the 732# resin that is filled with Hydrogen; In another part glutamic acid mother liquor, add sulfuric acid, make pH<0.5 of solution, the L-glutamic acid that adsorbs on the resin of the above-mentioned ion exchange column of wash-out then; At last the L-glutamic acid elutriant is extracted L-glutamic acid with isoelectric point method, wherein, extracting L-glutamic acid solution afterwards can recycle as elutriant once more;
3) in the mixing solutions of step 1), add Semen Maydis powder, bean dregs and vinasse, be stirred to pasty state while adding; Feed steam at last and be warming up to 105 ℃, distilled about 10 minutes; With after the distillment oven dry, pulverizing, add zinc sulfate and composite bacteria then, mix, obtain the powdery nutrient fodder; Composite bacteria is mixed by lactobacillus and the yeast mass ratio according to 1:1; Wherein, Semen Maydis powder, bean dregs and vinasse account for 5%, 2% and 1% of mixing solutions quality respectively, and zinc sulfate and composite bacteria account for the thousandth of mixing solutions quality respectively.
Lactobacillus and yeast reach 2.0-5.0 * 10 according to conventional fermentation culture mode viable count to the product 8Individual/gram.
After testing, this nutrient fodder protein content 41.5%, inorganic mineral content 3.5%, L-glutamic acid content 4.1%, all the other are starch, glucide and a small amount of other amino acid.
Following table is the supplies consumption and the yield contrast of traditional iso-electric point-ion exchange method and iso-electric point-ion exchange method of the present invention:
Table 1 supplies consumption and yield contrast
Figure 2013100858588100002DEST_PATH_IMAGE002
Through relatively finding, sulfuric acid of the present invention be example as eluent, produce L-glutamic acid per ton and can save the above sulfuric acid of 300kg, by producing 200000 tons of L-glutamic acid per year, this every year is cost-saved more than 2,400 ten thousand yuan as producer; And saved a large amount of alkali, traditional technology, is produced L-glutamic acid per ton and can be saved the above liquefied ammonia of 150kg as wash-out alkali lye with ammonia soln, and by producing 200000 tons of L-glutamic acid per year, this is annual cost-saved more than 9,000 ten thousand yuan as producer.Simultaneously, the present invention does not produce any unnecessary waste, has obtained nutritious animal feeding-stuff containing somatic protein, turns waste into wealth, and increases economic benefit.
Embodiment 2
The culture experiment of the nutrient fodder of embodiment 1 preparation
Choose 100 of month big weanling pigs, be divided into two groups, 50 every group, wherein experimental group is raised with the feed of the present invention's preparation, about 250 yuan of every 50kg, and control group is with honest feed (SSB-25 model), according to the about 300 yuan of calculating of every 50kg.Detect every index referring to table 1 after raising for 6 weeks.
Table 1
Index (every piglet) Control group Of the present invention group
Weanling pig body weight (kg) 5.34 5.23
Put on weight in 6 weeks (kg) 12.02 14.18
Survive number 44 49
Consume feed (kg) 16.4 17.1
Feed for nursing cost (unit) 98.4 85.5
Find that by above-mentioned contrast experiment utilize the nutrient fodder cost of the embodiment of the invention 1 preparation lower, piglet weight increase and survival rate obviously are better than pig starter feed commonly used on the market.
 
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.

Claims (4)

1. the separating and extracting method of a L-glutamic acid comprises the steps:
1) glutami acid fermentation liquor is collected trapped substance and filtered solution respectively through the micro-filtrate membrane filtration degerming; Then filtered solution is proceeded supermembrane and filtered, collect concentrated solution and L-glutamic acid scavenging solution; It is standby that above-mentioned trapped substance and concentrated solution are merged into mixing solutions;
2) earlier with sour regulating step 1) pH of the L-glutamic acid scavenging solution for preparing is to the L-glutamic acid iso-electric point, treat that electrolysiss such as L-glutamic acid in the solution go out after, obtain L-glutamic acid after filtration; Be divided into two parts of equal volume with separating mother liquor behind the L-glutamic acid; With a copy of it glutamic acid mother liquor pump in ion exchange column; In another part glutamic acid mother liquor, add acid, make pH<0.5 of solution, come the L-glutamic acid that adsorbs on the resin of the above-mentioned ion exchange column of wash-out as elutriant then; At last the L-glutamic acid elutriant is extracted L-glutamic acid with isoelectric point method;
3) toward step 1) preparation mixing solutions in add Semen Maydis powder, bean dregs and vinasse, be stirred to pasty state while adding; Feed steam at last and be warming up to 105 ℃, distilled about 10 minutes; With after the distillment oven dry, pulverizing, add zinc sulfate and composite bacteria then, mix, obtain the powdery nutrient fodder; Composite bacteria is mixed by lactobacillus and the yeast mass ratio according to 1:1; Wherein, Semen Maydis powder, bean dregs and vinasse account for 5%, 2% and 1% of mixing solutions quality respectively, and zinc sulfate and composite bacteria account for the thousandth of mixing solutions quality respectively.
2. the method for claim 1 is characterized in that, described microfiltration membrane is an inorganic ceramic film, and molecular weight cut-off is 2000MW, and the micro-filtration temperature is 40 ℃; The molecular weight cut-off of described ultra-filtration membrane is 300MW, and the ultrafiltration temperature is 40 ℃.
3. the method for claim 1, described ion exchange column is filled with hydrogen type strong acid type resin cation (R.C.), preferably is filled with Hydrogen 732# resin.
4. used acid is hydrochloric acid or sulfuric acid the method for claim 1, described step 2), preferably sulfuric acid.
CN201310085858.8A 2013-03-18 2013-03-18 Glutamic acid separating and extracting technology Active CN103224454B (en)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN104222704A (en) * 2014-10-16 2014-12-24 内蒙古阜丰生物科技有限公司 Feed prepared by threonine fermentation waste and preparation method thereof
CN104256056A (en) * 2014-10-14 2015-01-07 内蒙古阜丰生物科技有限公司 Animal feed prepared by glutamic acid fermentation waste
CN105111097A (en) * 2015-09-14 2015-12-02 宝鸡阜丰生物科技有限公司 Refining technology for glutamic acid
CN105646256A (en) * 2016-03-20 2016-06-08 内蒙古阜丰生物科技有限公司 Glutamic acid extraction crystallization process

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CN101434554A (en) * 2008-11-12 2009-05-20 山东阜丰生物科技开发有限公司 Method for all-film extraction of aminoglutaric acid
CN101456823A (en) * 2009-01-06 2009-06-17 天津科技大学 Novel process for separating and extracting L-aminoglutaric acid from fermentation liquor
CN102703537A (en) * 2012-06-26 2012-10-03 呼伦贝尔东北阜丰生物科技有限公司 Novel production method for glutamic acid

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US3325539A (en) * 1962-11-19 1967-06-13 Merck & Co Inc Ion exchange process for removing glutamic acid from a fermentation broth
CN1048702A (en) * 1990-04-13 1991-01-23 陈雪贞 A kind of method of extracting L-glutamic acid
US5279744A (en) * 1990-09-25 1994-01-18 Ajinomoto Co., Inc. Method for purification of an amino acid using ion exchange resin
CN1092404A (en) * 1993-03-15 1994-09-21 河南省基础及应用科学研究所 A kind of novel method of extracting acidic amino acid
CN1094708A (en) * 1993-05-06 1994-11-09 冯容保 Technique for recovering glutamic acid by using all mother liquor ion exchange process
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CN101434554A (en) * 2008-11-12 2009-05-20 山东阜丰生物科技开发有限公司 Method for all-film extraction of aminoglutaric acid
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104256056A (en) * 2014-10-14 2015-01-07 内蒙古阜丰生物科技有限公司 Animal feed prepared by glutamic acid fermentation waste
CN104222704A (en) * 2014-10-16 2014-12-24 内蒙古阜丰生物科技有限公司 Feed prepared by threonine fermentation waste and preparation method thereof
CN104222704B (en) * 2014-10-16 2016-05-25 内蒙古阜丰生物科技有限公司 A kind of feed prepared by Threonine Fermentation discarded object and preparation method thereof that utilizes
CN105111097A (en) * 2015-09-14 2015-12-02 宝鸡阜丰生物科技有限公司 Refining technology for glutamic acid
CN105646256A (en) * 2016-03-20 2016-06-08 内蒙古阜丰生物科技有限公司 Glutamic acid extraction crystallization process
CN105646256B (en) * 2016-03-20 2017-11-10 内蒙古阜丰生物科技有限公司 A kind of extracting glutamic acid crystallization processes

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