CN103071389A - Method for recovering threonine from threonine crystallization mother liquor - Google Patents

Method for recovering threonine from threonine crystallization mother liquor Download PDF

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CN103071389A
CN103071389A CN2012101445658A CN201210144565A CN103071389A CN 103071389 A CN103071389 A CN 103071389A CN 2012101445658 A CN2012101445658 A CN 2012101445658A CN 201210144565 A CN201210144565 A CN 201210144565A CN 103071389 A CN103071389 A CN 103071389A
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threonine
chamber
liquid
mother liquor
crystal mother
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丛威
杨鹏波
王倩
张圩玲
田原
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Institute of Process Engineering of CAS
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Abstract

The present invention relates to the field of amino acid production, particularly to a method for recovering threonine from a threonine crystallization mother liquor. The method comprises the following steps: 1) adopting a bipolar membrane electrodialysis technology or a common electrodialysis technology to remove inorganic salts from a threonine crystallization mother liquor to obtain an inorganic salt-removed threonine crystallization mother liquor, wherein the bipolar membrane electrodialysis technology is an acid-salt-alkali three-chamber bipolar membrane electrodialysis technology; and 2) adopting a cation exchange method to recover threonine from the inorganic salt-removed threonine crystallization mother liquor. With the present invention, recovery of the threonine from the threonine crystallization mother liquor is achieved, a threonine extraction yield is increased, complete utilization of various components in the threonine crystallization mother liquor can be further achieved, and the residue liquid can be treated by using the existing mature biotechnology so as to achieve standard discharge, and reduce pollution emission.

Description

From the threonine crystal mother liquor, reclaim the method for threonine
Technical field
The present invention relates to the amino acids production field, especially, relate to the method that from the threonine crystal mother liquor, reclaims threonine.
Background technology
Threonine, formal name used at school 2 amino 3 hydroxybutyric acid (Threonine Itaconic acid) is referred to as Thr), molecular formula is C 4H 9O 3N.Its proterties is white orthorhombic system or crystalline powder, odorless, it is little sweet to distinguish the flavor of, in the time of 25 ℃ in water solubility be 20.5g/100mL, be insoluble to ethanol, EC.L-threonine is a kind of essential amino acid, is mainly used in the aspects such as medicine, chemical reagent, food additive, feed addictive.
At present, fermentation method has become the main stream approach of producing threonine.The method utilizes its metabolism to produce threonine with the lactose fermentation bacillus as bacterial strain take dextrose plus saccharose as raw material under aeration condition, flows during the fermentation ammonification to replenish nitrogenous source and to regulate the pH value.Extract the relatively simple isoelectric point crystallization method (as shown in Figure 1) of the at present main adopting process flow process of threonine from zymotic fluid: the L-threonine zymotic fluid is through membrane filtration degerming, decolouring, removal of impurities, with the sulphur acid for adjusting pH value to 4.5-5.0, condensing crystallizing namely gets product after the L-threonine crystal drying that separation obtains.Because threonine solubility is larger, still contain the threonine up to 7% ~ 12% in the mother liquor behind the primary crystallization, contain in addition about 2% ~ 3% inorganic salts and the materials such as impurity amino acid (being mainly glutamic acid, alanine etc.), protein and residual sugar.For improving the threonine yield, Some Domestic manufacturing enterprise carries out again condensing crystallizing to threonine primary crystallization mother liquor.Secondary crystallization can make the threonine yield improve 6% ~ 7%, but still 20% the threonine of having an appointment remains in the mother liquor.
For crystalline mother solution, threonine manufacturing enterprise usually adopts following two kinds of methods to process: sell feed factory and make feed addictive or directly be discharged in the environment.It is not high to sell feed factory value with it, can cause significant wastage and pollution and directly be discharged in the environment.
Domestic patent (application number 200610014342.4) proposes will be through mixing with zymotic fluid through the membrane filtration degerming after the threonine mother liquor desalination of secondary crystallization, enter next circulation and extract the threonine crystal, adoptable desalination process comprises ion-exchange, nanofiltration and electrodialysis.But the various impurity component concentrations such as albumen, pigment, residual sugar further improve in the mother liquor behind the secondary crystallization, and color is dark, and viscosity is large, mobile extreme difference.Said method is difficult to it is carried out the desalination of efficient and cost-effective.In addition, although the threonine in the recyclable mother liquor of the method, mother liquor is not treated directly and zymotic fluid mixing capsule usefulness, has affected the dna purity of follow-up threonine, and the impurity in the mother liquor can accumulate in circulation, can not accomplish unlimited circulation.
Adopt in principle the threonine in the recyclable primary crystallization mother liquor of ion-exchange process.But contain a certain amount of inorganic salts in the primary crystallization mother liquor, the threonine ion ratio of positively charged is lower under mother liquor pH value environment, and inorganic ions can form strong competition with threonine in the ion exchange process, and mother liquor is directly from friendship, and resin adsorbs threonine hardly.Domestic patent (application number 201010587819.4) proposition is adjusted into 1.5-3.0 with the pH value of threonine primary crystallization mother liquor first, again with threonine in the ion-exchange absorption mother liquor, then be that the ammoniacal liquor of 10-14 carries out wash-out with the pH value, it is 1 eluent that collection begins to Baume degrees from wash-out, with the eluent and the threonine fermentation liquid mixing capsule usefulness that obtain, enter next circulation and extract the threonine crystal at last.Adopt ion-exchange process to reclaim threonine in the mother liquor, both can improve the total recovery of threonine, most impurity in the mother liquor can be removed again, guaranteed the quality of threonine.But the method still can't be removed inorganic ion interference to threonine absorption in ion exchange process, and mother liquor acid adjustment and ion-exchange elution step can increase considerably the soda acid consumption, the soda acids that consume enter from handing over waste liquid at last, so that threonine has increased difficulty of governance from handing over waste liquid to contain the salt content higher than threonine mother liquor.
Summary of the invention
The object of the invention is to overcome the existing threonine crystal mother liquor that produces when producing threonine and be difficult to the defective utilizing and be difficult to administer, a kind of method that reclaims threonine from the threonine crystal mother liquor is provided.
The method that reclaims threonine from the threonine crystal mother liquor of the present invention may further comprise the steps:
1) adopts bipolar membrane electrodialysis technology or common electrical osmotic technique from the threonine crystal mother liquor, inorganic salts to be removed, obtain taking off the threonine crystal mother liquor of inorganic salts; Wherein, described bipolar membrane electrodialysis technology is " acid-salt-alkali " three Room electrodialytic techniques
2) from the threonine crystal mother liquor that takes off inorganic salts, reclaim threonine with base exchange method.
The method according to this invention, described common electrical osmotic technique are " dense-light " two Room common electrical osmotic techniques.
In the technical scheme of the present invention, as adopt the bipolar membrane electrodialysis technology from the threonine crystal mother liquor, to remove inorganic salts, to adopt " Acid-Base-salt " three Room bipolar membrane electrodialysis technology, as shown in Figure 5, the threonine crystal mother liquor that will contain inorganic salts passes into the salt chamber, liquid is finished in the last sour chamber that obtains comprising regenerated acid in sour chamber, and liquid is finished in the alkali chamber that obtains regenerating alkali in the alkali chamber, obtains taking off the threonine crystal mother liquor of inorganic salts in the salt chamber.
Add the threonine crystal mother liquor in the salt chamber of bipolar membrane electrodialysis device, the alkali chamber can as the initial liquid in alkali chamber, directly obtain ammoniacal liquor, NaOH solution or KOH solution according to conventional method water, sig water (weak aqua ammonia, or NaOH solution, or KOH solution etc.) from the alkali chamber; Or according to a conventional method take water, NaOH solution, KOH solution or other strongly basic mediums as the initial liquid in alkali chamber, the ammonia that generates in the alkali chamber blown out with air or other inert gas obtain ammonia; Maybe the ammonia that blows out is further obtained liquefied ammonia with conventional condensation method liquefaction; Maybe the further water of the ammonia that blows out is absorbed and obtain ammoniacal liquor.Can be according to conventional method water, diluted acid (sulfuric acid, hydrochloric acid or nitric acid) the initial liquid as sour chamber to " acid-salt-alkali " three Room bipolar membrane electrodialysis devices
Finish in the liquid the sour chamber that obtains in sour chamber, and the concentration of the sulfuric acid of regeneration is 0.2 ~ 2mol/L; The concentration of hydrochloric acid of regeneration is 0.2 ~ 4mol/L; The concentration of nitric acid of regeneration is 0.2 ~ 4mol/L.
In technical scheme of the present invention, finish in the liquid alkali chamber that obtains in the alkali chamber, and the ammonia concn of regeneration is 0.2 ~ 4mol/L; The concentration of the NaOH of regeneration is 0.2 ~ 4mol/L; The concentration of the potassium hydroxide of regeneration is 0.2 ~ 4mol/L.
When the inorganic salts in the threonine crystal mother liquor were ammonium sulfate, ammonium chloride or ammonium nitrate, the ammonia available air or other inert gases that obtain in the alkali chamber of three Room bipolar membrane electrodialysis blew out; The ammonia that blows out can further obtain liquefied ammonia with conventional condensation method liquefaction, or the water absorption obtains ammoniacal liquor.
Described to blow ammonia operation be with increasing or reduce the pH value that the way of throughput is regulated the alkali chamber, and namely increase throughput when the pH of alkali chamber value is higher than the pH value of setting reduces throughput, thereby keeps the pH value of alkali chamber when the pH of alkali chamber value is lower than the pH value of setting.It is special value more than 9 that the pH value of alkali chamber maintains pH, adopts conventional pH control device.
Described bipolar membrane electrodialysis can carry out in " acid-salt-alkali " three Room bipolar membrane electrodialysis devices of routine.Fig. 5 shows the schematic diagram that the film stacking structure in " acid-salt-alkali " three Room bipolar membrane electrodialysis devices is arranged, and comprises two utmost point chambers, and some groups of acid chambers, salt chamber and alkali chambers being clipped in wherein and being separated by anion-exchange membrane A, cation-exchange membrane C and Bipolar Membrane BM.The organizational form of the bipolar membrane electrodialysis device among the present invention all can adopt one section of one-level or multistage multistage organizational form.The operation of bipolar membrane electrodialysis device can be adopted conventional method of operating, comprises constant current, constant voltage or unsteady flow, transformation mode.Under electric field action, the hydrone of Bipolar Membrane is dissociated into H +And OH -, migration enters sour chamber and alkali chamber, the cation M of salt respectively +With anion X -(for acid group) respectively migration enters alkali chamber and sour chamber.Then obtain sour HX in sour chamber, obtain alkali MOH in the alkali chamber.
In the technical scheme of the present invention, as adopt the common electrical osmotic technique from the threonine crystal mother liquor, to remove inorganic salts, to adopt " dense-light " two Room common electrical osmotic techniques, as shown in Figure 4, the threonine crystal mother liquor that will contain inorganic salts passes into light chamber, liquid is finished in the last dense chamber that obtains comprising inorganic salts in dense chamber, obtains taking off the threonine crystal mother liquor of inorganic salts in light chamber.
The light chamber of " dense-light " two Room common electrical dialyzers adds the threonine crystal mother liquor, and dense chamber can be according to conventional method water, dilute sulfuric acid salt (or hydrochloride, or nitrate) the initial liquid as dense chamber.
Described common electrical dialysis can be carried out in " dense-light " two Room common electrical dialyzers of routine.Fig. 4 shows the schematic diagram that the film stacking structure in " dense-light " two Room common electrical dialyzers is arranged, and comprises two utmost point chambers, and the some groups of dense chambers and the light chamber that are clipped in wherein and are separated by anion-exchange membrane A and cation-exchange membrane C.The organizational form of the common electrical dialyzer among the present invention all can adopt one section of one-level or multistage multistage organizational form.The operation of common electrical dialyzer can be adopted conventional method of operating, comprises constant current, constant voltage or unsteady flow, transformation mode.Under electric field action, the cation M of salt in the feed liquid of light chamber +With anion X -(for acid group) respectively migration enters the different dense chamber in both sides, light chamber.
In bipolar membrane electrodialysis device of the present invention and the common electrical dialyzer, utmost point chamber feed liquid consists of conventional industrial electro dialyzer utmost point chamber commonly used and forms, such as the sodium sulphate of 0.1 ~ 0.5mol/L or the aqueous solution of other indifferent electrolytes; The volume of utmost point chamber is conventional volume, usually can normal circulation get final product in membrane stack with utmost point chamber feed liquid.
In bipolar membrane electrodialysis device of the present invention and the common electrical dialyzer, each chamber (the sour chamber, alkali chamber, salt chamber, the utmost point chamber that comprise the bipolar membrane electrodialysis device, the dense chamber of common electrical dialyzer, light chamber, utmost point chamber) temperature of feed liquid adopts the temperature of conventional electrodialysis operation, usually is no more than 5 ~ 50 ℃ scope; The flow velocity of each chamber (the sour chamber, alkali chamber, salt chamber, the utmost point chamber that comprise the bipolar membrane electrodialysis device, the dense chamber of common electrical dialyzer, light chamber, utmost point chamber) adopts conventional flow velocity, usually is no more than the scope of 0.1 ~ 10cm/s; Current density adopts conventional current density, usually is no more than 1 ~ 200mA/cm 2Scope.
Bipolar membrane electrodialysis device among the present invention and cation-exchange membrane, anion-exchange membrane and the Bipolar Membrane in the common electrical dialyzer are the commercially available prod.
Example as cation-exchange membrane, such as: the Neosebta CL-2.5T of day Bender mountain Cao Da company production etc., the Selemion CMV that Japan AGC company produces etc., the AMFion C-60 that U.S.'s machinery and manufacturing company (AMF) produce etc., the Ionac MC-3142 that American I onac chemical company produces etc., the CM-1 that the court of a feudal ruler, Beijing profit membrane technology development corporation, Ltd. produces etc., the RXCM that light inferior company in Wenan, Hebei produces etc., and the commercially available cation-exchange membrane product of other companies' productions.
Example as anion-exchange membrane, such as: the Neosebta AV-4T of day Bender mountain Cao Da company production etc., the Aciplex CA-1 that Japan's Asahi Kasei Corporation is produced etc., the AMfionA-60 that U.S.'s machinery and manufacturing company (AMF) produce etc., the Ionac MA-3148 that American I onac chemical company produces etc., the AM-1 that the court of a feudal ruler, Beijing profit membrane technology development corporation, Ltd. produces etc., the RXAM that light inferior company in Wenan, Hebei produces etc., and the commercially available anion-exchange membrane product of other companies' productions.
Example as Bipolar Membrane, for example: the Neosebta BP-1 of day Bender mountain Cao Da company production, the FuMa-Tech FT-FBI that U.S. good fortune equine skill company (FuMa-Tech) produces etc., the BPM-1 that the court of a feudal ruler, Beijing profit membrane technology development corporation, Ltd. produces etc., or the RXBM of the inferior company of Wenan, Hebei light production etc., and the commercially available Bipolar Membrane product of other companies' productions.
In one embodiment of the present invention, the threonine crystal mother liquor that will contain inorganic salts passes in the salt chamber of " Acid-Base-salt " three Room bipolar membrane electrodialysis devices, opening the bipolar membrane electrodialysis device processes the threonine crystal mother liquor that passes into the salt chamber, the sulfuric acid, hydrochloric acid or the nitric acid that obtain regenerating in sour chamber, the ammonia, NaOH or the potassium hydroxide that obtain regenerating in the alkali chamber, obtain taking off the threonine crystal mother liquor of inorganic salts in the salt chamber, this pH of threonine crystal mother liquor that takes off inorganic salts is between 2 ~ 5.In the process that from the threonine crystal mother liquor, inorganic salts is removed with three Room bipolar membrane electrodialysis devices, inorganic cation and inorganic anion stride across respectively cation-exchange membrane and anion-exchange membrane enters alkali chamber and sour chamber, until the inorganic cation (NH in the material chamber feed liquid of bipolar membrane electrodialysis device 4 +, Na +Or K +) when being reduced to needed concentration, concentration stops electrodialysis operation.
In another embodiment of the present invention, the threonine crystal mother liquor that will contain inorganic salts passes in the light chamber of " dense-light " two Room common electrical dialyzers, opening the common electrical dialyzer processes the threonine crystal mother liquor that passes into light chamber, obtain the inorganic salt solution of liquid containing ammonium sulfate, ammonium chloride, ammonium nitrate, sodium sulphate, sodium chloride, sodium nitrate, potassium sulfate, potassium chloride or potassium nitrate in dense chamber, obtain taking off the threonine crystal mother liquor of inorganic salts in light chamber, this pH of threonine crystal mother liquor that takes off inorganic salts is between 3 ~ 7.In the process that from the threonine crystal mother liquor, inorganic salts is removed with the common electrical dialyzer, inorganic cation and inorganic anion stride across respectively cation-exchange membrane and anion-exchange membrane enters dense chamber, until the inorganic cation (NH in the material chamber feed liquid of bipolar membrane electrodialysis device 4 +, Na +Or K +) when being reduced to needed concentration, concentration stops electrodialysis operation.
Described " until the inorganic cation (NH in the light chamber feed liquid of the material chamber feed liquid of bipolar membrane electrodialysis device or common electrical dialyzer 4 +, Na +Or K +) concentration is reduced to needed concentration " refer to below 20% of initial concentration.For commercial Application, yes, and pursuit is as far as possible low, preferably is reduced to below 5% or 10% of initial concentration, and this is only relevant with cost accounting, and this concentration is fallen to such an extent that lower inevitable required power consumption is larger.Can monitor inorganic cation (NH by some existing methods 4 +, Na +Or K +) concentration, for example, can electricity be led with measuring, the method for electric current is come the ion concentration in the indirect determination solution, perhaps setting-up time rule of thumb.
Using the common electrical dialysis to remove the dense chamber of inorganic salts in the threonine crystal mother liquor finishes liquid and can further adopt the corresponding bronsted lowry acids and bases bronsted lowry of inorganic salts regeneration that bipolar membrane electrodialysis will be wherein.Employed bipolar membrane electrodialysis device and operating condition thereof are identical with bipolar membrane electrodialysis device and operating condition that aforesaid use bipolar membrane electrodialysis removes inorganic salts in the threonine crystal mother liquor.Liquid is finished in the sour chamber that obtains sulfur acid, hydrochloric acid or nitric acid in sour chamber, and liquid is finished in the alkali chamber that obtains containing ammonia, NaOH or potassium hydroxide in the alkali chamber.
Use bipolar membrane electrodialysis to remove in the threonine crystal mother liquor the sour chamber of inorganic salts and finish liquid, or use the common electrical dialysis remove the dense chamber of inorganic salts in the threonine crystal mother liquor finish liquid finish through the sour chamber that obtains behind the bipolar membrane electrodialysis regenerated acid and alkali liquid can be further directly or after concentrated for the acid adjustment step of threonine isoelectric point crystallization technique; Liquid is finished in the alkali chamber of using bipolar membrane electrodialysis to remove inorganic salts in the threonine crystal mother liquor, or uses the common electrical dialysis to remove in the threonine crystal mother liquor the dense chamber of inorganic salts and finish the alkali chamber of liquid through obtaining behind the bipolar membrane electrodialysis regenerated acid and alkali and finish liquid and can directly or after concentrated be used for Threonine Fermentation step adjusting pH further.
Employing bipolar membrane electrodialysis among the present invention removes the inorganic salts in the threonine crystal mother liquor, or when adopting bipolar membrane electrodialysis that the liquid regenerated acid and alkali is finished in dense chamber, can further adopt and contain the certain density feed liquid of threonine that contains as the initial liquid in sour chamber.
The described feed liquid that contains threonine comprises: the dislysate of the filtered fluid of threonine fermentation liquid, threonine fermentation liquid (seeing through liquid with what threonine fermentation liquid obtained after with method filtration sterilizations such as membrane filtrations), filtering fermentation liquor is (with threonine fermentation liquid during with micro-filtration or ultrafiltration membrance filter, the membrane flux that filters behind the concentration descends, simultaneously also in order to improve the yield that sees through threonine in the liquid of filtration, need to add water in the side of holding back of film, continue to filter, this moment to see through liquid be dislysate) or their dilution.
After the threonine crystal mother liquor aforesaid bipolar membrane electrodialysis of process or the common electrodialysis process, obtain taking off the threonine crystal mother liquor of inorganic salts, wherein contain the threonine of 50 ~ 100g/L.The present invention adopts base exchange method (comprising highly acidic cation exchange process and Subacidity cation exchange process), reclaims threonine from the threonine crystal mother liquor that takes off inorganic salts.
The threonine crystal mother liquor is after " acid-salt-alkali " three Room bipolar membrane electrodialysis technology or common electrical osmotic technique remove wherein inorganic salts, it is acid that the threonine crystal mother liquor that takes off inorganic salts that obtains is, threonine wherein exists with cationic form, therefore needs to adopt base exchange method recovery threonine wherein.
Method with cation exchange recovery threonine provided by the invention comprises: the aforesaid threonine crystal mother liquor that takes off inorganic salts is passed into Hydrogen cation exchange column absorption threonine, obtain simultaneously ion-exchange and see through liquid; With the threonine of the ammoniacal liquor of 0.2 ~ 4mol/L (or the sodium hydroxide solution of 0.2 ~ 4mol/L, or the potassium hydroxide solution of 0.2 ~ 4mol/L) wash-out absorption, what obtain simultaneously containing threonine frees liquid (being high flow point); Hydrochloric acid (or the sulfuric acid of 0.2 ~ 2mol/L with 0.2 ~ 4mol/L; Or the nitric acid of 0.2 ~ 4mol/L) cation regenerant exchange column, make it change Hydrogen into, can again be used for absorption, obtain simultaneously containing the regeneration of ammonium chloride, ammonium sulfate, ammonium nitrate, sodium chloride, sodium sulphate, sodium nitrate, potassium chloride, potassium sulfate or potassium nitrate through liquid.
When freeing of obtaining of wash-out stops to collect the liquid of freeing that contains threonine when threonine concentration is lower than 20 ~ 120g/L in the liquid, the wash-out that liquid (being the wash-out tail washings, low flow point) is used for next time or next ion exchange column of freeing that contains threonine that after this flows out.
Described cationic ion-exchange resin can adopt storng-acid cation exchange resin, weak-acid cation-exchange resin.
As the example of storng-acid cation exchange resin, such as Tianjin Nankai Hecheng S﹠T Co., Ltd. produce 001 * 7,002 * 7,003 * 7, D061, D001-CC etc.; Jiangsu Province, China Su Qing engineering of water treatment Group Co.,Ltd produce 001 * 7,001 * 7H, 001 * 8,001 * 10, D001 etc.; Anhui Samsung resin Science and Technology Ltd. produce 001 * 7 etc.; The JK008 that China Langfang Bel's specialization worker building materials Co., Ltd produces etc.; Hangzhou China win honour for that resin company produces 001 * 7, D001 etc.; And the commercially available storng-acid cation exchange resin product of other companies' productions.
As the example of weak-acid cation-exchange resin, D151, the D152 that produces such as Tianjin Nankai Hecheng S﹠T Co., Ltd., D113 etc.; Jiangsu Province, China Su Qing engineering of water treatment group Co., Ltd produce 112, D113 etc.; Anhui Samsung resin Science and Technology Ltd. produce 110, DK110 etc.; And the commercially available weak-acid cation-exchange resin product of other companies' productions.
Among the present invention, ion exchange column can adopt conventional ion-exchange unit, such as fixed bed, moving bed, simulation moving-bed or continuous ion exchange apparatus.The organizational form of ion exchange column can adopt conventional form, such as single-column, multicolumn series connection.Mode of operation comprises batch formula and continued operation.
Among the present invention, the flow velocity when taking off the threonine crystal mother liquor upper prop, wash-out of inorganic salts and regeneration is conventional flow velocity.Usually the flow velocity in the ion exchange column is in 0.5 ~ 10 column volume/hour scope.
Can be independent from the liquid of freeing that contains threonine that the cation exchange wash-out obtains, or process with the method and the step that merge the isoelectric point crystallization that adopts existing threonine through the threonine fermentation liquid of membrane filtration degerming, the threonine product obtained.
The method according to this invention can also be included in after the cation exchange, and the regeneration that contains ammonium chloride, ammonium sulfate, ammonium nitrate, sodium chloride, sodium sulphate, sodium nitrate, potassium chloride, potassium sulfate or potassium nitrate is seen through the step that liquid carries out acid-alkali regeneration.
Can further adopt bipolar membrane electrodialysis that wherein ammonium chloride, ammonium sulfate, ammonium nitrate, sodium chloride, sodium sulphate, sodium nitrate, potassium chloride, potassium sulfate or potassium nitrate are regenerated as corresponding acid (hydrochloric acid, sulfuric acid or nitric acid) and alkali (ammonia, NaOH or potassium hydroxide) from the regeneration that contains ammonium chloride, ammonium sulfate, ammonium nitrate, sodium chloride, sodium sulphate, sodium nitrate, potassium chloride, potassium sulfate or potassium nitrate that cation exchange obtains through liquid.The bipolar membrane electrodialysis device that adopts and method of operating thereof are identical with aforesaid bipolar membrane electrodialysis device and method of operating thereof for removing the use of threonine crystal mother liquor inorganic salts.
The ammoniacal liquor that the alkali chamber obtains (or sodium hydroxide solution, or potassium hydroxide solution) can be further used for the threonine of wash-out absorption from the cation exchange column.
The sulfuric acid that obtains of acid chamber (or hydrochloric acid, or nitric acid) can be further used for the regeneration of cation exchange column.
The method according to this invention can also be included in after the cation exchange, to see through the step of the further resource of liquid from friendship.
What absorption saw through the Hydrogen cation exchange column during threonine sees through liquid (seeing through liquid from handing over), mainly contains the various organic matters that threonine fermentation liquid brings, and can adopt various conventional method resources or improvement, such as producing methane.
The present invention preferably uses yeast to process from handing over and sees through liquid.Consume most of organic matter by culture yeasts, obtain simultaneously can be used as the yeast of forage protein.Waste liquid behind the culture yeasts can adopt conventional anaerobism, aerobic process to administer.
Adopt the method for cellar culture yeast, barms is added and should see through liquid from handing over.Used barms is the conventional barms that comprises candida tropicalis, candida utili, saccharomyces cidri, geotrichum candidum or saccharomyces cerevisiae etc.In the one embodiment of the present invention, use from handing over and see through liquid culture yeasts single culture, COD can be down to 4000 ~ 10000mg/L from 60000 ~ 120000mg/L, the yeast productive rate can reach 22g/L days.And the present invention can consume most ofly organic by culture yeasts, and the waste liquid behind the culture yeasts can adopt conventional anaerobism, aerobic process governance for reaching standard or reuse.And processing from handing over through the yeast that has also obtained can be used as forage protein in the liquid.
In view of very complicated through the composition of liquid from friendship, the single culture utilization is from handing over the nutriment that sees through liquid can have certain limitation, so more preferably, use a plurality of barmses, saccharomyces cidri for example, candida tropicalis and candida utili process from handing over to see through liquid by their Mixed culture, in order to utilize the complementarity of each bacterial classification nutritional need, can more subdue COD.In one embodiment of the present invention, use when hand over seeing through liquid and cultivate the mixture of above-mentioned three primary yeasts, the biomass that obtains does not almost have period of delay all greater than independent cultivation, the space-time yield of logarithmic phase can reach 1g/Lh, and COD can be down to 7000mg/L from 100000mg/L.
The method according to this invention can also be included in that the threonine crystal mother liquor carries out bipolar membrane electrodialysis or the common electrical dialysis removes before the inorganic salts, and the threonine crystal mother liquor is removed insoluble matter and except the step of albumen.
Adopt conventional means except insoluble matter, such as means and combinations thereof such as organic film, inorganic membrane filtration or press filtrations, necessary words can increase the operations such as flocculation, drainage, and the threonine crystal mother liquor is removed insoluble matter.
Adopt conventional except the albumen ultrafiltration technology.Can adopt molecular cut off is the milipore filter of 1K, 3K, 6K or 10K, and the threonine crystal mother liquor is removed albumen.
Pollute because insoluble matter and foreign protein can form films to the various films that use in bipolar membrane electrodialysis and the common electrical dialysis, can prolong bipolar membrane electrodialysis device and common electrodialytic operation cycle, reduce energy consumption except insoluble matter, except albumen thereby the present invention is about to first the threonine crystal mother liquor.
The method according to this invention can also be included in that the threonine crystal mother liquor carries out bipolar membrane electrodialysis or the common electrical dialysis removes before the inorganic salts, the threonine crystal mother liquor is purified the step of decalcification magnesium.
The enforcement of decalcification magnesium step is the method that adopts conventional ion-exchange, or adds the method that oxalic acid forms oxalate precipitation.
The ion exchange resin that ion-exchange of the present invention removes calcium in the crystalline mother solution, magnesium ion can adopt storng-acid cation exchange resin, weak-acid cation-exchange resin and chelating ion exchange resin.
Be commercially available storng-acid cation exchange resin as the storng-acid cation exchange resin example, as: D072, D061 etc. that Tianjin Nankai Hecheng S﹠T Co., Ltd. produces; D001, SQD-61 etc. that Jiangsu Province, China Su Qing engineering of water treatment Group Co.,Ltd produces; Anhui Samsung resin Science and Technology Ltd. produce 001 * 7 etc.; The JK008 that China Langfang Bel's specialization worker building materials Co., Ltd produces; And Hangzhou China win honour for that resin company produces 001 * 7, D001 etc.; And the commercially available storng-acid cation exchange resin product of other companies' productions.
Example as weak-acid cation-exchange resin is commercially available weak-acid cation-exchange resin, as: D151, D152 etc. that Tianjin Nankai Hecheng S﹠T Co., Ltd. produces; Jiangsu Province, China Su Qing engineering of water treatment group Co., Ltd produce 112 etc.; The DK110 that Anhui Samsung resin Science and Technology Ltd. produces, 724 etc.; And the commercially available weak-acid cation-exchange resin product of other companies' productions.
Example as chelating ion exchange resin is commercially available chelating ion exchange resin, as: D401, D418 that Tianjin Nankai Hecheng S﹠T Co., Ltd. produces, the D401D406 that Jiangsu Province, China Su Qing engineering of water treatment group Co., Ltd produces etc.; And the commercially available chelating amberlite fat prod of other companies' productions.
Preferred Tianjin Nankai Hecheng S﹠T Co., Ltd. produces among the present invention D072 or D418, or the chelating ion exchange resin D402 of Jiangsu Province, China Su Qing engineering of water treatment Group Co.,Ltd production.
Oxalate precipitation method of the present invention, the concrete operations condition is as follows: the concentration of the concentration of oxalic acid in the threonine crystal mother liquor is 0.01 ~ 5mol/L; Or the addition of oxalic acid is 1 ~ 5 times of total moles of calcium magnesium in the threonine crystal mother liquor.The form that oxalic acid adds is directly to drop into the oxalic acid solid or wiring solution-forming adds again.Precipitation reaction temperature is conventional.The method of removing calcium oxalate precipitation after precipitation reaction is finished is the forms such as centrifugal, filtration.
Because the high-valence cationic (mainly being calcium, magnesium ion) in the threonine crystal mother liquor can form membrane contaminant at cation-exchange membrane and Bipolar Membrane.Film pollutes and can increase resistance and energy consumption, increases the cleaning burden of bipolar membrane electrodialysis device and common electrical dialyzer.Therefore, the present invention carried out first the step of decalcification magnesium to the threonine crystal mother liquor before the threonine crystal mother liquor is passed into salt chamber or light chamber, was conducive to improve the efficient of bipolar membrane electrodialysis device or common electrical dialyzer and reduced energy consumption.
The method according to this invention can also be included in that the threonine crystal mother liquor carries out bipolar membrane electrodialysis or the common electrical dialysis removes before the inorganic salts, the step that the threonine crystal mother liquor is decoloured.
Conventional means is adopted in decolouring, such as means and combinations thereof such as resin decolorization or activated carbon decolorizings.
The example of resin as decolouring usefulness is commercially available decolorizing resin, D280, the D3520 etc. that produce such as Tianjin Nankai Hecheng S﹠T Co., Ltd.; D301-G, D301-F etc. that Jiangsu Province, China Su Qing engineering of water treatment group Co., Ltd produces; Anhui Samsung resin Science and Technology Ltd. produce 201 * 4,330 etc.; And the commercially available decolorizing resin product of other companies' productions.
The example of active carbon as decolouring usefulness is commercially available active carbon, comprise Powdered Activated Carbon and granular activated carbon, powdered active carbon such as Chemical Reagent Co., Ltd., Sinopharm Group's production, or Zhengzhou bamboo grove active carbon development corporation, Ltd. wood powder shaped activated carbon, the decolouring special-purpose activated charcoal produced, the 615 industrial decoloration active carbons that Liyang City Kang Hong active carbon factory produces, the decoloration active carbon that the good power charcoal industry in Nanjing Co., Ltd produces etc.; And the commercially available decoloration active carbon product of other companies' productions.
The D3520 that the preferred Tianjin Nankai Hecheng S﹠T Co., Ltd. of the present invention produces, or the ion exchange resin D301-F of Jiangsu Province, China Su Qing engineering of water treatment Group Co.,Ltd production, or the powdered active carbon of Chemical Reagent Co., Ltd., Sinopharm Group's production, or the decolouring special-purpose activated charcoal of Zhengzhou bamboo grove active carbon development corporation, Ltd. production.
Because the pigment in the threonine crystal mother liquor can form membrane contaminant.Film pollutes and can increase resistance and energy consumption, increases the cleaning burden of bipolar membrane electrodialysis device and common electrical dialyzer.Therefore, the present invention is passing into the threonine crystal mother liquor step of first the threonine crystal mother liquor being decoloured before salt chamber or the light chamber, is conducive to reduce the energy consumption of bipolar membrane electrodialysis device or common electrical dialyzer.
The method according to this invention can also be included in that the threonine crystal mother liquor carries out bipolar membrane electrodialysis or the common electrical dialysis removes before the inorganic salts, the step that the threonine crystal mother liquor is diluted.
Can adopt the means such as recirculated water that add in desalted water or condensed water or the technique, the threonine crystal mother liquor is diluted to 1 ~ 5 times of original volume.
The present invention first with the dilution of threonine crystal mother liquor, with the concentration of the impurity such as the carbohydrate in the reduction threonine crystal mother liquor, pigment, thereby reduced the energy consumption that removes the inorganic salts process on the whole before the threonine crystal mother liquor is passed into salt chamber or light chamber; But also can prolong service life of resin in the cation exchange column.
As required, the method that reclaims threonine from the threonine crystal mother liquor of the present invention is optionally selected above-mentioned with the barms fermentation, except insoluble matter with except albumen, decalcification magnesium, decolouring, dilution.Above-mentioned can arbitrarily adjust except insoluble matter with except the sequencing of albumen, decalcification magnesium, decolouring, dilution step, to reach preferably effect.An embodiment of the invention as shown in Figure 3, have namely been used successively with the barms fermentation, except insoluble matter with except overall processes such as albumen, decalcification magnesium, decolouring, dilutions.
The method that reclaims threonine from the threonine crystal mother liquor of the present invention is applicable to ammonia, NaOH or the potassium hydroxide alkali lye as sweat adjusting pH, with the threonine isoelectric point crystallization technique of the electric acidulants such as sulfuric acid, hydrochloric acid or nitric acid conduct.
The present invention has realized reclaiming threonine from the threonine crystal mother liquor, improved the extract yield of threonine, can also further realize taking full advantage of of each component in the threonine crystal mother liquor, and can make the ripe at present biotechnology governance for reaching standard of raffinate, reduce the discharging of polluting.In addition, with respect to the method for in the prior art threonine secondary crystallization mother liquor being processed, the present invention begins to carry out electrodialysis desalination from threonine primary crystallization mother liquor, reclaim wherein threonine with ion-exchange again after the desalination, need not again other acid adding or alkali, pollutant is few, saves cost, and industry can realize.
The concrete advantage that reclaims the method for threonine from the threonine crystal mother liquor of the present invention is:
1. remove ion-exchange and reclaimed in the threonine crystal mother liquor in the threonine process inorganic salts to the competitive Adsorption of threonine, thereby significantly improved the rate of recovery of threonine;
2. be the forage protein (price surpasses 3000 yuan/tons, and composite fertilizer's price about 600 yuan/tons) of high value with the organic matter transformation in the threonine crystal mother liquor, can realize organic resource and high-valued;
3. inorganic bronsted lowry acids and bases bronsted lowry is realized closed cycle, thus the decrease supplies consumption;
4. remove the bottleneck of waste liquid downstream biological treating, so that the ripe at present biotechnology governance for reaching standard of waste liquid fundamentally solves the pollution problem that high bisulfate waste liquor brings.
Description of drawings
Fig. 1 is that the isoelectric point crystallization method is produced the threonine process flow diagram.
Fig. 2 is the process flow diagram that reclaims the method for threonine from the threonine crystal mother liquor of the present invention.
Fig. 3 is the process flow diagram (it is recycling to contain desalination pre-treatment and intermediate product) that reclaims the method for threonine from the threonine crystal mother liquor of the present invention.
Film stacking structure in Fig. 4 common electrical dialyzer is arranged schematic diagram;
Wherein: A is anion-exchange membrane, and C is cation-exchange membrane, and " dense " represents dense chamber, and " light " represents light chamber, and M is the cation of salt, and X is the acid radical anion of salt.
Film stacking structure in Fig. 5 " acid-salt-alkali " three Room bipolar membrane electrodialysis devices is arranged schematic diagram;
Wherein: A is anion-exchange membrane, and C is cation-exchange membrane, and BM is Bipolar Membrane; " salt " expression salt chamber, " acid " represents sour chamber, " alkali " expression alkali chamber, M is the cation of salt, X is the acid radical anion of salt.
The specific embodiment
Embodiment 1
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is three Room bipolar membrane electrodialysis devices of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of amberplex is 210mm * 62mm, uses BP-1 type Bipolar Membrane, JAM-10 type anion-exchange membrane and JCM-1 type cation-exchange membrane.Bipolar Membrane, anion-exchange membrane, cation-exchange membrane form 5 pairs of three compartment film stacking structure (as shown in Figure 5) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made minus plate.Dividing plate and filter are polypropylene material, and dividing plate is without the loop dividing plate, and filter is the mesh grid type.
The threonine crystal mother liquor 2.5L that contains 19g/L sodium sulphate, 68g/L threonine of Ningxia, China Yi Pin biotech inc is passed into the salt chamber; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 0.5L, 0.05mol/L, and the initial liquid in alkali chamber is the sodium hydroxide solution of 0.5L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 1mS/cm, stop electrodialysis operation.In sour chamber, obtain the about 0.8L of sulfuric acid that concentration is about 0.34mol/L.Obtain the about 0.53L of NaOH that concentration is about 1.15mol/L in the alkali chamber.The threonine crystal mother liquor 1.98L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.29, contains threonine 70g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and 001 * 7 storng-acid cation exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.80L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 2 column volumes/hour.That collects about 1.88L at the bottom of the post sees through liquid from handing over, and its threonine content 1g/L, pH are 3.03, the about 20g/L of residual sugar.
The sodium hydroxide solution of the about 2.0mol/L of 0.8L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 172g/L of threonine free the about 0.66L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The liquid of freeing that 0.66L is contained the about 172g/L of threonine concentrates 4 times by the conventional concentrated isoelectric point crystallization technique of threonine, centrifugation obtains threonine crystal 64g, threonine in threonine fermentation liquid corresponding to 1.8L threonine crystal mother liquor is as calculation of total, this moment, the yield of threonine reached 94%, compare with adopting conventional threonine isoelectric point crystallization technique, the yield of threonine has improved 8%.
The sulfuric acid solution of the about 1.0mol/L of 0.9L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 128g/L of contains sodium sulfate at the bottom of post sees through the about 0.7L of liquid, and ion exchange column is regenerated as Hydrogen.
Acid-alkali regeneration: the regeneration that contains sodium sulfate concentration is about 128g/L sees through the salt chamber that liquid 0.7L passes into three Room bipolar membrane electrodialysis devices (with the bipolar membrane electrodialysis device of embodiment 1), the initial liquid in acid chamber is the dilution heat of sulfuric acid of 0.6L, 0.05mol/L, the initial liquid in alkali chamber is the sodium hydroxide solution of 0.6L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.Operating condition stops electrodialysis operation with the operating condition of embodiment 1 bipolar membrane electrodialysis device when electric conductivity value drops to 4 μ S/cm.In sour chamber, obtain the about 0.71L of sulfuric acid that concentration is about 0.90mol/L; Be used for the regeneration of next batch cation exchange column.Obtain the about 0.64L of sodium hydroxide solution of 1.8mol/L in the alkali chamber; Be used for the desorb of the cation exchange column of next batch absorption threonine.
Embodiment 2
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 3.6L that will contain 15g/L sodium chloride, 68g/L threonine passes into the salt chamber; The initial liquid in acid chamber is that the 1.0L threonine removes fermented liquid (wherein containing threonine 110g/L), and the initial liquid in alkali chamber is the sodium hydroxide solution of 1.0L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 1mS/cm, stop electrodialysis operation.In sour chamber, obtain the acidated threonine of the hydrochloric 0.64mol/L of being about except the about 1.22L of fermented liquid.Obtain the about 1.1L of NaOH that concentration is about 0.66mol/L in the alkali chamber.The threonine crystal mother liquor 2.90L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.22, contains threonine 69g/L.
The isoelectric point crystallization that the acidated threonine of the hydrochloric 0.64mol/L of being about that obtains in the sour chamber is used for the 1L threonine fermentation liquid (containing the about 116g/L of threonine) of another batch except fermented liquid, consume acidated threonine except the about 0.4L of fermented liquid, gained threonine crystal and traditional isoelectric point crystallization do not have marked difference.
With the concentrated 2 times of adjusting pH that are used for the Threonine Fermentation of another batch of sodium hydroxide solution that the alkali chamber obtains, effect and commodity NaOH do not have marked difference.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 800mm, 001 * Final 8 acid cation exchange resin that in-built 1.8L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces, the resin pattern is Hydrogen.
The threonine crystal mother liquor 2.8L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 2.9L at the bottom of the post sees through liquid from handing over, and its threonine content 1.5g/L, pH are 3.01, the about 22.8g/L of residual sugar.
The sodium hydroxide solution of the about 2.0mol/L of 1.4L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 172g/L of threonine free the about 1.06L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.After freeing liquid, continue to collect the wash-out tail washings 0.5L that contains about 52g/L threonine and 1.1mol/L NaOH, be used for the wash-out that the absorption of next batch or next root has the cation exchange column of threonine.
The liquid of freeing that 1.06L is contained the about 172g/L of threonine mixes with the threonine fermentation liquid of degerming, press the concentrated isoelectric point crystallization of the conventional concentrated isoelectric point crystallization technique of threonine, after the centrifugation than do not add contain threonine free liquid batch more obtain threonine crystal 88g, threonine in threonine fermentation liquid corresponding to 2.8L threonine crystal mother liquor is as calculation of total, this moment, the yield of threonine reached 92%, compare with adopting conventional threonine isoelectric point crystallization technique, the yield of threonine has improved 6%.
The hydrochloric acid solution of the about 1.6mol/L of 2.4L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.The regeneration of collecting the about 88g/L of sodium chloride-containing at the bottom of post sees through the about 1.8L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 3
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 2.8L that will contain 21g/L sodium nitrate, 88g/L threonine passes into the salt chamber; The initial liquid in acid chamber is the dilute nitric acid solution of 0.4L, 0.05mol/L, and the initial liquid in alkali chamber is the sodium hydroxide solution of 0.4L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.6mS/cm, stop electrodialysis operation.In sour chamber, obtain the about 0.66L of nitric acid that concentration is about 0.93mol/L.Obtain the about 0.43L of NaOH that concentration is about 1.43mol/L in the alkali chamber.The threonine crystal mother liquor 2.22L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.32, contains threonine 90g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, the D001 storng-acid cation exchange resin that in-built 1.2L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.7L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 1.86L at the bottom of the post sees through liquid from handing over, and its threonine content 0.8g/L, pH are 2.98, the about 23.6g/L of residual sugar.
Last batch of sodium hydroxide solution that the regeneration of cation exchange column is seen through the about 1.5mol/L of 1.2L that the alkali chamber of liquid regenerated acid and alkali obtains with bipolar membrane electrodialysis passed into to adsorb to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 120g/L of threonine free the about 1.15L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.Effect and commodity NaOH do not have marked difference.
The nitric acid of the about 1.0mol/L of 2.6L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.Collect the regeneration that contains the about 72g/L of sodium nitrate and see through the about 1.9L of liquid at the bottom of post, ion exchange column is regenerated as Hydrogen.
Embodiment 4
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 3.0L that will contain 18g/L ammonium sulfate, 81g/L threonine passes into the salt chamber; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.5L, 0.05mol/L, and the initial liquid in alkali chamber is the sodium hydroxide solution of 1.5L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.7mS/cm, stop electrodialysis operation.Pass into air in the material cylinder of alkali chamber, with the ammonia Air blowing of regeneration.PH value with the way control alkali chamber of regulating throughput that is: increases throughput when the pH of alkali chamber value is higher than the pH value of setting, reduce throughput when the pH of alkali chamber value is lower than the pH value of setting, thereby keeps the pH of alkali chamber.It is 11.0 that the pH value of alkali chamber maintains pH.Adopt the pH of conventional pH electrode monitoring alkali chamber.In sour chamber, obtain the about 1.8L of sulfuric acid that concentration is about 0.25mol/L.The ammonia that blows out from the alkali chamber absorbs with 0.1L water another container, obtains the ammoniacal liquor of mass concentration about 12%.The threonine crystal mother liquor 2.6L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.41, contains threonine 82g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and the D001-CC storng-acid cation exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.9L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1.5 column volumes/hour.That collects about 1.98L at the bottom of the post sees through liquid from handing over, and its threonine content 0.9g/L, pH are 3.22, the about 23.8g/L of residual sugar.
The ammonia spirit of the about 1.8mol/L of 1.1L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1.5 column volumes/hour.Collect at the bottom of the post contain the about 160g/L of threonine free the about 0.90L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
Last batch of sulfuric acid that the regeneration of cation exchange column is seen through the about 1.2mol/L of 1.6L that the sour chamber of liquid regenerated acid and alkali obtains with bipolar membrane electrodialysis is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1.5 column volumes/hour.The regeneration of collecting the about 156g/L of liquid containing ammonium sulfate at the bottom of post sees through the about 1.4L of liquid, and ion exchange column is regenerated as Hydrogen.The dilute sulfuric acid that effect and commodity diluting concentrated sulfuric acid obtain does not have significant difference.
Embodiment 5
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 2.2L that will contain 13.6g/L ammonium chloride, 86g/L threonine passes into the salt chamber; The initial liquid in acid chamber is the dilute hydrochloric acid solution of 0.6L, 0.05mol/L, and the initial liquid in alkali chamber is the sodium hydroxide solution of 0.6L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.5mS/cm, stop electrodialysis operation.Pass into air in the material cylinder of alkali chamber, with the ammonia Air blowing of regeneration, air-blowing quantity is 1L/min.In sour chamber, obtain the about 0.76L of hydrochloric acid that concentration is about 0.71mol/L.The ammonia that blows out from the alkali chamber absorbs with 0.2L water another container, obtains the ammoniacal liquor of mass concentration about 4%.The threonine crystal mother liquor 1.9L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.28, contains threonine 86g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produce 001 * 7 storng-acid cation exchange resin, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.8L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 2 column volumes/hour.That collects about 1.86L at the bottom of the post sees through liquid from handing over, and its threonine content 1.2g/L, pH are 3.12, the about 24.6g/L of residual sugar.
The ammonia spirit of the about 2.0mol/L of 1.1L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 180g/L of threonine free the about 0.76L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.After freeing liquid, continue to collect the wash-out tail washings 0.6L that contains about 46g/L threonine and 1.2mol/L ammonia, be used for the wash-out that the absorption of next batch or next root has the cation exchange column of threonine.
The hydrochloric acid of the about 1.0mol/L of 2.8L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 50g/L of containing ammonium chloride at the bottom of post sees through the about 2.1L of liquid, and ion exchange column is regenerated as Hydrogen.
Acid-alkali regeneration: the regeneration that containing ammonium chloride concentration is about 50g/L sees through the salt chamber that liquid 2.1L passes into three Room bipolar membrane electrodialysis devices (with the bipolar membrane electrodialysis device of embodiment 1), the initial liquid in acid chamber is the dilute hydrochloric acid solution of 2.0L, 0.05mol/L, the initial liquid in alkali chamber is the sodium hydroxide solution of 1.0L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.Operating condition stops electrodialysis operation with the operating condition of embodiment 1 bipolar membrane electrodialysis device when electric conductivity value drops to 3 μ S/cm.Pass into air in the material cylinder of alkali chamber, with the ammonia Air blowing of regeneration, air-blowing quantity is 1.0L/min.In sour chamber, obtain the about 2.2L of hydrochloric acid that concentration is about 1.0mol/L, be used for the regeneration of next batch cation exchange column.The ammonia that blows out from the alkali chamber passes into and places-60 ℃ of stainless steel coiled pipes in the refrigerator, obtains about 39 gram liquefied ammonia in the receiving bottle of the other end of coiled pipe, be diluted with water to 2mol/L ammoniacal liquor after, be used for the desorb of the cation exchange column of next batch absorption threonine.
Embodiment 6
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 2.9L that will contain 20g/L ammonium nitrate, 87g/L threonine passes into the salt chamber; The initial liquid in acid chamber is the dilute nitric acid solution of 0.4L, 0.05mol/L, and the initial liquid in alkali chamber is the sodium hydroxide solution of 0.4L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.8mS/cm, stop electrodialysis operation.Pass into air in the material cylinder of alkali chamber, with the ammonia Air blowing of regeneration, air-blowing quantity is 1.5L/min.In sour chamber, obtain the about 0.50L of nitric acid that concentration is about 1.26mol/L.The ammonia that blows out from the alkali chamber passes into and places-60 ℃ of stainless steel coiled pipes in the refrigerator, obtains about 10.5 gram liquefied ammonia in the receiving bottle of the other end of coiled pipe.The threonine crystal mother liquor 2.51L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.42, contains threonine 89g/L.
The nitric acid that obtains in the sour chamber is concentrated 2 times, be used for the isoelectric point crystallization of the 1L threonine fermentation liquid (containing the about 116g/L of threonine) of another batch, consume the about 0.07L of nitric acid, gained threonine crystal and traditional isoelectric point crystallization do not have marked difference.
The liquefied ammonia dilution that condensation is obtained is about 25% ammoniacal liquor for mass concentration, and the pH that is used for the Threonine Fermentation of another batch regulates, and effect does not have marked difference with the concentrated ammonia liquor that obtains with the liquid ammonia dilution.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and the D61 storng-acid cation exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.72L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 1.87L at the bottom of the post sees through liquid from handing over, and its threonine content 1.6g/L, pH are 2.87, the about 26g/L of residual sugar.
Last batch of ammonia spirit that the regeneration of cation exchange column is seen through the about 2.0mol/L of 1.1L that liquefied ammonia dilution that ammonia condensing that the alkali chamber of liquid regenerated acid and alkali blows out makes obtains with bipolar membrane electrodialysis passed into to adsorb to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 162g/L of threonine free the about 0.88L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.Effect does not have significant difference with the ammoniacal liquor that obtains with the liquid ammonia dilution.
The nitric acid of the about 1.0mol/L of 2.6L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.Collect the regeneration that contains the about 71.8g/L of ammonium nitrate and see through the about 1.6L of liquid at the bottom of post, ion exchange column is regenerated as Hydrogen.
Embodiment 7
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 2.7L that will contain 22g/L potassium sulfate, 75g/L threonine passes into the salt chamber; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 0.6L, 0.025mol/L, and the initial liquid in alkali chamber is the potassium hydroxide solution of 0.6L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.9mS/cm, stop electrodialysis operation.In sour chamber, obtain the about 0.71L of sulfuric acid that concentration is about 0.46mol/L.Obtain the about 0.62L of potassium hydroxide that concentration is about 1.15mol/L in the alkali chamber.The threonine crystal mother liquor 2.4L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.29, contains threonine 76g/L.
With 4 times of the sulphuric acid concentration that obtain in the sour chamber, be used for the isoelectric point crystallization of the 1L threonine fermentation liquid (containing the about 110g/L of threonine) of another batch, the about 0.02L of consumption sulfuric acid, gained threonine crystal and traditional isoelectric point crystallization do not have marked difference.
With the concentrated 2 times of adjusting pH that are used for the Threonine Fermentation of another batch of potassium hydroxide solution that the alkali chamber obtains, effect and commodity NaOH do not have marked difference.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai with become that Science and Technology Ltd. produces 003 * 7 storng-acid cation exchange resin, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.88L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1.8 column volumes/hour.That collects about 1.92L at the bottom of the post sees through liquid from handing over, and its threonine content 1.3g/L, pH are 3.51, the about 25.6g/L of residual sugar.
The potassium hydroxide solution of the about 2.0mol/L of 1.2L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1.8 column volumes/hour.Collect at the bottom of the post contain the about 177g/L of threonine free the about 0.72L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The sulfuric acid of the about 1.0mol/L of 1.4L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 156g/L of sulfur acid potassium at the bottom of post sees through the about 1.2L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 8
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 3.3L that will contain 18g/L potassium chloride, 66g/L threonine passes into the salt chamber; The initial liquid in acid chamber is the dilute hydrochloric acid solution of 1.0L, 0.05mol/L, and the initial liquid in alkali chamber is the potassium hydroxide solution of 1.0L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.7mS/cm, stop electrodialysis operation.In sour chamber, obtain the about 1.22L of hydrochloric acid that concentration is about 0.59mol/L.Obtain the about 1.1L of NaOH that concentration is about 0.62mol/L in the alkali chamber.The threonine crystal mother liquor 2.8L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.23, contains threonine 68g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 800mm, 001 * Final 8 acid cation exchange resin that in-built 1.8L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces, the resin pattern is Hydrogen.
The threonine crystal mother liquor 2.9L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 3.0L at the bottom of the post sees through liquid from handing over, and its threonine content 0.9g/L, pH are 3.11, the about 23.3g/L of residual sugar.
The potassium hydroxide solution of the about 1.0mol/L of 3.7L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 82g/L of threonine free the about 2.2L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.After freeing liquid, continue to collect the wash-out tail washings 0.54L that contains about 30g/L threonine and 0.6mol/L potassium hydroxide, be used for the wash-out that the absorption of next batch or next root has the cation exchange column of threonine.
Last batch of hydrochloric acid that the regeneration of cation exchange column is seen through the about 1.5mol/L of 2.8L that the sour chamber of liquid regenerated acid and alkali obtains with bipolar membrane electrodialysis is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.The regeneration of collecting the about 86g/L of chloride containing potassium at the bottom of post sees through the about 2.6L of liquid, and ion exchange column is regenerated as Hydrogen.Effect with do not have significant difference with commodity hydrochloric acid.
Embodiment 9
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
The threonine crystal mother liquor 2.8L that will contain 25g/L potassium nitrate, 90g/L threonine passes into the salt chamber; The initial liquid in acid chamber is the dilute nitric acid solution of 0.4L, 0.05mol/L, and the initial liquid in alkali chamber is the potassium hydroxide solution of 0.4L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.9mS/cm, stop electrodialysis operation.In sour chamber, obtain the about 0.48L of nitric acid that concentration is about 1.22mol/L.Obtain the about 0.42L of NaOH that concentration is about 1.45mol/L in the alkali chamber.The threonine crystal mother liquor 2.41L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.34, contains threonine 91g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 400mm, in-built 0.9L Nankai and 001 * 7 storng-acid cation exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.4L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 1.63L at the bottom of the post sees through liquid from handing over, and its threonine content 1.1g/L, pH are 2.96, the about 21.6g/L of residual sugar.
The potassium hydroxide solution of the about 1.5mol/L of 1.5L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 122g/L of threonine free the about 0.93L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The nitric acid of the about 1.0mol/L of 2.3L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.Collect the regeneration that contains the about 71.6g/L of potassium nitrate and see through the about 1.84L of liquid at the bottom of post, ion exchange column is regenerated as Hydrogen.
Acid-alkali regeneration: will contain the regeneration that potassium nitrate concentration is about 71.6g/L and see through the salt chamber that liquid 1.84L passes into three Room bipolar membrane electrodialysis devices (with the bipolar membrane electrodialysis device of embodiment 1), the initial liquid in acid chamber is the dilute nitric acid solution of 1.0L, 0.05mol/L, the initial liquid in alkali chamber is the potassium hydroxide solution of 1.0L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.Operating condition stops electrodialysis operation with the operating condition of embodiment 1 bipolar membrane electrodialysis device when electric conductivity value drops to 5 μ S/cm.In sour chamber, obtain the about 1.2L of sulfuric acid that concentration is about 1.1mol/L; Be used for the regeneration of next batch cation exchange column.Obtain the about 1.06L of potassium hydroxide solution of 1.3mol/L in the alkali chamber; Be used for the desorb of the cation exchange column of next batch absorption threonine.
Embodiment 10
Step 1: remove inorganic salts
The common electrical dialyzer is the common electrical dialyzer of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of amberplex is 210mm * 62mm, uses JAM-10 type anion-exchange membrane and JCM-1 type cation-exchange membrane.Anion-exchange membrane, cation-exchange membrane form 5 pairs of two compartment film stacking structure (as shown in Figure 4) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made minus plate.Dividing plate and filter are polypropylene material, and dividing plate is without the loop dividing plate, and filter is the mesh grid type.
The threonine crystal mother liquor 2.5L that contains 18.8g/L sodium sulphate, 70g/L threonine of Ningxia, China Yi Pin biotech inc is passed into light chamber; The initial liquid in dense chamber is the dilute sulfuric acid sodium solution of 0.5L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.6mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 0.7L of metabisulfite solution that concentration is about 0.42mol/L.The threonine crystal mother liquor 2.12L that takes off inorganic salts that obtains in light chamber records pH and is about 5.6, contains threonine 72g/L.
The metabisulfite solution 0.7L that the concentration that dense chamber is obtained is about 0.42mol/L passes into the salt chamber of three Room bipolar membrane electrodialysis devices (with the bipolar membrane electrodialysis device of embodiment 1), the initial liquid in acid chamber is that the 0.6L threonine is except fermented liquid (wherein containing threonine 115g/L), the initial liquid in alkali chamber is the sodium hydroxide solution of 0.6L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.Operating condition stops electrodialysis operation with the operating condition of embodiment 1 bipolar membrane electrodialysis device when electric conductivity value drops to 3 μ S/cm.In sour chamber, obtain the about 0.71L of sulfuric acid that concentration is about 0.44mol/L.Obtain the sodium hydroxide solution 0.62L that concentration is about 0.87mol/L in the alkali chamber.
The acidated threonine that the sulfur acid that obtains in the sour chamber is about 0.44mol/L is used for the isoelectric point crystallization of the 1L threonine fermentation liquid (containing the about 119g/L of threonine) of another batch except fermented liquid, consume acidated threonine except the about 0.3L of fermented liquid, gained threonine crystal and traditional isoelectric point crystallization do not have marked difference.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and the D152 weak-acid cation-exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 2.0L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 2 column volumes/hour.That collects about 2.16L at the bottom of the post sees through liquid from handing over, and its threonine content 1.3g/L, pH are 4.6, the about 20g/L of residual sugar.
The sodium hydroxide solution of the about 2.0mol/L of 1.0L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 174g/L of threonine free the about 0.72L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The sulfuric acid solution of the about 1.0mol/L of 1.7L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 126g/L of contains sodium sulfate at the bottom of post sees through the about 1.4L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 11
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 3.6L that will contain 14.5g/L sodium chloride, 68g/L threonine passes into light chamber; The initial liquid in dense chamber is the dilute sodium chloride solution of 1.0L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.4mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 1.22L of sodium chloride solution that concentration is about 0.64mol/L.The threonine crystal mother liquor 3.2L that takes off inorganic salts that obtains in light chamber records pH and is about 4.6, contains threonine 69g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, 001 * Final 8 acid cation exchange resin that in-built 1.2L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.92L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 2.06L at the bottom of the post sees through liquid from handing over, and its threonine content 1.2g/L, pH are 3.31, the about 19.8g/L of residual sugar.
The sodium hydroxide solution of the about 2.0mol/L of 1.0L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 171g/L of threonine free the about 0.72L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The hydrochloric acid of the about 1.6mol/L of 1.8L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.The regeneration of collecting the about 89g/L of sodium chloride-containing at the bottom of post sees through the about 1.58L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 12
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 2.8L that will contain 21g/L sodium nitrate, 87g/L threonine passes into light chamber; The initial liquid in dense chamber is rare sodium nitrate solution of 0.4L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.6mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 0.69L of sodium nitrate that concentration is about 0.89mol/L.The threonine crystal mother liquor 2.32L that takes off inorganic salts that obtains in light chamber records pH and is about 5.3, contains threonine 90g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 700mm, the D113 weak-acid cation-exchange resin that in-built 1.6L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces, the resin pattern is Hydrogen.
The threonine crystal mother liquor 2.3L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 2.4L at the bottom of the post sees through liquid from handing over, and its threonine content 1.4g/L, pH are 4.4, the about 21.6g/L of residual sugar.
The sodium hydroxide solution of the about 1.6mol/L of 1.8L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 162g/L of threonine free the about 1.15L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
Last batch of nitric acid that the regeneration of cation exchange column is seen through the about 1.0mol/L of 3.6L that the sour chamber of liquid regenerated acid and alkali obtains with bipolar membrane electrodialysis is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.Collect the regeneration that contains the about 72g/L of sodium nitrate and see through the about 2.7L of liquid at the bottom of post, ion exchange column is regenerated as Hydrogen.Effect and the dilution of commodity red fuming nitric acid (RFNA) obtain rare nitric acid does not have marked difference.
Embodiment 13
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 3.0L that will contain 17g/L ammonium sulfate, 82g/L threonine passes into light chamber; The initial liquid in dense chamber is the dilute ammonium sulfate solution of 1.5L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.7mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 1.8L of ammonium sulfate that concentration is about 0.25mol/L.The threonine crystal mother liquor 2.4L that takes off inorganic salts that obtains in light chamber records pH and is about 5.3, contains threonine 82g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and the D113 weak-acid cation-exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.96L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1.5 column volumes/hour.That collects about 2.04L at the bottom of the post sees through liquid from handing over, and its threonine content 1.1g/L, pH are 4.5, the about 21.8g/L of residual sugar.
The ammonia spirit of the about 1.8mol/L of 1.8L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 164g/L of threonine free the about 0.88L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The sulfuric acid of the about 1.2mol/L of 1.8L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.The regeneration of collecting the about 155g/L of liquid containing ammonium sulfate at the bottom of post sees through the about 1.66L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 14
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 2.2L that will contain 13g/L ammonium chloride, 87g/L threonine passes into light chamber; The initial liquid in dense chamber is rare ammonium chloride solution of 0.6L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.5mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 0.82L of ammonium chloride solution that concentration is about 0.70mol/L.The threonine crystal mother liquor 1.8L that takes off inorganic salts that obtains in light chamber records pH and is about 4.7, contains threonine 86g/L.
The ammonium chloride solution 0.82L that the concentration that dense chamber is obtained is about 0.70mol/L passes into the salt chamber of three Room bipolar membrane electrodialysis devices (with the bipolar membrane electrodialysis device of embodiment 1), the initial liquid in acid chamber is the dilute hydrochloric acid solution of 0.6L, 0.05mol/L, the initial liquid in alkali chamber is the sodium hydroxide solution of 0.6L 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.Operating condition stops electrodialysis operation with the operating condition of embodiment 1 bipolar membrane electrodialysis device when electric conductivity value drops to 2 μ S/cm.Pass into air in the material cylinder of alkali chamber, with the ammonia Air blowing of regeneration, air-blowing quantity is 1L/min.In sour chamber, obtain the about 0.71L of hydrochloric acid that concentration is about 0.81mol/L.The ammonia that blows out from the alkali chamber absorbs with 0.2L water another container, obtains the ammoniacal liquor of mass concentration about 4%.
The hydrochloric acid that obtains in the sour chamber is concentrated 4 times, be used for the isoelectric point crystallization of the 1L threonine fermentation liquid (containing the about 106g/L of threonine) of another batch, consume the about 0.025L of hydrochloric acid, gained threonine crystal and traditional isoelectric point crystallization do not have marked difference.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produce 001 * 7 storng-acid cation exchange resin, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.8L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1.5 column volumes/hour.That collects about 1.86L at the bottom of the post sees through liquid from handing over, and its threonine content 0.6g/L, pH are 3.8, the about 20.8g/L of residual sugar.
The ammonia spirit of the about 1.6mol/L of 1.2L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 143g/L of threonine free the about 0.96L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The hydrochloric acid of the about 1.0mol/L of 2.8L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1.6 column volumes/hour.The regeneration of collecting the about 48g/L of containing ammonium chloride at the bottom of post sees through the about 2.0L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 15
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 2.9L that will contain 19g/L sodium nitrate, 87g/L threonine passes into light chamber; The initial liquid in dense chamber is rare ammonium nitrate solution of 0.4L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.8mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 0.60L of ammonium nitrate that concentration is about 1.02mol/L.The threonine crystal mother liquor 2.41L that takes off inorganic salts that obtains in light chamber records pH and is about 4.5, contains threonine 89g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and the D61 storng-acid cation exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.76L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 1.89L at the bottom of the post sees through liquid from handing over, and its threonine content 0.8g/L, pH are 3.9, the about 20.2g/L of residual sugar.
The ammonia spirit of the about 2.0mol/L of 1.1L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 164g/L of threonine free the about 0.86L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The nitric acid of the about 1.0mol/L of 2.8L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1.8 column volumes/hour.Collect the regeneration that contains the about 71.2g/L of ammonium nitrate and see through the about 1.66L of liquid at the bottom of post, ion exchange column is regenerated as Hydrogen.
Embodiment 16
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 2.7L that will contain 21g/L potassium sulfate, 77g/L threonine passes into light chamber; The initial liquid in dense chamber is the dilute sulfuric acid potassium solution of 0.6L, 0.025mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.9mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 0.81L of sulfuric acid that concentration is about 0.40mol/L.The threonine crystal mother liquor 2.3L that takes off inorganic salts that obtains in light chamber records pH and is about 5.9, contains threonine 76g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and the D152 weak-acid cation-exchange resin that becomes Science and Technology Ltd., the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.88L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 1.91L at the bottom of the post sees through liquid from handing over, and its threonine content 1.2g/L, pH are 4.26, the about 21.2g/L of residual sugar.
Last batch of potassium hydroxide solution that the regeneration of cation exchange column is seen through the about 2.0mol/L of 1.4L that the alkali chamber of liquid regenerated acid and alkali obtains with bipolar membrane electrodialysis passed into to adsorb to be had in the cationic ion exchange column of threonine, flow be 1.8 column volumes/hour.Collect at the bottom of the post contain the about 175g/L of threonine free the about 0.73L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.The potassium hydroxide solution of effect and the preparation of commodity potassium hydroxide does not have marked difference.
The sulfuric acid of the about 1.0mol/L of 1.8L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 155g/L of sulfur acid potassium at the bottom of post sees through the about 1.22L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 17
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 3.3L that will contain 17g/L potassium chloride, 66g/L threonine passes into light chamber; The initial liquid in dense chamber is rare Klorvess Liquid of 1.0L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.7mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 1.32L of potassium chloride that concentration is about 0.53mol/L.The threonine crystal mother liquor 2.8L that takes off inorganic salts that obtains in light chamber records pH and is about 4.1, contains threonine 68g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 400mm, 001 * Final 8 acid cation exchange resin that in-built 0.9L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.4L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1.5 column volumes/hour.That collects about 1.46L at the bottom of the post sees through liquid from handing over, and its threonine content 1.3g/L, pH are 3.41, the about 23.3g/L of residual sugar.
The potassium hydroxide solution of the about 1.0mol/L of 2.0L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1.8 column volumes/hour.Collect at the bottom of the post contain the about 84g/L of threonine free the about 1.08L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The hydrochloric acid of the about 1.5mol/L of 1.44L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 85g/L of chloride containing potassium at the bottom of post sees through the about 1.30L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 18
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
The threonine crystal mother liquor 2.8L that will contain 24g/L potassium nitrate, 90g/L threonine passes into light chamber; The initial liquid in dense chamber is rare potassium nitrate solution of 0.4L, 0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.9mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 0.56L of nitric acid that concentration is about 1.12mol/L.The threonine crystal mother liquor 2.41L that takes off inorganic salts that obtains in light chamber records pH and is about 4.46, contains threonine 91g/L.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and 001 * 7 storng-acid cation exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.88L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1.5 column volumes/hour.That collects about 1.96L at the bottom of the post sees through liquid from handing over, and its threonine content 1.3g/L, pH are 3.43, the about 22.3g/L of residual sugar.
The potassium hydroxide solution of the about 1.5mol/L of 2.0L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 108g/L of threonine free the about 1.29L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The nitric acid of the about 1.0mol/L of 2.9L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.Collect the regeneration that contains the about 71.1g/L of potassium nitrate and see through the about 2.12L of liquid at the bottom of post, ion exchange column is regenerated as Hydrogen.
Embodiment 19
Except insoluble matter removes albumen: the threonine crystal mother liquor that contains 19.2g/L sodium sulphate, 70g/L threonine that will obtain filters through 0.2 μ m micro-filtration membrane and the 6K hyperfiltration membrane assembly of film sky film engineering Co., Ltd, obtains the threonine crystal mother liquor clear liquid 2.8L of the about 69g/L of threonine concentration.
Decalcification magnesium ion: add the oxalic acid of 0.025mol/L in the threonine crystal mother liquor clear liquid that obtains, mix rear room temperature and placed 4 hours, remove by filter precipitation.Remove the rear calcium ions and magnesium ions concentration of measuring threonine crystal mother liquor clear liquid of precipitation and be down to 60mg/L.
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
Warp just obtained above passes into the salt chamber except the threonine crystal mother liquor 2.5L that insoluble matter removes albumen and decalcification magnesium; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 0.5L, 0.05mol/L, and the initial liquid in alkali chamber is the sodium hydroxide solution of 0.5L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.9mS/cm, stop electrodialysis operation.In sour chamber, obtain the about 0.8L of sulfuric acid that concentration is about 0.35mol/L.Obtain the about 0.53L of NaOH that concentration is about 1.16mol/L in the alkali chamber.The threonine crystal mother liquor 1.97L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.28, contains threonine 71g/L.The energy loss-rate embodiment 1 of bipolar membrane electrodialysis regeneration unit mass sodium sulphate reduces by 20%.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and 001 * 7 storng-acid cation exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.81L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 2 column volumes/hour.That collects about 1.88L at the bottom of the post sees through liquid from handing over, and its threonine content 1.1g/L, pH are 3.04, the about 20.2g/L of residual sugar.
The sodium hydroxide solution of the about 2.0mol/L of 0.8L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 172g/L of threonine free the about 0.67L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The sulfuric acid solution of the about 1.0mol/L of 0.9L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 129g/L of contains sodium sulfate at the bottom of post sees through the about 0.68L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 20
Except insoluble matter removes albumen: the threonine crystal mother liquor that contains 13.6g/L ammonium chloride, 86g/L threonine that will obtain filters through 0.2 μ m micro-filtration membrane and the 3K hyperfiltration membrane assembly of film sky film engineering Co., Ltd, obtains the threonine crystal mother liquor clear liquid 3.0L of the about 86g/L of threonine concentration.
The decalcification magnesium ion: with the threonine crystal mother liquor clear liquid that obtains by being filled with 1.5L(resin floor height 1000mm * internal diameter 45mm) ion exchange column of H type D072 cationic ion-exchange resin, make calcium ions and magnesium ions in the threonine crystal mother liquor clear liquid by the H+ exchange adsorption.The upper prop flow be 2 column volumes/hour, at the bottom of post, collect the threonine crystal mother liquor clear liquid that about 3.2L contains the 84mg/L calcium ions and magnesium ions, measuring pH is 4.6.
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
Above-mentioned warp is passed into the salt chamber except the threonine crystal mother liquor 2.3L that insoluble matter removes albumen and decalcification magnesium; The initial liquid in acid chamber is the dilute hydrochloric acid solution of 0.6L, 0.05mol/L, and the initial liquid in alkali chamber is the sodium hydroxide solution of 0.6L, 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.5mS/cm, stop electrodialysis operation.Pass into air in the material cylinder of alkali chamber, with the ammonia Air blowing of regeneration, air-blowing quantity is 1L/min.In sour chamber, obtain the about 0.78L of hydrochloric acid that concentration is about 0.71mol/L.The ammonia that blows out from the alkali chamber absorbs with 0.2L water another container, obtains the ammoniacal liquor of mass concentration about 4.1%.The threonine crystal mother liquor 1.94L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.28, contains threonine 86g/L.The energy loss-rate embodiment 5 of bipolar membrane electrodialysis regeneration unit mass ammonium chloride reduces by 22%.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produce 001 * 7 storng-acid cation exchange resin, the resin pattern is Hydrogen.
The threonine crystal mother liquor 1.8L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 2 column volumes/hour.That collects about 1.86L at the bottom of the post sees through liquid from handing over, and its threonine content 1.2g/L, pH are 3.12, the about 24.6g/L of residual sugar.
The ammonia spirit of the about 2.0mol/L of 1.1L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 180g/L of threonine free the about 0.76L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The hydrochloric acid of the about 1.0mol/L of 2.8L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 50g/L of containing ammonium chloride at the bottom of post sees through the about 2.1L of liquid, and ion exchange column is regenerated as Hydrogen.
Embodiment 21
Except insoluble matter except albumen: the threonine crystal mother liquor that contains 18.8g/L sodium sulphate, 75g/L threonine of Ningxia, China Yi Pin biotech inc 0.2 μ m micro-filtration membrane and the 10K hyperfiltration membrane assembly through film sky film engineering Co., Ltd filtered, obtains the threonine crystal mother liquor clear liquid 2.8L of the about 74g/L of threonine concentration.
The decalcification magnesium ion: with the threonine crystal mother liquor clear liquid that obtains by being filled with 0.75L(resin floor height 500mm * internal diameter 45mm) exchange column of H type D402 chelating resin, make the exchanged absorption of calcium ions and magnesium ions in the threonine crystal mother liquor clear liquid.The upper prop flow be 1 column volume/hour, at the bottom of post, collect the threonine crystal mother liquor clear liquid that about 2.9L contains the 65mg/L calcium ions and magnesium ions, measuring pH is 4.8.
Dilution threonine crystal mother liquor: above-mentioned threonine crystal mother liquor except the insoluble matter removing calcium and magnesium is diluted 2 times with desalted water.
Step 1: remove inorganic salts
The common electrical dialyzer is with embodiment 10.
Above-mentioned threonine crystal mother liquor 5.1L except the insoluble matter removing calcium and magnesium is passed into light chamber; The initial liquid in dense chamber is the dilute sulfuric acid sodium solution of 0.5L0.05mol/L; Chamber, the two poles of the earth liquid is the metabisulfite solution of 1.0L, 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 0.6mS/cm, stop electrodialysis operation.In dense chamber, obtain the about 0.71L of metabisulfite solution that concentration is about 0.41mol/L.The threonine crystal mother liquor 4.6L that takes off inorganic salts that obtains in light chamber records pH and is about 5.8, contains threonine 36g/L.The energy loss-rate embodiment 10 that the common electrical dialysis removes unit mass sodium sulphate reduces by 22%.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 600mm, in-built 1.2L Nankai and the D152 weak-acid cation-exchange resin that becomes Science and Technology Ltd. to produce, the resin pattern is Hydrogen.
The threonine crystal mother liquor 4.0L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1.8 column volumes/hour.That collects about 4.26L at the bottom of the post sees through liquid from handing over, and its threonine content 0.5g/L, pH are 4.9, the about 10g/L of residual sugar.
The sodium hydroxide solution of the about 2.0mol/L of 1.0L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 2 column volumes/hour.Collect at the bottom of the post contain the about 175g/L of threonine free the about 0.71L of liquid, the threonine that obtains free liquid clarification, transparent, slightly yellow.
The sulfuric acid solution of the about 1.0mol/L of 1.7L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 2 column volumes/hour.The regeneration of collecting the about 126g/L of contains sodium sulfate at the bottom of post sees through the about 1.41L of liquid, and ion exchange column is regenerated as Hydrogen.
Culture yeasts: the yeast that uses is saccharomyces cidri (Saccharomyces cerevisiae, the As2.374 of China common micro-organisms DSMZ), candida utili (Candida utilis, As2.281) and candida tropicalis (Candida tropicalis, As 2.637).
The seed culture medium of three primary yeasts all is the YPD culture medium: glucose sugar 20g/L, peptone 10g/L, dusty yeast 10g/L, potassium dihydrogen phosphate 2g/L, ammonium sulfate 5g/L, magnesium sulfate 0.1g/L.Transferring Medium's PH Value with NaOH is about 6.Three primary yeast seeds are accessed respectively seed culture medium, and 300 rev/mins of shaking speed were cultivated 24 hours for 28 ℃, obtained the kind liquid of three primary yeasts.
Step 6) is adsorbed seeing through the about 1200mL of liquid and pack in the 2L fermentation tank from handing over behind the threonine, without sterilization.Access above-mentioned three all liquid by 5% inoculum concentration respectively.Cultivation temperature is controlled at 28 ± 0.5 ℃, and 180 rev/mins of speeds of agitator were cultivated 16 hours, and dry cell weight reaches 15g/L.
Embodiment 22
Dilution threonine crystal mother liquor: the threonine crystal mother liquor that contains 15g/L sodium chloride, 70g/L threonine that will obtain uses the recirculated water of processing through anaerobic-aerobic to dilute 2 times.
Except insoluble matter except albumen: the threonine crystal mother liquor that contains 7.5g/L sodium chloride, 35g/L threonine of above-mentioned dilution 0.2 μ m micro-filtration membrane and the 10K hyperfiltration membrane assembly through film sky film engineering Co., Ltd filtered, obtains the threonine crystal mother liquor clear liquid 8.0L of the about 34g/L of threonine concentration.
Decalcification magnesium ion: add the oxalic acid of 0.02mol/L in the threonine crystal mother liquor clear liquid that obtains, mix rear room temperature and placed 4 hours, remove by filter precipitation.Remove the rear calcium ions and magnesium ions concentration of measuring threonine crystal mother liquor clear liquid of precipitation and be down to 60mg/L.
Decolouring: add the 3%(mass ratio in the threonine crystal mother liquor clear liquid that removes calcium ions and magnesium ions that obtains) activated carbon powder, remain on 50 ℃ of decolourings 2 hours after mixing, remove by filter activated carbon powder, the absorbance of measuring threonine crystal mother liquor clear liquid after the decolouring is down to original 32%.
Step 1: remove inorganic salts
The bipolar membrane electrodialysis device is with embodiment 1.
Pass into salt chamber through dilution, except insoluble matter except the threonine crystal mother liquor 7.2L of albumen, decalcification magnesium and decolouring with above-mentioned; Acid chamber initial liquid be the 1.0L threonine except fermented liquid (wherein containing threonine 110g/L), the initial liquid in alkali chamber is the sodium hydroxide solution of 1.0L, 0.05mol/L, chamber, the two poles of the earth liquid is 1.0, the metabisulfite solution of 0.25mol/L.
Control current density 30mA/cm in the operating process 2, liquid flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 1mS/cm, stop electrodialysis operation.In sour chamber, obtain the acidated threonine of the hydrochloric 0.62mol/L of being about except the about 1.26L of fermented liquid.Obtain the about 1.12L of NaOH that concentration is about 0.66mol/L in the alkali chamber.The threonine crystal mother liquor 6.6L that takes off inorganic salts that obtains in the salt chamber records pH and is about 3.62, contains threonine 35g/L.The energy loss-rate embodiment 2 of bipolar membrane electrodialysis regeneration unit mass sodium chloride reduces by 34%.
Step 2: reclaim threonine with cation exchange
Ion-exchange column internal diameter 60mm, high 800mm, 001 * Final 8 acid cation exchange resin that in-built 1.8L Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produces, the resin pattern is Hydrogen.
The threonine crystal mother liquor 5.6L that takes off inorganic salts that the salt chamber of step 1 is obtained passes in the above-mentioned Hydrogen cation exchange column, flow be 1 column volume/hour.That collects about 5.7L at the bottom of the post sees through liquid from handing over, and its threonine content 1.5g/L, pH are 3.51, the about 11.4g/L of residual sugar.
The sodium hydroxide solution of the about 2.0mol/L of 1.4L is passed into absorption to be had in the cationic ion exchange column of threonine, flow be 1 column volume/hour.Collect at the bottom of the post contain the about 172g/L of threonine free the about 1.06L of liquid, the threonine that obtains free liquid clarification, transparent.
The hydrochloric acid solution of the about 1.6mol/L of 2.4L is passed in the cation exchange column that above-mentioned wash-out finishes, flow be 1 column volume/hour.The regeneration of collecting the about 88g/L of sodium chloride-containing at the bottom of post sees through the about 1.8L of liquid, and ion exchange column is regenerated as Hydrogen.
Culture yeasts: the yeast that uses is saccharomyces cidri (Saccharomyces cerevisiae, the As2.374 of China common micro-organisms DSMZ), candida utili (Candida utilis, As2.281) and candida tropicalis (Candida tropicalis, As 2.637).
The seed culture medium of three primary yeasts all is the YPD culture medium: glucose sugar 20g/L, peptone 10g/L, dusty yeast 10g/L, potassium dihydrogen phosphate 2g/L, ammonium sulfate 5g/L, magnesium sulfate 0.1g/L.Transferring Medium's PH Value with NaOH is about 6.Three primary yeast seeds are accessed respectively seed culture medium, and 300 rev/mins of shaking speed were cultivated 24 hours for 28 ℃, obtained the kind liquid of three primary yeasts.
Step 5) is adsorbed seeing through the about 1000mL of liquid and pack in the 2L fermentation tank from handing over behind the threonine, without sterilization.Access above-mentioned three all liquid by 5% inoculum concentration respectively.Cultivation temperature is controlled at 28 ± 0.5 ℃, and 180 rev/mins of speeds of agitator were cultivated 12 hours, and dry cell weight reaches 12g/L.

Claims (11)

1. method that reclaims threonine from the threonine crystal mother liquor may further comprise the steps:
1) adopts bipolar membrane electrodialysis technology or common electrical osmotic technique from the threonine crystal mother liquor, inorganic salts to be removed, obtain taking off the threonine crystal mother liquor of inorganic salts; Wherein, described bipolar membrane electrodialysis technology is " acid-salt-alkali " three Room bipolar membrane electrodialysis technology;
2) from the threonine crystal mother liquor that takes off inorganic salts, reclaim threonine with base exchange method.
2. method according to claim 1 is characterized in that, the inorganic salts that described step 1) removes adopt the corresponding acid solution of bipolar membrane electrodialysis regeneration and alkali lye.
3. method according to claim 2 is characterized in that, described acid solution can be used for the acid adjustment of threonine isoelectric point crystallization step; The pH that described alkali lye can be used for the Threonine Fermentation process regulates.
4. method according to claim 1 is characterized in that, to step 2) regeneration that obtains sees through liquid and adopts the bipolar membrane electrodialysis method to carry out acid-alkali regeneration, obtains acid solution and alkali lye.
5. method according to claim 4 is characterized in that, it is ammonium chloride, ammonium sulfate, ammonium nitrate, sodium chloride, sodium sulphate, sodium nitrate, potassium chloride, potassium sulfate or potassium nitrate solution that described regeneration sees through liquid.
6. method according to claim 4 is characterized in that, described acid solution can be used for cation exchange column regeneration in the base exchange method; Described alkali lye can be used for from base exchange method wash-out threonine on the cation exchange column.
7. method according to claim 1 is characterized in that, also is included in to carry out cation exchange and reclaim after the threonine, uses the further treatment step 2 of barms) ion-exchange that obtains sees through liquid, carries out the step of recycling treatment.
8. method according to claim 1 is characterized in that, also is included in to carry out before the step 1), and the threonine crystal mother liquor is removed insoluble matter and except the step of albumen.
9. method according to claim 1 is characterized in that, also is included in to carry out the threonine crystal mother liquor being purified the step of decalcification magnesium before the step 1).
10. method according to claim 1 is characterized in that, also is included in to carry out before the step 1) step that the threonine crystal mother liquor is decoloured.
11. method according to claim 1 is characterized in that, also is included in to carry out before the step 1) step that the threonine crystal mother liquor is diluted.
CN2012101445658A 2012-05-10 2012-05-10 Method for recovering threonine from threonine crystallization mother liquor Pending CN103071389A (en)

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Publication number Priority date Publication date Assignee Title
CN103964989A (en) * 2014-01-27 2014-08-06 重庆紫光化工股份有限公司 System for continuously separating and purifying amino acid from water solution of amino acid containing alkaline metal salt
CN103990382A (en) * 2014-05-13 2014-08-20 浙江赛特膜技术有限公司 Method for separating methoxamine from distillation liquid by using electrodialysis
CN103990382B (en) * 2014-05-13 2020-01-07 浙江赛特膜技术有限公司 Method for separating and extracting methoxyamine in distillate by using electrodialysis
CN104058844A (en) * 2014-06-09 2014-09-24 李学春 Method for preparing multielement chelate fertilizer by use of threonine mother liquor
CN104058844B (en) * 2014-06-09 2016-04-20 李学春 Threonine mother liquor is utilized to prepare the method for multicomponent chelate thing fertilizer
US11161746B2 (en) * 2015-10-30 2021-11-02 China Petroleum & Chemical Corporation Preparation of molecular sieve and treatment of silicon-containing wastewater therefrom
CN107721033A (en) * 2016-08-10 2018-02-23 通用电气公司 The system and method for handling salt solution
CN110272061A (en) * 2018-03-14 2019-09-24 国家能源投资集团有限责任公司 A kind of salt extraction process
CN110272061B (en) * 2018-03-14 2022-03-22 国家能源投资集团有限责任公司 Salt production method
CN110694479A (en) * 2019-10-31 2020-01-17 山东益丰生化环保股份有限公司 Purification method of cyanamide solution

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