CN1103063A - Glutaminic acid extracting new technology - Google Patents

Glutaminic acid extracting new technology Download PDF

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Publication number
CN1103063A
CN1103063A CN 94101444 CN94101444A CN1103063A CN 1103063 A CN1103063 A CN 1103063A CN 94101444 CN94101444 CN 94101444 CN 94101444 A CN94101444 A CN 94101444A CN 1103063 A CN1103063 A CN 1103063A
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acid
glutamic acid
liquid
ion
wash
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丛进阳
沈金玉
曹竹安
刘瑞芝
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Tsinghua University
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Tsinghua University
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Abstract

The present invention uses fed batch continuous isoelectric crystilline technology process to extract glutaminic acid from the fermented liquid of glutaminic acid. The sulphuric acid is used to regulate the isoelecric point, the crystilline mode of the obtained glutaminic acid is alpha mode. The yield can come up to 75-80%. The crystallized glutaminic acid in the mother liquid is adsorbed by strong acidic cation exchange resin, the saturated resin is elutriated in situ after the pH is regulated to 9.0 by the ion exchange waste liquid, the "pillar forming" phenomenon will not occurred. The yield of ion exchange section comes up to 95%. The total yield of isoelectric crystilline and ion exchange two sections comes up to 95% odd.

Description

Glutaminic acid extracting new technology
The present invention relates to a kind of stream and add isoelectric point crystallization and ion-exchange coupled extraction L-glutamic acid novel process, belong to the technical field of biological fermentation products production.
China is a glutamate production big country.It generally must eat monosodium glutamate with making sodium salt behind starch or the molasses fermented production L-glutamic acid, and its L-glutamic acid concentration in fermented liquid can reach 6-7%(starch respectively) and more than 10% (molasses).L-glutamic acid isolating method from fermented liquid generally has hydrochloride method, zincate process, isoelectric point crystallizing method, ion exchange method, isoelectric point crystallizing-ion exchange method etc.China adopts low temperature isoelectric point crystallizing method from saving acid-base consumption, reducing wastewater flow rate and environmental protection concept point more at present.Its yield is between 70-75%.The shortcoming of this method is that energy consumption is big, yield is low.Because also have the L-glutamic acid of 25-30% to go out of use.If original in addition aminoglutaric acid concentration is too high, then in crystallisation process, very easily produce the β N-type waferN, cause the L-glutamic acid yield sharply to descend.Past attempts was carried out production test to isoelectric point crystallizing-ion exchange method, but big owing to its ion-exchange part reagent consumption, wastewater flow rate is many, must heat with alkali during wash-out and reason such as the resin loss amount is big, indefinite attitude is held more by producer.University Of Tianjin in 1988 delivers patent and " reclaims the novel process of L-glutamic acid from isoelectric point crystallizing mother liquor ", number of patent application is 88103158, be characterized in from isoelectric point crystallizing mother liquor, reclaiming L-glutamic acid at normal temperatures, make the L-glutamic acid yield reach 95% with ammonium type storng-acid cation exchange resin.But this patent is because of with adjusted isoelectric point crystallizing mother liquor or the saturated resin of adjusted fermented liquid mother liquor wash-out L-glutamic acid, and L-glutamic acid excessive concentration in the elutriant can cause " knot post " phenomenon as wash-out in former post.Therefore have to adopt resin transfer is carried out the fluidization wash-out and washed eluted resins with clear water in independent wash-out post, thereby operation still do not want to take the trouble, and have extra waste water to produce.In the resin transfer process, also can cause the damage and the loss of resin inevitably.
The objective of the invention is to propose a kind of stream and add isoelectric point crystallization and ion-exchange coupled and extract the L-glutamic acid novel process, be characterized in that isoelectric point crystallizing is near carrying out continuously under the normal temperature.Aminoglutaric acid concentration can not produce the crystallization of β type in the original liquid in 6-10% and Geng Gao scope.The L-glutamic acid alpha-crystal particle that is produced is big, and settling velocity is fast, thereby unit equipment volume processing reduction of feed volume is big.Available computers or manual crystallization control pH value stably.The characteristics of this novel process ion-exchange part are to select strongly acidic cation-exchange for use, and its loading capacity is big, low price, and resin quality is stable.But column operation on the feed liquid carrier.Need not wash between absorption and the wash-out.Thereby simplified extraction process, saved reagent, reduced waste liquid, reduced cost.
Content of the present invention is: a kind of stream adds isoelectric point crystallization and the ion-exchange coupled extracts the L-glutamic acid novel process, and this technology comprises following each step:
(1) in the crystallizer that contains α type L-glutamic acid microcrystal, add glutami acid fermentation liquor and acid solution, the flow proportional of fermented liquid and acid solution is to make the pH value of mixing liquid between 3.0~3.5, under 30~50 rev/mins mixing speed, carry out continuous isoelectric point crystallizing, flow into settling bowl after feed liquid stops more than 6 hours and carry out solid-liquid separation in crystallizer, solid part is a glutamic acid crystallization, after whizzer dries, is dried to product.
(2) with the crystalline mother solution of the carrier that obtains after the above-mentioned the first step solid-liquid separation, with sulfuric acid adjust pH to 1.5~2.0, adsorb with storng-acid cation exchange resin then, adsorb the resin elutriant wash-out after saturated, elutriant is the back flow point liquid behind an ion-exchange raffinate and the last recycling elution, and the pH value of ion-exchanging eluent transfers to 8~10 with ammoniacal liquor.
(3) the wash-out effluent liquid behind the above-mentioned resin elution is divided into three flow points by the difference of contained aminoglutaric acid concentration: preceding flow point (aminoglutaric acid concentration approaches the concentration in the crystalline mother solution) is as next circulation absorption, middle flow point (L-glutamic acid that contains high density) returns the above-mentioned the first step, carry out isoelectric point crystallizing, back flow point (containing lower concentration L-glutamic acid) is as next round-robin elutriant; Ion exchange resin behind the wash-out is used for next round-robin L-glutamic acid absorption.
Effect of the present invention is not produce other waste water except that fermentation mother liquor in the leaching process.Because it is carry out the absorption and the wash-out of ion-exchange at normal temperatures, thereby energy-conservation in a large number.The present invention is the high benefit novel process, the waste liquid preparation elutriant that direct coupling, the ion-exchange resins that stream adds isoelectric point crystallization and ion-exchange needn't wash and use this technology to produce, thus simplified technology, saved reagent, reduced waste liquid.And the total recovery of L-glutamic acid can reach more than 95%.
Description of drawings:
Fig. 1 is a process flow sheet of the present invention.
Below in conjunction with accompanying drawing, introduce in detail technical process of the present invention. Among Fig. 1, the 1st, the glutami acid fermentation liquor reservoir, the 2nd, acid tank, the 3rd, the glutamic acid continuous crystalizer, the 4th, solid-liquid separation tank, the 5th, ion-exchange liquid groove, 6-1 to 6-5 totally 5 be ion exchange column, the 7th, eluant groove. Technology overall process of the present invention is: fermentation mother liquor is cooled to 20 ℃ in reservoir 1, then and the sulfuric acid in acid tank 2 be transported in certain proportion in the continuous crystalizer 3. PH value in the continuous crystalizer 3 remains between the 3.0-3.2, and temperature also maintains about 10 ℃. The magma that generates flows to an end of solid-liquid separation tank 4 from overfall, and supernatant flows to from handing in the material fluid bath 5 from the other end. And the thick magma that sedimentation goes out flows to the drying centrifuge from the other end of solid-liquid separation tank. Solid drying after the drying is packaged into product after pulverizing. The isolated liquid of centrifuge and the supernatant that flows out from solid-liquid separation tank 4 are pooled to ion-exchange liquid groove 5, enter ion exchange column after equaling 1.5 with the sulfuric acid adjust pH and carry out glutamic acid and adsorb. Ion exchange column 6(totally five be connected into loop system) in strong acid ion exchange resin is housed. Ion-exchange efflux discharging after the absorption is for manufacture order cell protein or other usefulness. Being adsorbed according to the order of sequence ion exchange column after saturated by glutamic acid disconnects from sorption cycle and carries out the glutamic acid wash-out. Eluent is in groove 7 interior preparations. It is to collect the rear flow point of wash-out efflux and part ion exchange raffinate to add the ammoniacal liquor adjust pH be 9.0 rear uses. The wash-out efflux as previously mentioned, can be divided into three flow points according to its content of glutamic acid difference, is transported to respectively in the storage tank separately. Treat to be risen to by wash-out at 9.0 o'clock from the efflux pH value of handing over post, stop wash-out. And this post string got back in the sorption cycle system as last post, and then carry out the wash-out of next post. Circulation goes down to accomplish continuous crystallisation, continuous adsorption, the closed circuit flow process of extraction glutamic acid of wash-out one by one according to this.
Parameters of technique process of the present invention is respectively:
The isoelectric point crystallizing process:
The ratio of feed liquid and acid solution guarantees that continuous isoelectric point crystallizing groove pH value is between 3.0-3.2;
The brilliant liquid temp of isoelectric point crystallizing keeps 10~20 ℃;
Feed velocity guarantees that the time of staying of crystal in crystallizer is more than 6 hours;
Aminoglutaric acid concentration can be between 5%-12% in the feed liquid, and the pH value is between the 6-7;
Feeding temperature remains on room temperature;
The concentration of ammonium ion is the 5-10 grams per liter;
The magma that overflows from crystallizer separates in solid-liquid separation tank, and the size of separate tank guarantees that the residence time of magma in the pond is more than 4 hours.
Continuous ionic exchange absorption L-glutamic acid process:
The acidity of absorption feed liquid is pH1.5-2.0; Used acid can be sulfuric acid or hydrochloric acid;
Ammonium concentration is the 5-10 grams per liter;
The adsorbed feed apparent velocity is 2.0 meters/hour;
During absorption without degerming.
The ion exchange column elution process:
It is that 9.0 backs are as elutriant that back flow point liquid behind ion-exchange tail washings or the ion-exchange wash-out is regulated the pH value with ammoniacal liquor;
Aminoglutaric acid concentration should be less than 10 grams per liters in the elutriant;
Wash-out employing anti-upper prop in former post carries out;
Carrier operation during wash-out.Do not carry out water washing before the wash-out;
The elutriant temperature is a normal temperature;
The elutriant apparent velocity: 1.5-2.0 rice/hour; Till being eluted to post effluent liquid pH value and equaling 9.0 o'clock.
Absorption can be 732 with storng-acid cation exchange resin, D001, D61 or 742.
Embodiments of the invention are as follows:
Embodiment 1
Initial aminoglutaric acid concentration is that the vitriol oil Continuous Flow of 9.92% carry disease germs fermented liquid and dilution in 1: 1 is added in the isoelectric point crystallization device with spiral coil cooling tube.PH value and the temperature of computerizeing control in the isoelectric point crystallization device is respectively 3.2 and 10 ℃.Double-deck slurry formula stirring arm stirs with 50 rev/mins of revolutions.The residence time of crystal in crystallizer is 5.2 hours.The magma that overflows carries out liquid-solid natural separation in settling bowl.Supernatant liquor and back as follow-up ion exchange extraction L-glutamic acid from the effusive centrifugate merging of crystal drier.Iso-electric point continuous crystallisation part L-glutamic acid yield is 83.8%, and aminoglutaric acid concentration is 16.1% grams per liter in the supernatant liquor, and L-glutamic acid purity is 93.7%, and principal crystal grain mainly is distributed in about 0.2mm.
Strong-acid ion exchange resin is loaded in 4 * 100 centimetres of series connection ion exchange columns of five Φ.The total bed height of the resin of five posts is 3.85 meters.Contain L-glutamic acid 21.1 grams per liters in the crystalline mother solution of fermented liquid after isoelectric point crystallizing extracts L-glutamic acid, ammonium concentration is 9.84 grams per liters, pH3.2.With this feed liquid with sulfuric acid to transfer pH be 1.5 backs with 3.65 meters/time the anti-upper prop of linear velocity adsorb.Treat that the saturated back of first post transfers pH to carry out wash-out after 9.0 with the absorption lean solution that contains 0.3 grams per liter L-glutamic acid and 15 grams per liter ammoniums with ammoniacal liquor.Flow point was 0.79 liter before the wash-out result got, and contained L-glutamic acid 14.2 grams per liters.1.15 liters of high flow points, aminoglutaric acid concentration 32.0 grams per liters.1.02 liters of back flow points contain L-glutamic acid 5.5 grams per liters.The wash-out yield of L-glutamic acid reaches 97.5%, and the L-glutamic acid total recovery reaches 95%.
Embodiment 2
Isoelectric point crystallization and ion-exchange unit and working method thereof be all with example 1, but aminoglutaric acid concentration is 8.32% after isoelectric point crystallization extraction continuously in the initial fermented liquid, and the yield of L-glutamic acid is 82.4%, and the concentration of L-glutamic acid is 15.4 grams per liters in the supernatant liquor.The purity of L-glutamic acid reaches 95.1%.Principal crystal grain still is distributed in about 0.2mm.Above-mentioned isoelectric point crystallization dries centrifugate and enter ion-exchange after transferring pH.The ion-exchange absorption rate of L-glutamic acid is 99.2%, and eluting rate is 91.3%.From handing over part L-glutamic acid yield is 98.3%.
Embodiment 3
Isoelectric point crystallization and ion-exchange unit and working method thereof be all with example 1, but aminoglutaric acid concentration is 6.10% after isoelectric point crystallization extraction continuously in the initial fermented liquid, and the yield of L-glutamic acid is 74.9%, and the concentration of L-glutamic acid is 16.0 grams per liters in the supernatant liquor.The purity of L-glutamic acid reaches 94.4%.Principal crystal grain still is distributed in about 0.2mm.Above-mentioned isoelectric point crystallization dries centrifugate and enter ion-exchange after transferring pH.The ion-exchange absorption rate of L-glutamic acid is 98.2%, and eluting rate is 90.0%.From handing over part L-glutamic acid yield is 97.0%.

Claims (4)

1, a kind of stream adds isoelectric point crystallization and ion-exchange coupled extraction L-glutamic acid novel process, it is characterized in that this technology comprises following each step:
(1) in the crystallizer that contains α type L-glutamic acid microcrystal, add glutami acid fermentation liquor and acid solution, the flow proportional of fermented liquid and acid solution is to make the pH value of mixing liquid between 3.0~3.5, under 30~50 rev/mins mixing speed, carry out continuous isoelectric point crystallizing, flow into settling bowl after feed liquid stops more than 6 hours and carry out solid-liquid separation in crystallizer, solid part is a glutamic acid crystallization, after whizzer dries, is dried to product;
(2) with the crystalline mother solution of the carrier that obtains after the above-mentioned the first step solid-liquid separation, with acid solution adjust pH to 1.5~2.0, adsorb with storng-acid cation exchange resin then, adsorb the resin elutriant wash-out after saturated, elutriant is the back flow point liquid behind an ion-exchange raffinate and the last recycling elution, and the pH value of ion-exchanging eluent transfers to 8~10 with ammoniacal liquor;
(3) the wash-out effluent liquid behind the above-mentioned resin elution is divided into three flow points by the difference of contained aminoglutaric acid concentration: preceding flow point (aminoglutaric acid concentration approaches the concentration in the crystalline mother solution) is as next circulation absorption, middle flow point (L-glutamic acid that contains high density) returns the above-mentioned the first step, carry out isoelectric point crystallizing, back flow point (containing lower concentration L-glutamic acid) is as next round-robin elutriant; Ion exchange resin behind the wash-out is used for next round-robin L-glutamic acid absorption.
2, extraction process as claimed in claim 1 is characterized in that wherein said acid solution is sulfuric acid or hydrochloric acid.
3, extraction process as claimed in claim 1 is characterized in that wherein the isoelectric point crystallizing temperature of the first step is 10~20 ℃.
4, extraction process as claimed in claim 1 is characterized in that absorption is 732 with storng-acid cation exchange resin in wherein said second step, D001, any among the D61 or 742.
CN 94101444 1994-02-25 1994-02-25 Glutaminic acid extracting new technology Pending CN1103063A (en)

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CN 94101444 CN1103063A (en) 1994-02-25 1994-02-25 Glutaminic acid extracting new technology

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CN 94101444 CN1103063A (en) 1994-02-25 1994-02-25 Glutaminic acid extracting new technology

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100339358C (en) * 2005-07-24 2007-09-26 山东信乐味精有限公司 Novel process of extracting glutamic acid from glutamic acid fermentation liquor
CN101168515B (en) * 2007-11-15 2010-08-25 山东阜丰生物科技开发有限公司 Technique for utilizing glutamic acid production waste liquid
CN101973901A (en) * 2010-09-20 2011-02-16 江南大学 Glutamic acid continuous isoelectric crystallization method
CN106748871A (en) * 2016-11-29 2017-05-31 岳阳科罗德联合化学工业有限公司 A kind of green circulatory industrial production process of amino acid surfactant

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100339358C (en) * 2005-07-24 2007-09-26 山东信乐味精有限公司 Novel process of extracting glutamic acid from glutamic acid fermentation liquor
CN101168515B (en) * 2007-11-15 2010-08-25 山东阜丰生物科技开发有限公司 Technique for utilizing glutamic acid production waste liquid
CN101973901A (en) * 2010-09-20 2011-02-16 江南大学 Glutamic acid continuous isoelectric crystallization method
CN101973901B (en) * 2010-09-20 2013-10-30 江南大学 Glutamic acid continuous isoelectric crystallization method
CN106748871A (en) * 2016-11-29 2017-05-31 岳阳科罗德联合化学工业有限公司 A kind of green circulatory industrial production process of amino acid surfactant
CN106748871B (en) * 2016-11-29 2019-03-05 岳阳科罗德联合化学工业有限公司 A kind of green circulatory industrial production process of amino acid surfactant

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