CN102125252A - Multilevel processing method for regenerating acid base from glutamic acid isoelectric mother liquor - Google Patents
Multilevel processing method for regenerating acid base from glutamic acid isoelectric mother liquor Download PDFInfo
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- CN102125252A CN102125252A CN2010100341366A CN201010034136A CN102125252A CN 102125252 A CN102125252 A CN 102125252A CN 2010100341366 A CN2010100341366 A CN 2010100341366A CN 201010034136 A CN201010034136 A CN 201010034136A CN 102125252 A CN102125252 A CN 102125252A
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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 235000013922 glutamic acid Nutrition 0.000 title claims abstract description 180
- 239000004220 glutamic acid Substances 0.000 title claims abstract description 180
- 239000002253 acid Substances 0.000 title claims abstract description 105
- 239000012452 mother liquor Substances 0.000 title claims abstract description 37
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 10
- 238000003672 processing method Methods 0.000 title abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 211
- 239000012528 membrane Substances 0.000 claims abstract description 154
- 150000003839 salts Chemical class 0.000 claims abstract description 129
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 83
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 27
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 27
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 22
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 12
- 238000000909 electrodialysis Methods 0.000 claims description 139
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- 230000008929 regeneration Effects 0.000 claims description 56
- 238000011069 regeneration method Methods 0.000 claims description 56
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- 241000370738 Chlorion Species 0.000 claims description 11
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- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 8
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 3
- 241000283073 Equus caballus Species 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 3
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- 229910001424 calcium ion Inorganic materials 0.000 description 3
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- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 2
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- 240000004808 Saccharomyces cerevisiae Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
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- FLNKWZNWHZDGRT-UHFFFAOYSA-N azane;dihydrochloride Chemical compound [NH4+].[NH4+].[Cl-].[Cl-] FLNKWZNWHZDGRT-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 1
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- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
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- 125000000291 glutamic acid group Chemical group N[C@@H](CCC(O)=O)C(=O)* 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
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 the acid room is increased.
Description
Technical field
The invention belongs to the monosodium glutamate industry, particularly a kind of in glutamate production from the multistep treatment method of electric mother liquors such as glutamic acid regeneration soda acid.
Background technology
Monosodium glutamate, formal name used at school monosodium glutamate (Monosodium Glutamate abbreviates MSG as).Monosodium glutamate is a kind of important food additives, can enrich and improve flavours in food products, 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 to be made with extra care by the glutamic acid (claiming bran acid) that fermentation is extracted.
China mainly produces glutamic acid with amylofermentation, constantly adds ammonia during the fermentation and keeps the pH of zymotic fluid and maintain about 7.After the fermentation ends, adopt the isoelectric point crystallization step to extract glutamic acid, promptly the pH that regulates zymotic fluid with the concentrated sulfuric acid makes glutamic acid crystallization (being called for short " grade ") to the isoelectric point of 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 glutamic acid, 30～40 grams per liters and the ammonium root of 10～15 grams per liters in the remaining supernatant of glutamic acid crystal and isolate, pH is about 3.0, is called " waiting electric mother liquor ".
Present industrial production adopts cation exchange to extract remaining glutamic acid usually from wait electric mother liquor.Concrete grammar is pH value to 1.8～2.0 (being called acidifying) with electric mother liquors such as concentrated sulfuric acid adjustings, the electric mother liquor that waits after the acidifying enters cation exchange column (Hydrogen) with glutamic acid exchange absorption 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 cation exchange column of ammoniacal liquor wash-out, what obtain containing 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 procedure is called " isoelectric point crystallization-ion-exchange " technology, is called for short " wait electricity-from handing over " technology, as shown in Figure 1.In " wait electricity-from hand over " technology, wait remaining glutamic acid in the electric mother liquor though extracted, cost is to consume sulfuric acid and ammonia more, causes 1 ton of glutamic acid of every production will consume the about 900kg of sulfuric acid (100%), the about 400kg of consumption liquefied ammonia.Sulfuric acid that consume and ammonia enter glutamic acid from handing over waste liquid at last, make glutamic acid from handing over waste liquid to contain than more substantial sulfate radical of electric mother liquors such as glutamic acid and ammonium root, are difficult to more administer.
For this reason, existing part glutamate production enterprise adopts " concentrate-waiting " technology, promptly 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 glutamic acid of about 30 grams per liters, and pH 2～3.Usually, the electric mother liquor that waits that should " concentrate-waiting " technology obtains no longer extracts wherein glutamic acid, makes composite fertilizer but will wait directly to concentrate behind the electric mother liquor separating thallus.In " concentrate-waiting " technology, 1 ton of 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 " technology obtain from handing over waste liquid, the still electric mother liquor such as grade that obtains of " concentrate-waiting " technology all contains the sulfate radical and the ammonium of high concentration, can run into problems with existing processing method.For example, during with bio anaerobic and Aerobic Process for Treatment, suppressed by the high-concentration sulfuric acid ammonium; Ammonium sulfate itself also is difficult to degraded; When being used for culture yeasts, suppressed by the high-concentration sulfuric acid ammonium, the growth rate 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, 2007,55, disclose a kind of employing bipolar membrane electrodialysis technology among the 274-280 and from electric mother liquors such as glutamic acid, ammonium sulfate has been regenerated as corresponding sulfuric acid and NH
3Method.Yet, in the process of this use bipolar membrane electrodialysis device regeneration soda acid, when the sulfuric acid concentration of regeneration 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 higher energy consumption increase that can make that also sulfate radical is moved into sour chamber from the salt chamber of the sulfate concentration of sour chamber is because sulfate radical need overcome higher concentration gradient.
Summary of the invention
The objective of the invention is to overcome the defective that has now in the method for handling electric mother liquors such as glutamic acid, thereby a kind of multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid that can cut down the consumption of energy is provided.Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention is by reducing the concentration difference of inorganic acid radical in the 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 multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of raising current efficiency.
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention is by adopting multistage bipolar membrane electrodialysis process, change the flow direction of salt chamber liquid and sour chamber liquid in the bipolar membrane electrodialysis device simultaneously, from the electric mother liquors such as 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.
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda 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 electric mother liquors such as glutamic acid the 1st grade salt chamber, in the end the initial liquid in sour chamber is injected in Ji sour chamber; In at different levels, the sour chamber initial liquid of liquid as the corresponding levels is finished in the sour chamber of later one-level, finishes the salt chamber initial liquid of liquid as the corresponding levels with the salt chamber of previous stage; The final salt chamber of level in the end obtains taking off the electric mother liquor that waits of inorganic salts, 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, multistep treatment method from electric mother liquors such as glutamic acid regeneration soda 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 migration velocity improve 29%, thereby energy consumption reduce by 24% during with the contrary concentration gradient migration of inorganic acid radical.In addition, the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid provided by the invention has also been alleviated the H of sour chamber to the 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 glutamic acid process flow diagram from intergrowth of waiting;
Fig. 2 produces the glutamic acid process flow diagram for the existing electricity that concentrate-waits;
Fig. 3 is the schematic diagram from electric mother liquors such as glutamic acid regeneration soda acid technology 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 schematic diagram;
Fig. 5 is that film stacking structure is arranged schematic diagram in " acid-salt " two Room bipolar membrane electrodialysis devices;
The schematic diagram (the feed liquid cross-flow of alkali chamber) that Fig. 6 adopts for the present invention that three Room bipolar membrane electrodialysis devices carry out from the multistep treatment method of electric mother liquors such as glutamic acid regeneration soda acid;
The schematic diagram that Fig. 7 adopts for the present invention that " acid-salt " two Room bipolar membrane electrodialysis devices carry out from the multistep treatment method of electric mother liquors such as glutamic acid regeneration soda acid;
The schematic diagram (alkali chamber feed liquid adverse current) that Fig. 8 adopts for the present invention that three Room bipolar membrane electrodialysis devices carry out from the multistep treatment method of electric mother liquors such as glutamic acid regeneration soda acid;
Wherein:
A anion-exchange membrane C cation-exchange membrane BM Bipolar Membrane
M
+The cation X of salt
-The acid radical anion of salt.
The specific embodiment
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention is by adopting multistage bipolar membrane electrodialysis process, change the flow direction of salt chamber liquid and sour chamber liquid in the bipolar membrane electrodialysis device simultaneously, from the electric mother liquors such as 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
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda 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 electric mother liquors such as 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, the sour chamber initial liquid of liquid as the corresponding levels is finished in the sour chamber of later one-level, finishes the salt chamber initial liquid of liquid as the corresponding levels with the salt chamber of previous stage; The final salt chamber of level in the end obtains taking off the electric mother liquor that waits of inorganic salts, 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.
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention is carried out with the bipolar membrane electrodialysis process more than or equal to secondary, preferred secondary or three grades.
With the two stage treatment method from electric mother liquors such as glutamic acid regeneration soda acid is example, it is for to be decomposed into secondary with three Room bipolar membrane electrodialysis or two Room bipolar membrane electrodialysis processes, inject electric mother liquors such as 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 salts 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.
With the tertiary treatment method from electric mother liquors such as glutamic acid regeneration soda acid is example, it is for to be decomposed into three grades with three Room bipolar membrane electrodialysis or two Room bipolar membrane electrodialysis processes, inject electric mother liquors such as 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 salts 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 the 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 anion 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
+Concentration is corresponding with the inorganic acid radical concentration of sour chamber.
In the 1st grade, will contain NH
4 +The electric mother liquors such as glutamic acid of sulfate, hydrochloride or nitrate feed the salt chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices; Liquid is finished in the sour chamber of three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices in feeding the 2nd grade in the acid chamber, as the 1st grade the initial liquid in sour chamber.Open the bipolar membrane electrodialysis device electric mother liquors such as glutamic acid that feed the salt chamber are handled, sulfate radical, chlorion or nitrate concentration in the electric mother liquors such as glutamic acid that enter the salt chamber are reduced to needed concentration.
In the 2nd grade, the salt chamber that liquid feeds 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; Liquid is finished in the sour chamber that feeds three Room bipolar membrane electrodialysis devices in the 3rd level or " acid-salt " two Room bipolar membrane electrodialysis devices in the acid chamber, as the 2nd grade the initial liquid in sour chamber.Open the bipolar membrane electrodialysis device electric mother liquors such as glutamic acid that feed the salt chamber are handled, sulfate radical, chlorion or nitrate concentration in the electric mother liquors such as glutamic acid that enter the salt chamber are reduced to needed concentration.
In the 3rd level, liquid is finished in the 2nd grade salt chamber feed three Room bipolar membrane electrodialysis devices of 3rd level or the salt chamber of " acid-salt " two Room bipolar membrane electrodialysis devices; Can feed water, diluted acid (sulfuric acid, hydrochloric acid or nitric acid) the initial liquid in sour chamber according to conventional method in the acid chamber as 3rd level; Open the bipolar membrane electrodialysis device electric mother liquors such as glutamic acid that feed the salt chamber are handled, sulfate radical, chlorion or nitrate concentration in the electric mother liquors such as glutamic acid that enter the salt chamber are reduced to needed concentration, finish the processing to electric mother liquors such as glutamic acid.
To " acid-salt-alkali " three Room bipolar membrane electrodialysis devices, with alkali chamber at different levels according to conventional method water, weak aqua 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 inert gas obtain ammonia, alkali chamber feed liquid is not at each inter-stage flow (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 inert gas obtain ammonia (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 the salt chamber of Ji three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices obtain taking off inorganic salts 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, employing contains the sour chamber initial liquid of the feed liquid (water and the diluted acid that replace conventional method to adopt) of glutamic acid as the bipolar membrane electrodialysis device of last level, the final feed liquid (liquid is finished in sour chamber) that obtains containing sulfuric acid, hydrochloric acid or the nitric acid of glutamic acid and regeneration the 1st grade sour chamber.The described feed liquid that contains glutamic acid comprises: the dislysate of the filtered fluid 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, thalline concentrates the membrane flux that filters the back and descends, simultaneously also in order to improve the yield that sees through glutamic acid in the liquid of filtration, need add water in the side of holding back of film, continue to filter, the liquid that sees through of this moment is called dislysate) or their dilution; Or adopt the liquid of freeing that contains glutamic acid that when handing over step wash-out glutamic acid, obtains in traditional " wait electricity-from handing over " technology.
To " acid-salt-alkali " three Room bipolar membrane electrodialysis devices, in the end the initial liquid (as Fig. 8) of the alkali chamber of water, the last level of weak aqua ammonia conduct is injected in the alkali chamber of level, and the alkali chamber initial liquid of liquid (ammoniacal liquor) as previous stage is finished in the alkali chamber of alkali at different levels chamber.Still to divide three grades to be example: 3rd level can be according to conventional method water, weak aqua ammonia as the initial liquid in alkali chamber, the alkali chamber of 3rd level is finished liquid and is fed 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 fed 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 " sulfate radical, chlorion or nitrate concentration in the electric mother liquors such as glutamic acid that enter the salt chamber are reduced to needed concentration " is meant " slough sulfate radical, chlorion or nitrate anion total amount in the electric mother liquors such as glutamic acid that are equivalent to enter the 1st grade of salt chamber 20～60% " in the salt chamber of each grade.For the salt chamber of three Room bipolar membrane electrodialysis devices of final level in the end or " acid-salt " two Room bipolar membrane electrodialysis devices obtain take off inorganic salts etc. the concentration of sulfate radical, chlorion or the nitrate anion in the electric mother liquor, for commercial Application, yes, and pursuit is low as far as possible, preferably be reduced to below 10% or 5% of sulfate radical, chlorion or nitrate concentration in the electric mother liquors such as glutamic acid that enter the 1st grade of salt chamber, this is only relevant with cost accounting, and this concentration is fallen to such an extent that low more inevitable required power consumption is just big more.Can monitor the concentration of sulfate radical, chlorion or nitrate anion by some existing methods, 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.
Handle 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 glutamic acid, calculate the salinity of the initial liquid of acid concentration and afterbody salt chamber of the 1st grade of initial liquid in sour chamber in advance 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 afterbody; For flow process shown in Figure 8, calculate alkali (ammonia) concentration of the 1st grade of initial liquid in alkali chamber in advance 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 afterbody is finished dealing with, salt chamber that liquid feeds next stage is finished as initial liquid in the 1st grade the salt chamber that obtains, sour chamber that liquid feeds previous stage is finished as initial liquid in the sour chamber of the afterbody that obtains; Alkali chamber that liquid feeds previous stage is finished as initial liquid in the alkali chamber of the afterbody that obtains.The rest may be inferred, all finishes first bipolar membrane electrodialysis device and handle up at different levels, finishes the startup of flow process.After this, handle electric mother liquors such as glutamic acid again and again 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 regenerated hydrochloric acid is 0.3～4mol/L; The concentration of the nitric acid of regeneration is 0.3～4mol/L.The isoelectric point crystallization step that liquid can be directly or adopted through being used for after fermentation ends after concentrating is finished in this acid chamber, makes glutamic acid crystallization with the pH of 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 zymotic fluid when can be used for fermenting and producing glutamic acid, and/or the described ammoniacal liquor glutamic acid that can be used for waiting the wash-out from the cation exchange column of electricity-when handing over step to adsorb.Use described ammonia when (containing ammonia gas) can through or feed fermentation 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 throughput, 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 throughput, 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 throughput, 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 schematic diagram that the film stacking structure in " acid-salt-alkali " three Room bipolar membrane electrodialysis devices is arranged, some groups of acid chambers 10, salt chamber 20 and alkali chambers 30 comprising two utmost point chambers 40 and be clipped in wherein and separated by anion-exchange membrane A, cation-exchange membrane C and Bipolar Membrane BM.Fig. 5 shows film stacking structure arrangement schematic 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 method of operating, and for example, constant current, constant voltage or transformation or unsteady flow mode are operated the bipolar membrane electrodialysis device.Under electric field action, the hydrone in the Bipolar Membrane is dissociated into H
+And OH
-, migration enters sour chamber and alkali chamber, the cation M of salt respectively
+With anion X
-(X
-Be acid group) respectively migration enter alkali chamber and sour chamber.Then obtain sour HX, obtain alkali MOH in the alkali chamber in sour 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 sulphate of 0.1～0.5mol/L or other indifferent electrolyte; The volume of utmost point chamber is conventional volume, can normal circulation get final product in membrane stack with utmost point chamber feed liquid usually.
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, is no more than 5～50 ℃ scope usually; The flow velocity of each chamber adopts conventional flow velocity, is no more than the scope of 0.1～10cm/s usually; Current density adopts conventional current density, is no more than 1～200mA/cm usually
2Scope.
In embodiments of the present invention, for three Room bipolar membrane electrodialysis devices, the initial 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 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 initial 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.
Cation-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 cation-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 company of Asahi Chemical Industry produces, 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 is produced, 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 is produced, 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 Co., Ltd produces, the ACM that dimension Filmtec Corp. in sky, Shandong produces, the CMB that Ministry of Nuclear Industry Beijing five is produced, 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 company of Asahi Chemical Industry produces, 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 is produced, 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 Co., Ltd produces, the DF-120 that sky, Shandong dimension membrane technology Co., Ltd 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 produced 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.
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention also can compriseBefore carrying out bipolar membrane electrodialysis, electric mother liquors such as glutamic acid are carried out degerming and remove the step of albumen.
Adopt conventional degerming means, as means and combinations thereof such as organic membrane filtration, inorganic membrane filtration or press filtrations, necessary words can increase flocculation, help operation such as filter, and electric mother liquors such as glutamic acid are carried out degerming.
Adopting the conventional albumen ultrafiltration technology that removes, is the milipore filter of 1K, 3K, 6K or 10K as adopting molecular cut off, and electric mother liquors such as 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 earlier electric mother liquor degerming such as glutamic acid, remove albumen can prolong the bipolar membrane electrodialysis device operation cycle, cut down the consumption of energy.
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention also can compriseBefore carrying out bipolar membrane electrodialysis, electric mother liquors such as 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, weak-acid cation-exchange resin and chelating ion exchange resin.
As for example various commercially available storng-acid cation exchange resins of the example of storng-acid cation exchange resin, 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 China Jiangsu 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 Co., Ltd produces, and Chinese Zhengguang Resin Co., Ltd. produce 001 * 7, D001.
As for example various commercially available weak-acid cation-exchange resins of the example of weak-acid cation-exchange resin, as: Chinese Chemical Plant of Nankai Univ. produce 110, D151, D152, D113, DLT-1, Chinese Jiangsu Su Qing engineering of water treatment Group Co.,Ltd produce 112, D113-III.
As for example various commercially available chelating ion exchange resins of the example of chelating ion exchange resin, as D401, the D418 that: Chemical Plant of Nankai Univ. produces, D190, D401, D402, D403, D405, D406, D407 that Chinese Jiangsu 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 that produces of Chinese Jiangsu Su Qing engineering of water treatment Group Co.,Ltd.
Oxalate precipitation method of the present invention, the concrete operations condition is as follows: the addition 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 precipitation reaction is finished is 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 on cation-exchange membrane and Bipolar Membrane, form membrane contaminant, and film pollutes meeting increase resistance and energy consumption, increases the cleaning burden of bipolar membrane electrodialysis device.Therefore, the present invention carried out the step of decalcification magnesium earlier to electric mother liquors such as glutamic acid before electric mother liquors such as glutamic acid are fed the salt chamber, helped improving the efficient of bipolar membrane electrodialysis device and cutting down the consumption of energy.
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention also can compriseBefore carrying out bipolar membrane electrodialysis, the step that electric mother liquors such as glutamic acid are concentrated.
Can adopt means such as conventional evaporation, multiple-effect evaporation or film concentrate, electric mother liquors such as glutamic acid are concentrated into 1/6～1 of original volume.
The concentration of the ammonium sulfate concentrations that the present invention will wait electric mother liquor to concentrate earlier before electric mother liquors such as glutamic acid are fed the salt chamber can to improve electric mother liquors such as glutamic acid and the acid of regeneration reduces the energy consumption of regeneration soda acid process on the whole.
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention is applicable to the isoelectric point crystallization technology with electric acidulants such as sulfuric acid, hydrochloric acid or nitric acid works.Described isoelectric point crystallization comprises electric various crystallization processes such as electricity, normal temperature etc. such as concentrate waiting electricity, low temperature are electric, continuous.
As required, the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention is optionally selected above-mentioned degerming for use and is removed albumen, decalcification magnesium, concentrates, wherein degerming and remove the albumen step and carry out before also can being placed on isoelectric point crystallization.In an embodiment of the invention, as shown in Figure 3, promptly used degerming successively and remove albumen, decalcification magnesium, overall process such as concentrate.
Effect of the present invention
Multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid of the present invention is decomposed into the bipolar membrane electrodialysis process multistage, its benefit is: the concentration difference that has 1. reduced the inorganic acid radical ion between sour chamber and salt chamber generally, make the inorganic acid radical migration velocity improve 29%, the migration energy consumption reduces by 24%.2. alleviated the H of sour chamber to the 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 electric mother liquors such as glutamic acid regeneration soda acid, adopt three Room bipolar membrane electrodialysis devices of three platform independent operation, every as one-level, sees also Fig. 6.Every three Room bipolar membrane electrodialysis device is identical, sees also Fig. 4.Liquid flow path direction in the adjacent compartments adopts and is 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 are formed 5 pairs of three compartment film stacking structure (as Fig. 4) repeated arrangement.Every is provided with pair of electrodes, uses titanium to be coated with ruthenium electrode and makes positive plate, and stainless steel electrode is made minus plate.Dividing plate and filter are polypropylene material, and dividing plate is a no loop dividing plate, and filter is the mesh grid type.
The salt chamber of the 1st grade of electric dialyzator feeds the electric mother liquor 5.4L such as glutamic acid that contain 42g/L ammonium sulfate, 18g/L glutamic acid of LiaoNing, China Shenyang red plum Gourmet Powder Factory, feeding sulfuric acid concentration in acid chamber is that liquid 1.1L is finished as initial liquid in the 2nd grade of electrodialysis acid chamber of 0.9mol/L, alkali chamber feeding mass concentration is 0.5% the initial liquid of ammoniacal liquor 0.3L conduct, and 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 electric dialyzator, 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 glutamic acid that contain 24g/L ammonium sulfate, 18g/L glutamic acid that obtain in the salt chamber with the 1st grade of electric dialyzator feed the salt chamber of the 2nd grade of electric dialyzator as initial liquid, the initial liquid in sour chamber of the 2nd grade of electric dialyzator is that liquid 1.05L is finished in the sour chamber of the 3rd level electric dialyzator of sulfuric acid concentration 0.3mol/L, alkali chamber feeding mass concentration is 0.5% the initial liquid of ammoniacal liquor 0.3L conduct, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of the 2nd grade of electric dialyzator 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 feeds the 1st grade of electric dialyzator 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 glutamic acid that contain 9g/L ammonium sulfate, 18g/L glutamic acid that obtain in the salt chamber with the 2nd grade of electric dialyzator feed the salt chamber of 3rd level electric dialyzator as initial liquid, the initial liquid in sour chamber of 3rd level electric dialyzator is 1.0L 0.05mol/L dilution heat of sulfuric acid, alkali chamber feeding mass concentration is 0.5% the initial liquid of ammoniacal liquor 0.3L conduct, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of 3rd level electric dialyzator 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 feeds the 2nd grade of electric dialyzator as initial liquid.What obtain taking off ammonium sulfate in the 3rd level salt chamber waits electric mother liquor reduced sugar 4.5g/L after measured, 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 glutamic acid is 2.83kWh/kg, than under the same operating condition during not classification energy consumption descend 24%, when reclaiming under the same operating condition of acid solution concentration ratio not classification, the acid chamber improves 9%, the electric mother liquor pH values such as 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 glutamic acid that take off ammonium sulfate that obtain under the same operating condition during not classification is 1.9.
Embodiment 2
Be divided into three grades from the bipolar membrane electrodialysis process of electric mother liquors such as glutamic acid regeneration soda acid, adopt three Room bipolar membrane electrodialysis devices of three platform independent operation, every as one-level, sees also Fig. 6.Three Room bipolar membrane electrodialysis devices are with embodiment 1.
See also Fig. 3.
Degerming, remove albumen: 0.2 μ m micro-filtration membrane and the 3K hyperfiltration membrane assembly of electric mother liquors such as glutamic acid through Tianjin MoTian Membrane Engineering Technology Co., Ltd filtered, obtain about 6 liters of clear liquid, contain 34g/L ammonium chloride, 17g/L glutamic acid.
The salt chamber of the 1st grade of electric dialyzator feeds the process degerming, removes the electric mother liquor 5.8L such as glutamic acid of albumen, liquid 1.1L is finished as initial liquid in the 2nd grade of electrodialysis acid chamber that it is 1.8mol/L that the acid chamber feeds concentration of hydrochloric acid, contain the about 18g/L of glutamic acid, the alkali chamber feeds 0.05mol/L sodium hydroxide solution 1.1L as initial liquid, and 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.Bubbling air in the material cylinder of alkali chamber blows out the ammonia of regenerating with air, air-blowing quantity is 1 liter/minute.The ammonia that blows out from the alkali chamber feeds and places-60 ℃ of stainless steel coiled pipes in the refrigerator, and the coiled pipe other end is collected liquefied ammonia with receiving flask.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.Obtain in the sour chamber of the 1st grade of electric dialyzator that concentration of hydrochloric acid is about 3.05mol/L, about 1.15 liters of liquid is finished in the sour chamber that contains the about 18g/L of glutamic acid.
The partially desalted electric mother liquors such as glutamic acid that contain 21g/L ammonium chloride, 17g/L glutamic acid that obtain in the salt chamber with the 1st grade of electric dialyzator feed the salt chamber of the 2nd grade of electric dialyzator as initial liquid, liquid 1.05L is finished in the sour chamber that the initial liquid in sour chamber of the 2nd grade of electric dialyzator is concentration of hydrochloric acid 0.6mol/L, contain the 3rd level electric dialyzator of the about 19g/L of glutamic acid, the initial liquid in alkali chamber is 1.05L 0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of the 2nd grade of electric dialyzator is identical with the 1st grade.Alkali chamber material cylinder aeration condition is identical with the 1st grade, and the ammonia that blows out from the alkali chamber feeds and places-60 ℃ of stainless steel coiled pipes in the refrigerator, and the coiled pipe other end reclaims liquefied ammonia with receiving flask.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.Obtain in the 2nd grade sour chamber that concentration of hydrochloric acid is about 1.8mol/L, liquid 1.1L is finished in the sour chamber that contains the about 18g/L of glutamic acid, with its sour chamber that feeds the 1st grade of electric dialyzator as initial liquid.
The partially desalted electric mother liquors such as glutamic acid that contain 8g/L ammonium chloride ammonium, 17g/L glutamic acid that obtain in the salt chamber with the 2nd grade of electric dialyzator feed the salt chamber of 3rd level electric dialyzator as initial liquid, the pH2.5 that the initial liquid in sour chamber of 3rd level electric dialyzator is 1.0L when having adsorbed the ion exchange column wash-out glutamic acid of glutamic acid, contain the preceding flow point of glutamic acid 20g/L, the initial liquid in alkali chamber is 1.1L 0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of the 2nd grade of electric dialyzator is identical with the 1st grade.Alkali chamber material cylinder aeration condition is identical with the 1st grade, and the ammonia that blows out from the alkali chamber feeds and places-60 ℃ of stainless steel coiled pipes in the refrigerator, and the coiled pipe other end reclaims liquefied ammonia with receiving flask.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 6 μ S/cm, stop electrodialysis operation.Obtain in 3rd level acid chamber that concentration of hydrochloric acid is about 0.6mol/L, liquid 1.05L is finished in the sour chamber that contains the about 19g/L of glutamic acid, with its sour chamber that feeds the 2nd grade of electric dialyzator as initial liquid.Obtain the electric mother liquors such as glutamic acid of dechlorination ammonium in the 3rd level electric dialyzator salt chamber, reduced sugar 4.4g/L after measured, the pH value is about 3.3.Liquefied ammonia 44g is reclaimed in the three-stage electrodialysis operation altogether.
The energy consumption that three grade of three Room bipolar membrane electrodialysis removes ammonium chloride in the electric mother liquors such as glutamic acid is 2.55kWh/kg, than under the same operating condition during not classification energy consumption descend 21%, when reclaiming under the same operating condition of acid solution concentration ratio not classification, the acid chamber improves 8%, the electric mother liquor pH values such as glutamic acid of the dechlorination ammonium that the salt chamber obtains are 3.3, and the pH value of the electric mother liquors such as glutamic acid of the dechlorination ammonium that obtains during not classification under the same operating condition is 2.5.
Embodiment 3
Be divided into three grades from the bipolar membrane electrodialysis process of electric mother liquors such as glutamic acid regeneration soda acid, adopt three Room bipolar membrane electrodialysis devices of three platform independent operation, every as one-level, sees also Fig. 8.The bipolar membrane electrodialysis device is with embodiment 1.
See also Fig. 3.
Degerming, remove albumen: 0.2 μ m micro-filtration membrane and the 10K hyperfiltration membrane assembly of electric mother liquors such as glutamic acid through Tianjin MoTian Membrane Engineering Technology Co., Ltd filtered, obtain about 6 liters of clear liquid, contain 51g/L ammonium nitrate, 19g/L glutamic acid.
Concentrate and wait electric mother liquor: the clear liquid heating of electric mother liquors such as above-mentioned glutamic acid is concentrated 2 times.
Decalcification magnesium ion: in above-mentioned concentrated clear liquid, add the oxalic acid of 0.05mol/L, mix the back room temperature and placed 4 hours, remove by filter precipitation.The calcium ions and magnesium ions concentration of removing electric mother liquors such as post precipitation mensuration is 65mg/L.
The salt chamber of the 1st grade of electric dialyzator feeds through degerming, removes albumen, concentrates, the electric mother liquor 2.2L such as glutamic acid of decalcification magnesium ion, liquid 1.05L is finished as initial liquid in the 2nd grade of electrodialysis acid chamber that to feed concentration of nitric acid in the acid chamber be 1.38mol/L, contain the about 37g/L of glutamic acid, the initial liquid in alkali chamber is that the ammoniacal liquor 0.5L that liquid is mass concentration 5.5% is finished in the 2nd grade of electric dialyzator alkali chamber, and 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 17 μ S/cm, stop electrodialysis operation.Obtain in the sour chamber of the 1st grade of electric dialyzator that concentration of nitric acid is about 2.42mol/L, about 1.08 liters of liquid is finished in the sour chamber that contains the about 36g/L of glutamic acid, in the alkali chamber, obtain the ammoniacal liquor 0.5L of mass concentration about 9%.
The partially desalted electric mother liquors such as glutamic acid that contain 29g/L ammonium nitrate, 19g/L glutamic acid that obtain in the salt chamber with the 1st grade of electric dialyzator feed the salt chamber of the 2nd grade of electric dialyzator as initial liquid, liquid 1.03L is finished in the sour chamber that the initial liquid in sour chamber of the 2nd grade of electric dialyzator is concentration of nitric acid 0.57mol/L, contain the 3rd level electric dialyzator of the about 38g/L of glutamic acid, the initial liquid in alkali chamber is that the ammoniacal liquor 0.5L that liquid is mass concentration 2.4% is finished in the alkali chamber of 3rd level electric dialyzator, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of the 2nd grade of electric dialyzator 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.Obtain in the 2nd grade sour chamber that concentration of nitric acid is about 1.38mol/L, liquid 1.05L is finished in the sour chamber that contains the about 37g/L of glutamic acid, with its sour chamber that feeds the 1st grade of electric dialyzator as initial liquid; The alkali chamber of the 2nd grade of electric dialyzator obtains mass concentration and is about 5.5% ammoniacal liquor 0.5L, with its alkali chamber that feeds the 1st grade of electric dialyzator as initial liquid.
The partially desalted electric mother liquors such as glutamic acid that contain 11g/L ammonium nitrate, 19g/L glutamic acid that obtain in the salt chamber with the 2nd grade of electric dialyzator feed the salt chamber of 3rd level electric dialyzator as initial liquid, the initial liquid in sour chamber of 3rd level electric dialyzator is the dislysate that 1.0L contains the glutami acid fermentation liquor membrane filtration of the about 40g/L of glutamic acid, the initial liquid in alkali chamber is 0.6% ammoniacal liquor for the 0.5L mass concentration, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of 3rd level electric dialyzator 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 6 μ S/cm, stop electrodialysis operation.Obtain in the sour chamber of 3rd level electric dialyzator that concentration of nitric acid is about 0.57mol/L, liquid 1.03L is finished in the sour chamber that contains the about 38g/L of glutamic acid, with its sour chamber that feeds the 2nd grade of electric dialyzator as initial liquid; The alkali chamber of 3rd level electric dialyzator obtains mass concentration and is about 2.4% ammoniacal liquor 0.5L, with its alkali chamber that feeds the 2nd grade of electric dialyzator as initial liquid; Obtain the electric mother liquors such as glutamic acid of denitrated acid ammonium in the 3rd level electric dialyzator salt chamber, reduced sugar 4.6g/L after measured, the pH value is about 2.9.
With the low temperature isoelectric point crystallization that the concentration of nitric acid that obtains in the 1st grade of sour chamber is about 2.42mol/L, the 1L glutami acid fermentation liquor (containing the about 107g/L of glutamic acid) that liquid is used for another batch is finished in the sour chamber that contains the about 36g/L of glutamic acid, consume about 0.33 liter, gained glutamic acid crystal and traditional isoelectric point crystallization do not have marked difference; The pH that is used for the electric mother liquors such as 1L glutamic acid of another batch regulates, and its pH is adjusted to 2.0 from 3.1, consumes about 0.24 liter, last H
+The glutamic acid adsorption rate of type 732 resin columns and conventional ion exchange absorption do not have marked difference.
The mass concentration that obtains in the 1st grade of alkali chamber is about the pH that 9% ammoniacal liquor is used for the glutamic acid fermentation of another batch regulates, effect with dilute the concentrated ammonia liquor that obtains with commodity liquefied ammonia and do not have marked difference; Be used to prepare eluent, from having adsorbed 732 cation exchange column wash-out glutamic acid of glutamic acid, obtain containing the glutamic acid mass concentration and be 4.9% high flow point, effect is suitable with the elute effect of preparing the eluent that obtains with commodity liquefied ammonia.
The energy consumption that three grade of three Room bipolar membrane electrodialysis removes ammonium nitrate in the electric mother liquors such as glutamic acid is 2.39kWh/kg, than under the same operating condition during not classification energy consumption descend 23%, when reclaiming under the same operating condition of acid solution concentration ratio not classification, the acid chamber improves 8%, the electric mother liquor pH values such as glutamic acid of the denitrated acid ammonium that the salt chamber obtains are 2.9, and the pH value of the electric mother liquors such as glutamic acid of the denitrated acid ammonium that obtains during not classification under the same operating condition is 2.3.
Embodiment 4
Be divided into three grades from the bipolar membrane electrodialysis process of electric mother liquors such as glutamic acid regeneration soda acid, adopt " acid-salt " two Room bipolar membrane electrodialysis devices of three platform independent operation, every as one-level, sees also Fig. 7.Every two Room bipolar membrane electrodialysis device is identical, sees also Fig. 5.Liquid flow path direction in the adjacent compartments adopts and is streamed.The area of amberplex is 210mm * 62mm, uses BP-1 type Bipolar Membrane and JAM-10 type anion-exchange membrane.Bipolar Membrane, anion-exchange membrane are formed 5 pairs of two compartment film stacking structure (as Fig. 5) repeated arrangement.Every is provided with pair of electrodes, uses titanium to be coated with ruthenium electrode and makes positive plate, and stainless steel electrode is made minus plate.Dividing plate and filter are polypropylene material, and dividing plate is a no loop dividing plate, and filter is the mesh grid type.
See also Fig. 3.
Degerming, remove albumen: the electric mother liquors such as glutamic acid of the red plum in LiaoNing, China Shenyang Gourmet Powder Factory 0.2 μ m micro-filtration membrane and the 6K hyperfiltration membrane assembly through Tianjin MoTian Membrane Engineering Technology Co., Ltd filtered, obtain about 6 liters of clear liquid, contain 42g/L ammonium sulfate, 18g/L glutamic acid.
The decalcification magnesium ion: with the above-mentioned sulfur acid ammonium that obtains wait the electric mother liquor clear liquid by being filled with the adsorption column of 1.4L (resin floor height 950mm * internal diameter 45mm) D402 huge legendary turtle mould assembly ion exchange resin, the calcium ions and magnesium ions in the electric mother liquor is adsorbed.The upper prop flow be 1.5 column volumes/hour, at the bottom of post, collect the electric mother liquor that waits that about 5L contains the 60mg/L calcium ions and magnesium ions.
The salt chamber of the 1st grade of electric dialyzator feeds the process degerming, removes the electric mother liquor 4.5L such as glutamic acid of albumen, decalcification magnesium ion, feeding sulfuric acid concentration in acid chamber is that liquid 1.05L is finished as initial liquid in the 2nd grade of electrodialysis acid chamber of 0.8mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.Open the 1st grade of 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.Bubbling air in the material cylinder of salt chamber blows out the ammonia of regenerating with air, air-blowing quantity is 0.5 liter/minute, and the ammonia that blows out absorbs with 0.5 premium on currency in another container.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 electric dialyzator, obtain the sour chamber that sulfuric acid concentration is about 1.28mol/L and finish about 1.1 liters of liquid.
The partially desalted electric mother liquors such as glutamic acid that contain 24g/L ammonium sulfate, 18g/L glutamic acid that obtain in the salt chamber with the 1st grade of electric dialyzator feed the salt chamber of the 2nd grade of electric dialyzator as initial liquid, the initial liquid in sour chamber of the 2nd grade of electric dialyzator is that liquid 1.03L is finished in the sour chamber of the 3rd level electric dialyzator of sulfuric acid concentration 0.35mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of the 2nd grade of electric dialyzator is identical with the 1st grade.The 2nd grade of salt chamber material cylinder aeration condition is identical with the 1st grade, and the ammonia that blows out feeds in the same absorption container and absorbs.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 0.8mol/L and finish liquid 1.05L, with its sour chamber that feeds the 1st grade of electric dialyzator as initial liquid.
The partially desalted electric mother liquors such as glutamic acid that contain 9g/L ammonium sulfate, 18g/L glutamic acid that obtain in the salt chamber with the 2nd grade of electric dialyzator feed the salt chamber of 3rd level electric dialyzator as initial liquid, the initial liquid in sour chamber of 3rd level electric dialyzator is 1.0L 0.1mol/L dilution heat of sulfuric acid, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L 0.25mol/L.The operating condition of 3rd level electric dialyzator is identical with the 1st grade.3rd level salt chamber material cylinder aeration condition is identical with the 1st grade, and the ammonia that blows out feeds in the same absorption container and absorbs.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop electrodialysis operation.Liquid 1.03L is finished in the sour chamber that obtains sulfuric acid concentration in the sour chamber of 3rd level and be 0.35mol/L, with its sour chamber that feeds the 2nd grade of electric dialyzator as initial liquid.In absorbing container, obtain the ammonia mass concentration and be about about 0.5 liter of 9% ammoniacal liquor.The electric mother liquor such as grade that takes off ammonium sulfate that obtains in the salt chamber is reduced sugar 4.7g/L after measured, and the pH value is about 10.05.
The low temperature isoelectric point crystallization of the 1L glutami acid fermentation liquor (containing the about 105g/L of glutamic acid) that liquid is used for another batch is finished in the sour chamber that the sulfuric acid concentration that obtains in the 1st grade of sour chamber is about 1.28mol/L, consume about 0.28 liter, gained glutamic acid crystal and traditional isoelectric point crystallization do not have marked difference; The pH that is used for the electric mother liquors such as 1L glutamic acid of another batch regulates, and its pH is adjusted to 1.8 from 3.1, consumes about 0.23 liter, last H
+The glutamic acid adsorption rate of type 732 resin columns and conventional ion exchange absorption do not have marked difference.
Be about the pH that 9% ammoniacal liquor is used for the glutamic acid fermentation of another batch and regulate absorbing the mass concentration that obtains in the container, effect with dilute the concentrated ammonia liquor that obtains with commodity liquefied ammonia and do not have marked difference; Be used to prepare eluent, from having adsorbed 732 cation exchange column wash-out glutamic acid of glutamic acid, obtain containing the glutamic acid mass concentration and be 4.7% high flow point, effect is suitable with the elute effect of preparing the eluent that obtains with commodity liquefied ammonia.
The energy consumption that three grades " acid-salt " two Room bipolar membrane electrodialysis remove ammonium sulfate in the electric mother liquors such as glutamic acid is 3.6kWh/kg, than under the same operating condition during not classification energy consumption descend 27%, when reclaiming under the same operating condition of acid solution concentration ratio not classification, the acid chamber improves 8.5%, the electric mother liquor pH values such as glutamic acid of taking off ammonium sulfate that the salt chamber obtains are 10.05, and the pH value of the electric mother liquors such as glutamic acid that take off ammonium sulfate that obtain during not classification under the same operating condition is 9.2.
Claims (12)
1. multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid, it is for passing through to adopt multistage bipolar membrane electrodialysis process, change the flow direction of salt chamber liquid and sour chamber liquid in the bipolar membrane electrodialysis device simultaneously, from the electric mother liquors such as 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
2. the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid according to claim 1, it is characterized in that: described multistage bipolar membrane electrodialysis process comprises: in three Room bipolar membrane electrodialysis devices or " acid-salt " two Room bipolar membrane electrodialysis devices, inject electric mother liquors such as glutamic acid the 1st grade salt chamber, in the end the initial liquid in sour chamber is injected in Ji sour chamber; In at different levels, the sour chamber initial liquid of liquid as the corresponding levels is finished in the sour chamber of later one-level, finishes the salt chamber initial liquid of liquid as the corresponding levels with the salt chamber of previous stage; The final salt chamber of level in the end obtains taking off the electric mother liquor that waits of inorganic salts, 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.
3. the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid according to claim 1 and 2, it is characterized in that: described multistage bipolar membrane electrodialysis process is secondary or three grades of bipolar membrane electrodialysis process.
4. according to claim 1,2 or 3 described multistep treatment methods from electric mother liquors such as glutamic acid regeneration soda acid, it is characterized in that: when carrying out bipolar membrane electrodialysis, employing contains the sour chamber initial liquid of the feed liquid of glutamic acid as the bipolar membrane electrodialysis device of last level, the final feed liquid that obtains containing sulfuric acid, hydrochloric acid or the nitric acid of glutamic acid and regeneration the 1st grade sour chamber.
5. the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid according to claim 4, it is characterized in that: the described feed liquid that contains glutamic acid is: the filtered fluid of glutami acid fermentation liquor, glutami acid fermentation liquor, the dislysate of filtering fermentation liquor or their dilution; Or adopt the liquid of freeing that contains glutamic acid that when handing over step wash-out glutamic acid, obtains in traditional " wait electricity-from handing over " technology.
6. the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid according to claim 2, it is characterized in that: at three Room bipolar membrane electrodialysis devices, in the end the initial liquid of the alkali chamber of water, the last level of weak aqua ammonia conduct is injected in the alkali chamber of level, and the alkali chamber initial liquid of liquid as previous stage is finished in the alkali chamber of alkali at different levels chamber.
7. the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid according to claim 1 and 2 is characterized in that: sulfate radical, chlorion or the nitrate anion of sloughing in the salt chamber of each grade is equivalent to enter 20～60% of sulfate radical, chlorion or nitrate anion total amount in the electric mother liquors such as glutamic acid of the 1st grade of salt chamber.
8. the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid according to claim 1 and 2, 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 regenerated hydrochloric acid 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 that is adopted through being used for after fermentation ends after concentrating in this acid chamber, makes glutamic acid crystallization with the pH of electric stostes such as adjusting.
9. the multistep treatment method from electric mother liquors such as glutamic acid regeneration soda acid according to claim 2, 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 zymotic fluid when being used to fermenting and producing glutamic acid, and/or the described ammoniacal liquor glutamic acid that can be used for waiting the wash-out from the cation exchange column of electricity-when handing over step to adsorb; When using described ammonia through or feed fermentation tank behind the storage tank and regulate pH.
10. according to claim 1,2 or 3 described multistep treatment methods, it is characterized in that: also be included in and carry out before the bipolar membrane electrodialysis, electric mother liquors such as glutamic acid are carried out degerming and remove the step of albumen from electric mother liquors such as glutamic acid regeneration soda acid.
11., it is characterized in that: also be included in and carry out electric mother liquors such as glutamic acid being purified the step of decalcification magnesium before the bipolar membrane electrodialysis according to claim 1,2 or 3 described multistep treatment methods from electric mother liquors such as glutamic acid regeneration soda acid.
12., it is characterized in that: also be included in and carry out before the bipolar membrane electrodialysis, the step that electric mother liquors such as glutamic acid are concentrated according to claim 1,2 or 3 described multistep treatment methods from electric mother liquors such as glutamic acid regeneration soda acid.
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| CN102935333A (en) * | 2012-10-29 | 2013-02-20 | 中国科学院过程工程研究所 | Method for separating glutamic acid and lactic acid from fermentation waste liquor by packed bed electrodialysis |
| CN110372527A (en) * | 2019-08-13 | 2019-10-25 | 江南大学 | A method of glutamic acid is recycled from the electric mother liquors such as glutamic acid concentration |
| CN110437088A (en) * | 2019-08-13 | 2019-11-12 | 江南大学 | A method of recycling glutamic acid from the electric mother liquors such as glutamic acid |
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| CN101407350B (en) * | 2008-10-13 | 2010-09-15 | 中国科学院过程工程研究所 | Method for processing ion exchange waste liquor of lysine production by fermentation method |
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| CN102935333A (en) * | 2012-10-29 | 2013-02-20 | 中国科学院过程工程研究所 | Method for separating glutamic acid and lactic acid from fermentation waste liquor by packed bed electrodialysis |
| CN102935333B (en) * | 2012-10-29 | 2014-12-24 | 中国科学院过程工程研究所 | Method for separating glutamic acid and lactic acid from fermentation waste liquor by packed bed electrodialysis |
| CN110372527A (en) * | 2019-08-13 | 2019-10-25 | 江南大学 | A method of glutamic acid is recycled from the electric mother liquors such as glutamic acid concentration |
| CN110437088A (en) * | 2019-08-13 | 2019-11-12 | 江南大学 | A method of recycling glutamic acid from the electric mother liquors such as glutamic acid |
| CN110437088B (en) * | 2019-08-13 | 2020-08-04 | 江南大学 | Method for recovering glutamic acid from glutamic acid isoelectric mother liquor |
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