CN102125252B

CN102125252B - Multilevel processing method for regenerating acid base from glutamic acid isoelectric mother liquor

Info

Publication number: CN102125252B
Application number: CN2010100341366A
Authority: CN
Inventors: 丛威; 王倩; 杨鹏波; 石绍渊; 吴霞
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2010-01-18
Filing date: 2010-01-18
Publication date: 2013-10-16
Anticipated expiration: 2030-01-18
Also published as: CN102125252A

Abstract

The invention relates to a multilevel processing method for regenerating acid base from glutamic acid isoelectric mother liquor. In the method, a multilevel bipolar membrane electroosmosis method is adopted; the flow direction of salt room liquid and acid room liquid in a bipolar membrane electrodialyzer is changed; and regenerating ammonium sulfate, ammonium chloride or ammonium nitrate in the glutamic acid isoelectric mother liquor comprising the ammonium sulfate, the ammonium chloride or the ammonium nitrate into corresponding sulfuric acid, hydrochloric acid or nitric acid and ammonia (NH3). By the multilevel processing method, concentration difference of inorganic acid radical ions between the acid room and the salt room is totally reduced; the migration rate of the inorganic acid radical is increased by 29 percent; migration energy consumption is reduced by 24 percent; H<+> leakage from the acid room to the salt room is remitted; and concentration of acid liquor recovered by theacid room is increased.

Description

A kind of multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid

Technical field

The invention belongs to the monosodium glutamate industry, particularly a kind of in glutamate production from the multistage treatment method of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid.

Background technology

Monosodium glutamate, formal name used at school monosodium glutamate (Monosodium Glutamate is referred to as MSG).Monosodium glutamate is a kind of important foodstuff additive, can enrich and improve the local flavor of food, is widely used in food and food-processing industry.China is glutamate production big country, and annual production is near 2,000,000 tons.Monosodium glutamate is refining by the L-glutamic acid of fermented extracted (claiming bran acid).

China mainly produces L-glutamic acid with amylofermentation, constantly adds during the fermentation ammonia and keeps the pH of fermented liquid and maintain about 7.After the fermentation ends, adopt the isoelectric point crystallization step to extract L-glutamic acid, the pH that namely regulates fermented liquid with the vitriol oil makes glutamic acid crystallization (being called for short " waiting electricity ") to the iso-electric point of L-glutamic acid.The glutamic acid crystal of telling forms monosodium glutamate through refining (dissolving, neutralization, decolouring, crystallization), also contain the sulfate radical of 15～20g/L L-glutamic acid, 30～40 grams per liters and the ammonium root of 10～15 grams per liters in the remaining supernatant liquor of glutamic acid crystal and isolate, pH is about 3.0, is called " waiting electric mother liquor ".

Present industrial production adopts cationic exchange to extract remaining L-glutamic acid usually from wait electric mother liquor.Concrete grammar is with the pH value to 1.8 of the electric mother liquors such as vitriol oil adjusting～2.0 (being called acidifying), the electric mother liquor that waits after the acidifying enters cationic exchange coloum (Hydrogen) with L-glutamic acid exchange adsorption upper prop, see through liquid and be the sulfate radical that contains 40～50 grams per liters and 15～20 grams per liters the ammonium root from handing over waste liquid.With this cationic exchange coloum of ammoniacal liquor wash-out, what obtain containing L-glutamic acid frees liquid (this strand material is commonly referred to " high flow point "), this is freed liquid return the isoelectric point crystallization step.

Above-mentioned Production Flow Chart is called " isoelectric point crystallization-ion-exchange " technique, is called for short " wait electricity-from handing over " technique, as shown in Figure 1.In " wait electricity-from hand over " technique, wait remaining L-glutamic acid in the electric mother liquor although extracted, cost is to consume more sulfuric acid and ammonia, causes 1 ton of L-glutamic acid of every production will consume the about 900kg of sulfuric acid (100%), the about 400kg of consumption liquefied ammonia.The sulfuric acid that consume and ammonia enter L-glutamic acid from handing over waste liquid, so that L-glutamic acid is difficult to administer from handing over waste liquid to contain than the more substantial sulfate radical of the electric mother liquors such as L-glutamic acid and ammonium root more at last.

For this reason, existing part glutamate production enterprise adopts " concentrate-waiting electricity " technique, namely adds the step of concentrated broth before the isoelectric point crystallization step, as shown in Figure 2.The isoelectric point crystallization step is separated the electric mother liquor that waits that obtains behind the glutamic acid crystal and is contained the ammonium root of the sulfate radical of 100 grams per liters of having an appointment, about 35～40 grams per liters and the L-glutamic acid of about 30 grams per liters, and pH 2～3.Usually, the electric mother liquor such as grade that this " concentrate-waiting electricity " technique obtains no longer extracts L-glutamic acid wherein, but directly concentrates composite fertilizer processed after will waiting the electric mother liquor separating thallus.In " concentrate-waiting electricity " technique, 1 ton of L-glutamic acid of every production consumes the about 400kg of sulfuric acid (100%), consumes the about 300kg of liquefied ammonia.

No matter be " wait electricity-from handing over " technique obtain from handing over waste liquid, the electric mother liquor such as grade that the technique that still " concentrate-waits electricity " obtains all contains sulfate radical and the ammonium of high density, can run into problems with existing treatment process.For example, during with bio anaerobic and aerobic treatment, suppressed by the high-concentration sulfuric acid ammonium; Ammonium sulfate itself is hard degradation also; When being used for culturing yeast, suppressed by the high-concentration sulfuric acid ammonium, the growth velocity of yeast is low; And it is concentrated when producing ammonium sulfate composite fertilizer or crystalline sulfuric acid ammonium, energy consumption is excessive, causes secondary pollution.

Document 1:Separation and Purification Technology has disclosed a kind of employing bipolar membrane electrodialysis technology and ammonium sulfate has been regenerated as corresponding sulfuric acid and NH from the electric mother liquors such as L-glutamic acid among 2007,55, the 274-280 ₃Method.Yet, in the process of this use bipolar membrane electrodialysis device regenerated acid and alkali, when the sulfuric acid concentration of regenerating is higher, have H ⁺Stride across the anion-exchange membrane seepage from sour chamber and enter the salt chamber, " leakage hydrogen " causes current efficiency reduction, the energy consumption of bipolar membrane electrodialysis device to increase; In addition, in the later stage of reaction, the sulfate concentration of sour chamber higher also can be so that sulfate radical be moved into from the salt chamber energy consumption of sour chamber increase because sulfate radical need to overcome higher concentration gradient.

Summary of the invention

The object of the invention is to overcome the defective that has now in the method for processing the electric mother liquors such as L-glutamic acid, thereby a kind of multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid that can reduce energy consumption is provided.Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention passes through to reduce inorganic acid radical in the concentration difference of anion-exchange membrane both sides, thus energy consumption when reducing the contrary concentration gradient migration of inorganic acid radical.

The present invention also aims to provide a kind of and can alleviate the leakage hydrogen problem that in bipolar membrane electrodialysis, occurs, thus the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of raising current efficiency.

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention is by adopting multistage bipolar membrane electrodialysis process, change simultaneously the flow direction of salt chamber liquid and sour chamber liquid in the bipolar membrane electrodialysis device, from the electric mother liquors such as L-glutamic acid that contain ammonium sulfate, ammonium chloride or ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium nitrate are regenerated as corresponding sulfuric acid, hydrochloric acid or nitric acid, and NH ₃

Among the present invention, described progression is more than or equal to secondary, preferred secondary or three grades.

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention can adopt three Room bipolar membrane electrodialysis devices (as shown in Figure 6) or " acid-salt " two Room bipolar membrane electrodialysis devices (as shown in Figure 7) to carry out, comprise: inject the electric mother liquors such as L-glutamic acid the 1st grade salt chamber, in the end the initial liquid in sour chamber is injected in the sour chamber of level; In at different levels, liquid is finished as the initial liquid in sour chamber of the corresponding levels in the sour chamber of later one-level, finishes liquid as the initial liquid in salt chamber of the corresponding levels with the salt chamber of previous stage; The final in the end salt chamber of level obtains taking off the electric mother liquor that waits of inorganic salt, obtains containing the feed liquid of sulfuric acid, hydrochloric acid or the nitric acid of regeneration the 1st grade sour chamber, and the ammonia that obtains regenerating.

With now technology compare, multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid provided by the invention has reduced the concentration difference of the inorganic acid radical ion between sour chamber and salt chamber generally, make the inorganic acid radical travelling speed improve 29%, thus Energy Intensity Reduction 24% during with the contrary concentration gradient migration of inorganic acid radical.In addition, the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid provided by the invention has also been alleviated sour chamber to the H of salt chamber ⁺Seepage has improved the concentration that acid solution is reclaimed in sour chamber, has improved current efficiency.

Description of drawings

Fig. 1 is the existing electricity-produce the L-glutamic acid process flow diagram from intergrowth of waiting;

Fig. 2 is that the existing electricity that concentrate-waits is produced the L-glutamic acid process flow diagram;

Fig. 3 is the synoptic diagram from electric mother liquor regenerated acid and alkali techniques such as L-glutamic acid according to an embodiment of the present invention;

Fig. 4 is that the film stacking structure in " acid-salt-alkali " three Room bipolar membrane electrodialysis devices is arranged synoptic diagram;

Fig. 5 is that film stacking structure is arranged synoptic diagram in " acid-salt " two Room bipolar membrane electrodialysis devices;

Fig. 6 is the synoptic diagram (the feed liquid cross-flow of alkali chamber) from the multistage treatment method of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid that the present invention adopts that three Room bipolar membrane electrodialysis devices carry out;

Fig. 7 is the synoptic diagram from the multistage treatment method of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid that the present invention adopts that " acid-salt " two Room bipolar membrane electrodialysis devices carry out;

Fig. 8 is the synoptic diagram (alkali chamber feed liquid adverse current) from the multistage treatment method of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid that the present invention adopts that three Room bipolar membrane electrodialysis devices carry out;

Wherein:

A anion-exchange membrane C cationic exchange membrane BM Bipolar Membrane

Sour chambers 10, salt chambers 20

Utmost point chambers 40, alkali chambers 30

M ⁺The positively charged ion X of salt ^-The acid radical anion of salt.

Embodiment

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention can adopt three Room bipolar membrane electrodialysis devices (as shown in Figure 6) or " acid-salt " two Room bipolar membrane electrodialysis devices (as shown in Figure 7) to carry out, comprise: inject the electric mother liquors such as L-glutamic acid the 1st grade salt chamber, in the end the initial liquid in sour chamber is injected in the sour chamber of level (N level); In at different levels, liquid is finished as the initial liquid in sour chamber of the corresponding levels in the sour chamber of later one-level, finishes liquid as the initial liquid in salt chamber of the corresponding levels with the salt chamber of previous stage; The final in the end salt chamber of level obtains taking off the electric mother liquor that waits of inorganic salt, obtains containing the feed liquid of sulfuric acid, hydrochloric acid or the nitric acid of regeneration the 1st grade sour chamber, and the ammonia that obtains regenerating.

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention carries out with the bipolar membrane electrodialysis process more than or equal to secondary, preferred secondary or three grades.

Take from the second-stage treatment method of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid as example, it is for being secondary with three Room bipolar membrane electrodialysis or two Room bipolar membrane electrodialysis Process Decompositions, inject the electric mother liquors such as L-glutamic acid the 1st grade salt chamber, inject the initial liquid in sour chamber the 2nd grade sour chamber; Finish liquid as the 1st grade the initial liquid in sour chamber with the 2nd grade sour chamber, finish liquid as the 2nd grade the initial liquid in salt chamber with the 1st grade salt chamber; The final electric mother liquor that waits that obtains taking off inorganic salt the 2nd grade salt chamber obtains containing the feed liquid of sulfuric acid, hydrochloric acid or the nitric acid of regeneration the 1st grade sour chamber, and the ammonia that obtains regenerating.

Take from the tertiary treatment method of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid as example, it is for being three grades with three Room bipolar membrane electrodialysis or two Room bipolar membrane electrodialysis Process Decompositions, inject the electric mother liquors such as L-glutamic acid the 1st grade salt chamber, inject the initial liquid in sour chamber in the sour chamber of 3rd level; Finish liquid respectively as the initial liquid in sour chamber of the 2nd grade and the 1st grade with the sour chamber of 3rd level and the 2nd grade, finish liquid respectively as the initial liquid in salt chamber of 3rd level and the 2nd grade with the salt chamber of the 2nd grade and the 1st grade; The final electric mother liquor that waits that obtains taking off inorganic salt in the salt chamber of 3rd level obtains containing the feed liquid of sulfuric acid, hydrochloric acid or the nitric acid of regeneration the 1st grade sour chamber, and the ammonia that obtains regenerating.

In this method, the concentration of ammonium sulfate, ammonium chloride or ammonium nitrate descends step by step the salt chamber feed liquid from the 1st grade to 3rd level; The concentration of sulfate radical, chlorion or nitrate radical descends step by step the sour chamber feed liquid from the 1st grade to 3rd level.The flow direction of salt chamber and sour chamber feed liquid is opposite, and the inorganic acid radical concentration of salt chamber and sour chamber is all higher in the 1st grade, and inorganic acid radical concentration is all lower in the 3rd level, the H of sour chamber ⁺The inorganic acid radical relative concentration of concentration and sour chamber should.

In the 1st grade, will contain NH ₄ ⁺The electric mother liquors such as L-glutamic acid of vitriol, hydrochloride or nitrate pass into the salt chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices; Acid passes into the sour chamber of three Room bipolar membrane electrodialysis devices in the 2nd grade or " acid-salt " two Room bipolar membrane electrodialysis devices in the chamber and finishes liquid, as the 1st grade the initial liquid in sour chamber.Open the bipolar membrane electrodialysis device electric mother liquors such as L-glutamic acid that pass into the salt chamber are processed, until the sulfate radical, chlorion or the nitrate concentration that enter in the electric mother liquors such as L-glutamic acid of salt chamber are reduced to needed concentration.

In the 2nd grade, the salt chamber that liquid passes into three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices of the 2nd grade is finished in the 1st grade salt chamber; Acid passes into the sour chamber of three Room bipolar membrane electrodialysis devices in the 3rd level or " acid-salt " two Room bipolar membrane electrodialysis devices in the chamber and finishes liquid, as the 2nd grade the initial liquid in sour chamber.Open the bipolar membrane electrodialysis device electric mother liquors such as L-glutamic acid that pass into the salt chamber are processed, until the sulfate radical, chlorion or the nitrate concentration that enter in the electric mother liquors such as L-glutamic acid of salt chamber are reduced to needed concentration.

In the 3rd level, the salt chamber that liquid passes into three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices of 3rd level is finished in the 2nd grade salt chamber; Can pass into water, diluted acid (sulfuric acid, hydrochloric acid or nitric acid) as the initial liquid in sour chamber of 3rd level according to ordinary method in the acid chamber; Open the bipolar membrane electrodialysis device electric mother liquors such as L-glutamic acid that pass into the salt chamber are processed, until the sulfate radical, chlorion or the nitrate concentration that enter in the electric mother liquors such as L-glutamic acid of salt chamber are reduced to needed concentration, finish the processing to electric mother liquors such as L-glutamic acid.

To " acid-salt-alkali " three Room bipolar membrane electrodialysis devices, with alkali chamber at different levels according to ordinary method water, the weak ammonia initial liquid as the alkali chamber, finally obtain ammoniacal liquor from alkali chamber at different levels, perhaps, with NaOH solution, KOH solution or other strongly basic medium initial liquid as the alkali chamber, the ammonia that generates in the alkali chamber blown out with air or other rare gas element obtain ammonia, alkali chamber feed liquid is not at each inter-stage flow (such as Fig. 6); To " acid-salt " two Room bipolar membrane electrodialysis devices, the ammonia that generates in the salt chamber blown out with air or other rare gas element obtain ammonia (such as Fig. 7).The ammonia that blows out can further obtain liquefied ammonia with conventional condensation method liquefaction, or the water absorption obtains ammoniacal liquor.In the end three Room bipolar membrane electrodialysis devices of level or the salt chamber of " acid-salt " two Room bipolar membrane electrodialysis devices obtain taking off inorganic salt etc. electric mother liquor.Obtain containing the feed liquid (liquid is finished in sour chamber) of sulfuric acid, hydrochloric acid or the nitric acid of regeneration in the sour chamber of the 1st grade three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices.

In embodiments of the present invention, when carrying out bipolar membrane electrodialysis, the feed liquid (replace ordinary method adopt water and diluted acid) that employing contains L-glutamic acid is as the initial liquid in sour chamber of the bipolar membrane electrodialysis device of rear class, the final feed liquid (liquid is finished in sour chamber) that obtains containing sulfuric acid, hydrochloric acid or the nitric acid of L-glutamic acid and regeneration the 1st grade sour chamber.The described feed liquid that contains L-glutamic acid comprises: the dialyzate of the filtered liquid of glutami acid fermentation liquor, glutami acid fermentation liquor (seeing through liquid with what glutami acid fermentation liquor obtained after with method filtration sterilizations such as membrane filtrations), filtering fermentation liquor is (with glutami acid fermentation liquor 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 the liquid Glutamic Acid of filtration, need to add water in the side of holding back of film, continue to filter, the liquid that sees through of this moment is called dialyzate) or their diluent; Or adopt in traditional " wait electricity-from handing over " technique the liquid of freeing that contains L-glutamic acid that obtains when handing over step wash-out L-glutamic acid.

To " acid-salt-alkali " three Room bipolar membrane electrodialysis devices, can also be in the end the alkali chamber injected water, weak ammonia of level as the initial liquid (such as Fig. 8) of the alkali chamber of rear class, liquid (ammoniacal liquor) is finished as the initial liquid in alkali chamber of previous stage in the alkali chamber of alkali at different levels chamber.Still to divide three grades as example: 3rd level can be according to ordinary method water, weak ammonia as the initial liquid in alkali chamber, the alkali chamber of 3rd level is finished liquid and is passed into the 2nd grade alkali chamber as the 2nd grade the initial liquid in alkali chamber, the 2nd grade alkali chamber is finished liquid and is passed into the 1st grade alkali chamber as the 1st grade the initial liquid in alkali chamber, finally obtains ammoniacal liquor the 1st grade alkali chamber.

In the present invention, described " until the sulfate radical, chlorion or the nitrate concentration that enter in the electric mother liquors such as L-glutamic acid of salt chamber are reduced to needed concentration " refers to " slough sulfate radical, chlorion or nitrate radical total amount in the electric mother liquors such as L-glutamic acid that are equivalent to enter the 1st grade of salt chamber 20～60% " in the salt chamber of every one-level.For the salt chamber of three Room bipolar membrane electrodialysis devices of final in the end level or " acid-salt " two Room bipolar membrane electrodialysis devices obtain take off inorganic salt etc. the concentration of sulfate radical, chlorion or the nitrate radical in the electric mother liquor, for industrial application, yes, and pursuit is as far as possible low, preferably be reduced to below 10% or 5% of sulfate radical, chlorion or nitrate concentration in the electric mother liquors such as L-glutamic acid that enter the 1st grade of salt chamber, this is only relevant with cost keeping, and this concentration is fallen to such an extent that lower inevitable required power consumption is just larger.Can monitor by some existing methods the concentration of sulfate radical, chlorion or nitrate radical, for example, can electricity be led with measuring, the method for electric current is come the ionic concn in the indirect measurement solution, perhaps setting-up time rule of thumb.

Process at Fig. 6, Fig. 7 or multistage bipolar membrane electrodialysis device shown in Figure 8 in the electric mother liquor flow process initial start-up such as L-glutamic acid, calculate in advance the salt concn of the initial liquid of acid concentration and last step salt chamber of the 1st grade of initial liquid in sour chamber according to the above-mentioned desalination amounts of bearing at different levels, and manually prepare the 1st grade the initial liquid in sour chamber and the initial liquid in salt chamber of last step; For flow process shown in Figure 8, calculate in advance alkali (ammonia) concentration of the 1st grade of initial liquid in alkali chamber according to the above-mentioned desalination amounts of bearing at different levels, and manually prepare the 1st grade the initial liquid in alkali chamber.After the first bipolar membrane electrodialysis device of the 1st grade and last step is finished dealing with, salt chamber that liquid passes into next stage is finished as initial liquid in the 1st grade the salt chamber that obtains, sour chamber that liquid passes into previous stage is finished as initial liquid in the sour chamber of the last step that obtains; Liquid is finished in the alkali chamber of the last step that obtains pass into the alkali chamber of previous stage as initial liquid.The rest may be inferred, until at different levelsly all finish first bipolar membrane electrodialysis device and process, finishes the startup of flow process.After this, process again and again the electric mother liquors such as L-glutamic acid with multistage bipolar membrane electrodialysis device according to Fig. 6, Fig. 7 or flow process shown in Figure 8.

In embodiments of the present invention, finish in the liquid the sour chamber that obtains in sour chamber, and the concentration of the sulfuric acid of regeneration is 0.15～2.0mol/L; The concentration of the hydrochloric acid of regeneration is 0.3～4mol/L; The concentration of the nitric acid of regeneration is 0.3～4mol/L.Liquid is finished in this acid chamber can be directly or the isoelectric point crystallization step through being used for after concentrated adopting after fermentation ends, makes glutamic acid crystallization with the pH of the electric stostes such as adjusting.

In embodiments of the present invention, the ammoniacal liquor that obtains in the alkali chamber of three Room bipolar membrane electrodialysis devices at different levels, blow the ammonia that ammonia obtains from the alkali chamber of three Room bipolar membrane electrodialysis devices at different levels or the salt chamber of " acid-salt " at different levels two Room bipolar membrane electrodialysis devices, and the ammonia that blows out absorbed the ammoniacal liquor that obtains with liquefied ammonia or the water that condensation method liquefaction obtains, regulate the pH of fermented liquid when can be used for fermentative production L-glutamic acid, and/or the described ammoniacal liquor L-glutamic acid that can be used for waiting the wash-out from the cationic exchange coloum of electricity-when handing over step to adsorb.Use described ammonia when (containing ammonia gas) can through or pass into fermentor tank behind the storage tank and regulate pH.

In embodiments of the present invention, it is described that to blow ammonia operation be the pH value of regulating the salt chamber of the alkali chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices with increase or the way that reduces air flow, that is: when being higher than the pH value of setting, the pH value of the salt chamber of the alkali chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices increases air flow, when the pH value of the salt chamber of the alkali chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices is lower than the pH value of setting, reduce air flow, thereby keep the pH of the salt chamber of the alkali chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices.It is certain numerical value more than 9 that the pH value of the salt chamber of the alkali chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices maintains pH.Adopt conventional pH control device.

In the technical scheme of the present invention, described bipolar membrane electrodialysis can carry out in " acid-salt-alkali " three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices.Fig. 4 shows the synoptic diagram that the film stacking structure in " acid-salt-alkali " three Room bipolar membrane electrodialysis devices is arranged, comprise two utmost point chambers 40, and some groups of acid chambers 10, salt chamber 20 and alkali chambers 30 being clipped in wherein and being separated by anion-exchange membrane A, cationic exchange membrane C and Bipolar Membrane BM.Fig. 5 shows film stacking structure arrangement synoptic diagram in " acid-salt " two Room bipolar membrane electrodialysis devices, comprise two utmost point chambers 40, with some groups of acid chambers 10 that are clipped in wherein and separated by anion-exchange membrane A and Bipolar Membrane BM and salt chamber 20, this salt chamber is equivalent to " salt-alkali " two Room among Fig. 4 are merged.

Bipolar membrane electrodialysis device among the present invention can adopt conventional working method, and for example, constant current, constant voltage or transformation or unsteady flow mode operate the bipolar membrane electrodialysis device.Under electric field action, the water molecules in the Bipolar Membrane is dissociated into H ⁺And OH ^-, migration enters sour chamber and alkali chamber, the positively charged ion M of salt respectively ⁺With negatively charged ion X ^-(X ^-Be acid group) respectively migration enter alkali chamber and sour chamber.Then obtain sour HX in sour chamber, obtain alkali MOH in the alkali chamber.In the present invention, pending feed liquid contains NH ₄ ⁺And SO ₄ ^2-, then obtain H in sour chamber ₂SO ₄, obtain NH in the alkali chamber ₃

In the bipolar membrane electrodialysis device of the present invention, the feed liquid in the utmost point chamber is conventional industrial bipolar membrane electrodialysis device feed liquid, for example aqueous solution of the sodium sulfate of 0.1～0.5mol/L or other indifferent electrolyte; 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 the bipolar membrane electrodialysis device of the present invention, the temperature of feed liquid that comprises each chamber of sour chamber, alkali chamber, salt chamber, utmost point chamber adopts the temperature of conventional electrodialysis operation, usually is no more than 5～50 ℃ scope; The flow velocity of each 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.

In embodiments of the present invention, for three Room bipolar membrane electrodialysis devices, the original volume of acid chamber and alkali chamber feed liquid and the volume ratio of salt chamber are as the criterion with the cycles of concentration that reaches predetermined bronsted lowry acids and bases bronsted lowry, and wherein the volume ratio of the initial feed liquid in alkali chamber and salt chamber feed liquid is 0.05～2: 1; For " acid-salt " two Room bipolar membrane electrodialysis devices, the original volume of sour chamber feed liquid and the volume ratio of salt chamber are as the criterion with the cycles of concentration that reaches predetermined acid.

Cationic exchange membrane, anion-exchange membrane and Bipolar Membrane in the bipolar membrane electrodialysis device among the present invention are the commercially available prod.

As the example of cationic exchange membrane for example: the NeosebtaCL-2.5T that day Bender mountain Cao Da company produces, Neosebta CLS-2.5T, the Aciplex CK-1 that Japan's Asahi Kasei Corporation is produced, AciplexCK-2, the Selemion CMV that Japan AGC company produces, Selemion CSV, the AMfion C-60 that U.S.'s machinery and manufacturing company (AMF) produce, AMfion C-300, the Ionac MC-3142 that American I onac chemical company produces, Ionac MC-3470, the NeptonCR61AZL183 that Ion America Inc. (Ionics) produces, Nepton CR61AZL065, the Fumasep FTCM that U.S. good fortune equine skill company (Fumatech) produces, Fumasep FKS, Fumasep FKB, Fumasep FKL, Fumasep FKE, the DS-01 that National Bureau of Oceanography two produces, DS-02, the QF-1 that former chemical plant, morning twilight chemical research institute sky produces, the KM that Ministry of Nuclear Industry Beijing five produces, the F that Chinese Academy of Sciences's Shanghai nuclear research is produced ₄₆1, F ₄₆3, F ₄₆5, NF-1, the global profit in Beijing reaches JCM-10, the JCM-15 that environmental protection equipment company limited produces, the ACM that dimension Filmtec Corp. in sky, Shandong produces, the CMB that Ministry of Nuclear Industry Beijing five produces, or the 3361BW of Shanghai Water-Treatment Material Co., Ltd., Shanghai's production.

As the example of anion-exchange membrane for example: the NeosebtaAV-4T that day Bender mountain Cao Da company produces, Neosebta AFS-4T, DFM, the Aciplex CA-1 that Japan's Asahi Kasei Corporation is produced, AciplexCA-3, the SelemionAMV that Japan AGC company produces, SelemionASV, DMV, the AMfion A-60 that U.S.'s machinery and manufacturing company (AMF) produce, AMfion A-300, the Ionac MA-3148 that American I onac chemical company produces, Ionac MA-3475, the NeptonAR111BZL183 that Ion America Inc. (Ionics) produces, NeptonAR111BZL065, the Fumasep FTAM that U.S. good fortune equine skill company (Fumatech) produces, Fumasep FAB, Fumasep FAA, Fumasep FAP, FumasepFAB-PK, Fumasep FAS, Fumasep FAD, the D that morning twilight chemical research institute produces ₁, D ₂, the F that the Shanghai nuclear research is produced ₄₆2, F ₄₆4, F ₄₆6, the EPA-1 that National Bureau of Oceanography two produces, the organic F201 that produces in Chinese Academy of Sciences Shanghai, the global profit in Beijing reaches JAM-10, the JAM-15 that environmental protection equipment company limited produces, the DF-120 that sky, Shandong dimension membrane technique company limited produces, ED9010, ED120, ED-100 that Zhejiang Qianqiu Environmental Water Treatment Co., Ltd. produces, the 3362BW that Shanghai Water-Treatment Material Co., Ltd., Shanghai produces, or the AMB that produces of Ministry of Nuclear Industry Beijing five.

As the example of Bipolar Membrane for example: the Fumasep FBM that the Neosebta BP-1 that day Bender mountain Cao Da company produces or U.S.'s good fortune equine skill are produced.

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention also can compriseBefore carrying out bipolar membrane electrodialysis, the electric mother liquors such as L-glutamic acid are carried out degerming and except the step of albumen.

Adopt conventional degerming means, such as means and combinations thereof such as organic membrane filtration, inorganic membrane filtration or press filtrations, necessary words can increase the operations such as flocculation, drainage, and the electric mother liquors such as L-glutamic acid are carried out degerming.

Adopting the conventional albumen ultrafiltration technology that removes, is the ultra-filtration membrane of 1K, 3K, 6K or 10K as adopting molecular weight cut-off, and the electric mother liquors such as L-glutamic acid are removed albumen.

Pollute because thalline and foreign protein can form films to the various films that use in the bipolar membrane electrodialysis, thus the present invention be about to first the electric mother liquor degerming such as L-glutamic acid, except albumen can prolong the bipolar membrane electrodialysis device operational cycle, reduce energy consumption.

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention also can compriseBefore carrying out bipolar membrane electrodialysis, the electric mother liquors such as L-glutamic acid are purified the step of decalcification magnesium.

The enforcement of the step of decalcification magnesium is to adopt conventional base exchange method, or the oxalate precipitation method.

Base exchange method of the present invention can adopt storng-acid cation exchange resin, weakly acidic cation-exchange resin and chelating ion exchange resin.

As the example of storng-acid cation exchange resin various commercially available storng-acid cation exchange resins for example, as: 001 * 1 of Chinese Chemical Plant of Nankai Univ. production, 001 * 2,001 * 3,001 * 4,001 * 7,002 * 7,003 * 7,004 * 7,001 * 8,001 * 7 * 7,001 * 14.5, D072, D061, D001-CC, NKC-9, D001SS, 001 * 4 of Jiangsu Province, China Su Qing engineering of water treatment Group Co.,Ltd production, 001 * 4H, 001 * 7,001 * 7H, 001 * 10,001 * 16, D001, the JK008 that China Langfang Bel's specialization worker building materials company limited produces, and Hangzhou China win honour for that resin company limited produces 001 * 7, D001.

As the example of weakly acidic cation-exchange resin various commercially available weakly acidic cation-exchange resins for example, as: Chinese Chemical Plant of Nankai Univ. produce 110, D151, D152, D113, DLT-1, Jiangsu Province, China Su Qing engineering of water treatment Group Co.,Ltd produce 112, D113-III.

As the example of chelating ion exchange resin various commercially available chelating ion exchange resins for example, as: D401, D418 that Chemical Plant of Nankai Univ. produces, D190, D401, D402, D403, D405, D406, D407 that Jiangsu Province, China Su Qing engineering of water treatment Group Co.,Ltd produces.

The storng-acid cation exchange resin D072 that preferred Chinese Chemical Plant of Nankai Univ. produces among the present invention, 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 add-on of oxalic acid is 1～5 times of the total moles that waits calcium magnesium in the electric 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 precipitin reaction is finished is the forms such as centrifugal, filtration.

Owing to wait the high-valence cationic (mainly being calcium, magnesium ion) in the electric mother liquor can move the alkali chamber that enters the bipolar membrane electrodialysis device, and form membrane contaminant at cationic exchange membrane and Bipolar Membrane, and film pollutes meeting increase resistance and energy consumption, increases the cleaning burden of bipolar membrane electrodialysis device.Therefore, the present invention carried out first the step of decalcification magnesium to electric mother liquors such as L-glutamic acid before the electric mother liquors such as L-glutamic acid are passed into the salt chamber, was conducive to improve the efficient of bipolar membrane electrodialysis device and reduced energy consumption.

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention also can compriseBefore carrying out bipolar membrane electrodialysis, the step that the electric mother liquors such as L-glutamic acid are concentrated.

Can adopt the conventional means such as evaporation, multiple-effect evaporation or membrane concentration, the electric mother liquors such as L-glutamic acid are concentrated into 1/6～1 of original volume.

The present invention will wait first the concentration of the acid of the concentrated ammonium sulfate concentrations that can improve the electric mother liquors such as L-glutamic acid of electric mother liquor and regeneration before the electric mother liquors such as L-glutamic acid are passed into the salt chamber, reduce on the whole the energy consumption of regenerated acid and alkali process.

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention is applicable to the isoelectric point crystallization technique with electric souring agents such as sulfuric acid, hydrochloric acid or nitric acid works.Described isoelectric point crystallization comprises the concentrated electric various crystallization processes such as electricity, the normal temperature etc. such as electricity, low temperature are electric, continuous that wait.

As required, the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention is optionally selected above-mentioned degerming and except albumen, decalcification magnesium, concentrated, wherein degerming and carry out before also can being placed on isoelectric point crystallization except the albumen step.In an embodiment of the invention, as shown in Figure 3, namely used successively degerming and except albumen, decalcification magnesium, the whole process such as concentrated.

Effect of the present invention

Multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid of the present invention is multistage with the bipolar membrane electrodialysis Process Decomposition, its benefit is: the concentration difference that has 1. reduced generally the inorganic acid radical ion between sour chamber and salt chamber, make the inorganic acid radical travelling speed improve 29%, migration Energy Intensity Reduction 24%.2. alleviated sour chamber to the H of salt chamber ⁺Seepage has improved the concentration that acid solution is reclaimed in sour chamber.

Embodiment 1

Be divided into three grades from the bipolar membrane electrodialysis process of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid, adopt three Room bipolar membrane electrodialysis devices of three platform independent operations, every as one-level, sees also Fig. 6.Every three Room bipolar membrane electrodialysis devices are identical, see also Fig. 4.Liquid flow path direction in the adjacent compartments adopts and is streamed.The area of ion-exchange membrane is 210mm * 62mm, uses BP-1 type Bipolar Membrane, JAM-10 type anion-exchange membrane and JCM-1 type cationic exchange membrane.Bipolar Membrane, anion-exchange membrane, cationic exchange membrane form 5 pairs of three compartment film stacking structure (such as Fig. 4) repeated arrangement.Every arranges pair of electrodes, uses titanium to be coated with ruthenium electrode and makes positive plate, and stainless steel electrode is made negative 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 salt chamber of the 1st grade of electrodialyzer passes into the electric mother liquor 5.4L such as L-glutamic acid that contain 42g/L ammonium sulfate, 18g/L L-glutamic acid of LiaoNing, China Shenyang red plum Gourmet Powder Factory, it is that liquid 1.1L is finished as initial liquid in the 2nd grade of electrodialysis acid chamber of 0.9mol/L that the acid chamber passes into sulfuric acid concentration, the alkali chamber pass into mass concentration be 0.5% ammoniacal liquor 0.3L as initial liquid, chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.Open the 1st grade of three Room bipolar membrane electrodialysis equipment, 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 18 μ S/cm, stop electrodialysis operation.In the sour chamber of the 1st grade of electrodialyzer, obtain the sour chamber that sulfuric acid concentration is about 1.47mol/L and finish about 1.15 liters of liquid, in the alkali chamber, obtain the ammoniacal liquor 0.3L of mass concentration about 7%.

The partially desalted electric mother liquors such as L-glutamic acid that contain 24g/L ammonium sulfate, 18g/L L-glutamic acid that obtain in the salt chamber with the 1st grade of electrodialyzer pass into the salt chamber of the 2nd grade of electrodialyzer as initial liquid, the initial liquid in sour chamber of the 2nd grade of electrodialyzer is that liquid 1.05L is finished in the sour chamber of the 3rd level electrodialyzer of sulfuric acid concentration 0.3mol/L, the alkali chamber pass into mass concentration be 0.5% ammoniacal liquor 0.3L as initial liquid, chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operational condition of the 2nd grade of electrodialyzer is identical with the 1st grade.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 9 μ S/cm, stop electrodialysis operation.In the 2nd grade sour chamber, obtain the sour chamber that sulfuric acid concentration is about 0.9mol/L and finish liquid 1.1L, its sour chamber that passes into the 1st grade of electrodialyzer as initial liquid, is obtained the ammoniacal liquor 0.3L of mass concentration about 7.3% in the alkali chamber.

The partially desalted electric mother liquors such as L-glutamic acid that contain 9g/L ammonium sulfate, 18g/L L-glutamic acid that obtain in the salt chamber with the 2nd grade of electrodialyzer pass into the salt chamber of 3rd level electrodialyzer as initial liquid, the initial liquid in sour chamber of 3rd level electrodialyzer is 1.0L 0.05mol/L dilution heat of sulfuric acid, the alkali chamber pass into mass concentration be 0.5% ammoniacal liquor 0.3L as initial liquid, chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operational condition of 3rd level electrodialyzer is identical with the 1st grade.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 4 μ S/cm, stop electrodialysis operation.In 3rd level acid chamber, obtain the sour chamber that sulfuric acid concentration is about 0.3mol/L and finish liquid 1.05L, with its sour chamber that passes into the 2nd grade of electrodialyzer as initial liquid.What obtain taking off ammonium sulfate in the 3rd level salt chamber waits after measured reducing sugar 4.5g/L of electric mother liquor, and the pH value is about 2.4, obtains the ammoniacal liquor 0.3L of mass concentration about 3.3% in the alkali chamber.

The energy consumption that three grade of three Room bipolar membrane electrodialysis removes ammonium sulfate in the electric mother liquors such as L-glutamic acid is 2.83kWh/kg, than under the same operation conditions during not classification energy consumption descend 24%, when reclaiming under the acid solution concentration ratio same operation conditions not classification, the acid chamber improves 9%, the electric mother liquor pH values such as L-glutamic acid of taking off ammonium sulfate that the salt chamber obtains are 2.4, and the pH value of the electric mother liquors such as L-glutamic acid that take off ammonium sulfate that obtain under the same operation conditions during not classification is 1.9.

Embodiment 2

Be divided into three grades from the bipolar membrane electrodialysis process of the electric mother liquor regenerated acid and alkalis such as L-glutamic acid, adopt three Room bipolar membrane electrodialysis devices of three platform independent operations, every as one-level, sees also Fig. 6.Three Room bipolar membrane electrodialysis devices are with embodiment 1.

Claims

1. multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid, it is for passing through to adopt multistage bipolar membrane electrodialysis process, change simultaneously the flow direction of salt chamber liquid and sour chamber liquid in the bipolar membrane electrodialysis device, from the electric mother liquors such as L-glutamic acid that contain ammonium sulfate, ammonium chloride or ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium nitrate are regenerated as corresponding sulfuric acid, hydrochloric acid or nitric acid, and NH ₃

Wherein, described multistage bipolar membrane electrodialysis process comprises: in three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices, inject the electric mother liquors such as L-glutamic acid the 1st grade salt chamber, in the end the initial liquid in sour chamber is injected in the sour chamber of level; In at different levels, liquid is finished as the initial liquid in sour chamber of the corresponding levels in the sour chamber of later one-level, finishes liquid as the initial liquid in salt chamber of the corresponding levels with the salt chamber of previous stage; The final in the end salt chamber of level obtains taking off the electric mother liquor that waits of inorganic salt, obtains containing the feed liquid of sulfuric acid, hydrochloric acid or the nitric acid of regeneration the 1st grade sour chamber, and the ammonia that obtains regenerating;

Wherein, pass into water, sulfuric acid, hydrochloric acid or nitric acid as the initial liquid in sour chamber of rear class according to ordinary method in the acid chamber, or adopt the feed liquid contain L-glutamic acid as the initial liquid in sour chamber of the bipolar membrane electrodialysis device of rear class, the final feed liquid that obtains containing sulfuric acid, hydrochloric acid or the nitric acid of L-glutamic acid and regeneration the 1st grade sour chamber;

Wherein, to three Room bipolar membrane electrodialysis devices, alkali chamber at different levels finally obtains ammoniacal liquor from alkali chamber at different levels according to ordinary method water, the weak ammonia initial liquid as the alkali chamber; Perhaps, use NaOH solution, KOH solution or other strongly basic medium as the initial liquid of alkali chamber, the ammonia that generates in the alkali chamber is blown out with air or other rare gas element obtain ammonia.

2. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1, it is characterized in that: described multistage bipolar membrane electrodialysis process is secondary or three grades of bipolar membrane electrodialysis process.

3. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1, it is characterized in that: the described feed liquid that contains L-glutamic acid is: the filtered liquid of glutami acid fermentation liquor, glutami acid fermentation liquor, the dialyzate of filtering fermentation liquor or their diluent; Or the liquid of freeing that contains L-glutamic acid that obtains during wash-out L-glutamic acid from the cationic exchange coloum with ammoniacal liquor.

4. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1, it is characterized in that: at three Room bipolar membrane electrodialysis devices, in the end the alkali chamber injected water, weak ammonia of level are finished liquid as the initial liquid in alkali chamber of previous stage as the initial liquid of the alkali chamber of rear class with the alkali chamber of alkali at different levels chamber.

5. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1 is characterized in that: sulfate radical, chlorion or the nitrate radical of sloughing in the salt chamber of every one-level is equivalent to enter 20～60% of sulfate radical, chlorion or nitrate radical total amount in the electric mother liquors such as L-glutamic acid of the 1st grade of salt chamber.

6. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1, it is characterized in that: finish in the liquid the sour chamber that obtains in sour chamber, and the concentration of the sulfuric acid of regeneration is 0.15～2.0mol/L; The concentration of the hydrochloric acid of regeneration is 0.3～4mol/L; The concentration of the nitric acid of regeneration is 0.3～4mol/L; Liquid is finished directly or the isoelectric point crystallization step through being used for after concentrated adopting in this acid chamber after fermentation ends, make glutamic acid crystallization with the pH of the electric stostes such as adjusting.

7. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1, it is characterized in that: the ammoniacal liquor that obtains in the alkali chamber of three Room bipolar membrane electrodialysis devices at different levels, blow the ammonia that ammonia obtains from the alkali chamber of three Room bipolar membrane electrodialysis devices at different levels or the salt chamber of " acid-salt " at different levels two Room bipolar membrane electrodialysis devices, and the ammonia that blows out absorbed the ammoniacal liquor that obtains with liquefied ammonia or the water that condensation method liquefaction obtains, regulate the pH of fermented liquid when being used to fermentative production L-glutamic acid, and/or the described ammoniacal liquor L-glutamic acid that can be used for waiting the wash-out from the cationic exchange coloum of electricity-when handing over step to adsorb; When using described ammonia through or pass into fermentor tank behind the storage tank and regulate pH.

8. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1 and 2 is characterized in that: also be included in and carry out before the bipolar membrane electrodialysis, the electric mother liquors such as L-glutamic acid are carried out degerming and except the step of albumen.

9. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1 and 2 is characterized in that: also be included in and carry out the electric mother liquors such as L-glutamic acid being purified the step of decalcification magnesium before the bipolar membrane electrodialysis.

10. the multistage treatment method from electric mother liquor regenerated acid and alkalis such as L-glutamic acid according to claim 1 and 2 is characterized in that: also be included in and carry out before the bipolar membrane electrodialysis, the step that the electric mother liquors such as L-glutamic acid are concentrated.