CN101407350B

CN101407350B - Method for processing ion exchange waste liquor of lysine production by fermentation method

Info

Publication number: CN101407350B
Application number: CN2008102237800A
Authority: CN
Inventors: 丛威; 焦扬; 杨鹏波; 任洪艳; 王倩; 吴霞; 石绍渊; 张勇
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2008-10-13
Filing date: 2008-10-13
Publication date: 2010-09-15
Anticipated expiration: 2028-10-13
Also published as: CN101407350A

Abstract

The invention belongs to the ferment industry, in particular relates to a treatment method of ion exchange waste liquor in lysine production by a fermentation method. The invention adopts a common electrodialysis technology to recycle ammonium sulfate, ammonium chloride or ammonium nitrate in the lysine ion exchange waste liquor produced by extracting the lysine from lysine fermentation production to water solution of ammonium sulfate, ammonium chloride or ammonium nitrate, or adopts a bipolar membrane electrodialysis technology to regenerate sulfuric acid, hydrochloric acid or nitric acid and NH3 by ammonium sulfate, ammonium chloride or ammonium nitrate in the lysine ion exchange waste liquor produced by extracting the lysine from the lysine fermentation production, or adopts the combination of the common electrodialysis technology and the bipolar membrane electrodialysis technology to recycle ammonium sulfate, ammonium chloride or ammonium nitrate in the lysine ion exchange waste liquor produced by extracting the lysine from the lysine fermentation production and regenerate sulfuric acid, hydrochloric acid or nitric acid and NH3. The invention realizes the resource recycling ofthe ion exchange waste liquor and clean production.

Description

In the fermentative Production Methionin from the treatment process of handing over waste liquid

Technical field

The invention belongs to fermentation industry, Methionin is from the treatment process of handing over waste liquid, to realize realizing cleaner production from the resource utilization of handing over waste liquid in particularly a kind of fermentative Production L-Methionin.

Background technology

L-Methionin (hereinafter to be referred as Methionin) is one of eight kinds of indispensable amino acids of humans and animals nutrition.It is to regulating the internal metabolism balance, improve in the body absorption to grain protein, improving human diet nutrition and Animal nutrition, promotion and grow and all play an important role, be mainly used in medicine, food and fodder industry at present, on consumption structure, it is nearly 90% that the consumption of Methionin in feed has accounted for, and only account for 10% in the consumption of food and medicine intermediate.

Methionin is important additive in the fodder industry, is one of most active kind in fodder additives market in recent years.Because global aquaculture fast development, the demand of Methionin increases gradually, and output enlarges rapidly, and the overall throughput in the whole world is about 900,000 tons/year at present, and the aggregated capacity of China has reached 350,000 tons/year.Methionin has become the second largest amino acid product of output behind L-glutamic acid.Traditional Methionin extraction process flow process is seen Fig. 1.Wherein:

Fermentation: lysine fermentation process need add ammonium sulfate to keep certain ammonium concentration.The ammonia consumption that fermenting process also wants other ammonification (form with liquefied ammonia is supplied with, and the moment that enters fermentor tank from pipeline is a gaseous state) to be used for replenishing synthetic lysine maintains pH about 7 simultaneously.The ammonia that adds is used for the synthetic of Methionin basically; The ammonium sulfate that adds finally enters Methionin from handing over waste liquid, concentrating and become composite fertilizer then.

Acidifying: add sulfuric acid and regulate pH to 3, purpose is to make Methionin positively charged, last cationic exchange coloum.The sulfuric acid that adds (ammonia that ammonium sulfate that adds together with fermenting process and back wash-out are used) enters Methionin from handing over waste liquid, concentrating and become composite fertilizer then.

Ion-exchange: the fermented liquid after the acidifying passes through or go up cationic exchange coloum after degerming, and Methionin is exchanged absorption, and the waste liquid that sees through ion exchange column is (of the present invention) Methionin from handing over waste liquid.Methionin is that 20000～40000mg/L, pH are 3～3.5 from handing over waste liquid sulfur acid ammonium to be about 60～80g/L, COD.Prepare elutriant with ammonia, the Methionin of wash-out absorption obtains freeing liquid from the cationic exchange coloum.

Concentrated, crystallization: free the Methionin that liquid contains wash-out, add hydrochloric acid, multiple-effect evaporation concentrates, crystallization gets the lysine hydrochloric acid product salt.

From handing over waste liquid to concentrate: waste liquid evaporation concentrates, spray granulating from handing over Methionin, makes ammonium sulfate composite fertilizer.

Owing to will add the Methionin ammoniacal liquor desorb that will use sulfuric acid acidation, absorption on ammonium sulfate, the fermented liquid before the cationic exchange coloum during fermenting lysine, thus produce ammonium persulfate, high organic, hang down pH from the friendship waste liquid.Ammonium sulfate itself is difficult to biological degradation (biological desulphurization and biological denitrificaion cost are very high, are difficult to industrialization, and are difficult to reclaim resource), and the anaerobism governance process of severe inhibition routine brings difficulty for sophisticated anaerobic treatment process on the contrary.

Present production technique is that the evaporation concentration energy consumption is huge, and causes atmospheric pollution when spray granulating with, spray granulating system ammonium sulfate composite fertilizer concentrated from the friendship waste liquid evaporation to Methionin from the processing of handing over waste liquid.If produce liquid fertilizer inconvenience storage and transportation again, the purity of producing the crystalline sulfuric acid ammonium does not reach the purity of technical grade ammonium sulfate.Huge steam output not only consumes a large amount of steam, and consumes a large amount of water coolants, causes 160～180 tons of present Methionin per ton (hydrochloride) water consumptions.

Domestic had producer to adopt some improved extraction processes.As earlier use the ultrafiltration membrance filter degerming before the fermented liquid upper prop, filtering Methionin yield can reach 97%, and the filter residue oven dry is afterwards capable of using as feed, and the loading capacity that can increase resin is more than 10%, and effectively prolongs resin life.Adopt single-column from friendship in the traditional technology, yield is less than 90%.Used instead basically in recent years continuously from friendship, total yield of products is brought up to about 96%.Have producer to propose to concentrate replacement with nanofiltration and free the evaporation concentration of liquid, concentrated average cost is 20 yuan of/ton water, and cost is lower than evaporation concentration.Also there is producer on ion exchange column, to introduce the regeneration of hydrochloric acid resin, can reduces the generation of ammonium sulfate.All there is not really to solve the sulfur acid ammonium from the problem of handing over waste liquid but so far, each improves technology.

In sum, also there are problems in Methionin from the treatment process of handing over waste liquid.Directly suppressed by the high-concentration sulfuric acid ammonium with bio anaerobic and aerobic treatment, ammonium sulfate itself also is difficult to degraded.Directly utilize from handing over waste liquid production yeast growth speed low, still very high, uneconomical economically behind the culturing yeast from the friendship waste liquid COD.Excessive from handing over waste liquid to concentrate the energy consumption of producing ammonium sulfate composite fertilizer, cause secondary pollution.

Summary of the invention

The purpose of this invention is to provide a kind of fermentative Production Methionin from the treatment process of handing over waste liquid, overcome the existing sulfur acid ammonium that produces when producing Methionin from handing over waste liquid to be difficult to administer and the defective of utilization etc.

In the prior art, the ammonium sulfate that lysine fermentation process need add can be changed into ammonium chloride or ammonium nitrate, change the sulfuric acid that is used for regulating the fermented liquid pH (being the acidifying of Fig. 1) before the cationic exchange coloum into hydrochloric acid or nitric acid, the inorganic salt of the Methionin of gained in handing over waste liquid are ammonium chloride or ammonium nitrate.

Thinking of the present invention is: from handing over waste liquid behind heat sterilization, adopt the common electrical osmotic technique ammonium sulfate, ammonium chloride or ammonium nitrate to be reclaimed from handing over waste liquid from Methionin Methionin; Or adopt the bipolar membrane electrodialysis technology from handing over waste liquid, ammonium sulfate, ammonium chloride or ammonium nitrate to be regenerated as sulfuric acid, hydrochloric acid or nitric acid and ammonia from Methionin; Or adopt common electrical osmotic technique and bipolar membrane electrodialysis technology to combine, from Methionin from handing over waste liquid, ammonium sulfate, ammonium chloride or ammonium nitrate is recovered as the aqueous solution of ammonium sulfate, ammonium chloride or ammonium nitrate and be regenerated as sulfuric acid, hydrochloric acid or nitric acid and ammonia (as adopting the bipolar membrane electrodialysis technology earlier, adopt the common electrical osmotic technique again, can be regenerated as Methionin behind sulfuric acid, hydrochloric acid or nitric acid and the ammonia from handing over waste liquid to carry out the recovery of further ammonium sulfate, ammonium chloride or ammonium nitrate carrying out ammonium persulphate, ammonium chloride or ammonium nitrate; And, adopt the bipolar membrane electrodialysis technology again to adopting earlier the common electrical osmotic technique, can be to the Methionin after Methionin reclaims ammonium sulfate, ammonium chloride or ammonium nitrate from handing over waste liquid from handing over waste liquid to carry out further black sulfuric acid, hydrochloric acid or nitric acid and ammonia).When being used for fermentative production Methionin, ammonium sulfate, ammonium chloride or the ammonium nitrate circulation of reclaiming replenish ammonium sulfate, ammonium chloride or ammonium nitrate; Add ammonia to fermented liquid when regenerated ammonia circulation is used for fermentative production Methionin, and/or be used for the Methionin of wash-out absorption from the cationic exchange coloum that is adsorbed with Methionin; The pH (being the acidifying of Fig. 1) that regenerated sulfuric acid, hydrochloric acid or nitric acid circulation is used to regulate the fermented liquid before the cationic exchange coloum.Can get through the inhibition bottleneck of ammonium persulfate when handing over the waste liquid biological treating thus, also can save a large amount of acid and alkali consumptions, also avoid generating the ammonium sulfate byproduct of low value.The Methionin that inorganic salt is reclaimed and/or are regenerated as (after the desalination) behind the corresponding bronsted lowry acids and bases bronsted lowry is from handing over waste liquid only surplus organic, can be used to cultivate the higher fodder yeast of value, after consuming most of organic matter, adopt conventional biological treating technology to reach emission standard or middle water reuse; Also can directly adopt conventional anaerobism, aerobe to administer after the desalination.Because the high density inorganic salt of Methionin in handing over waste liquid have been recovered and/or have been regenerated as bronsted lowry acids and bases bronsted lowry, removed inhibition from friendship waste liquid bio-transformation or improvement, make and accelerate greatly from the speed of handing over waste liquid to cultivate thalline or anaerobism improvement, from handing over the waste liquid culturing yeast to become feasible economically, can realize the resource utilization of waste liquid organic matter.Thinking of the present invention can fundamentally solve Methionin from the pollution problem of handing over waste liquid, realizes cleaner production, and process flow diagram is shown in Fig. 2,3,4.

The common electrical osmotic technique principle that the present invention adopts is seen Fig. 5.Fig. 5 is common electrodialytic film stacking structure synoptic diagram.Wherein A is an anion-exchange membrane, and C is a cationic exchange membrane; " salt " expression salt chamber (feeding processed Methionin from handing over waste liquid), " dense " represents dense chamber, " utmost point " expression " utmost point chamber ".Under electric field action, the positively charged ion M of salt ⁺(M ⁺Be ammonium ion in the present invention) and negatively charged ion X ^-(X ^-Be acid group) pass the migration of cationic exchange membrane and anion-exchange membrane respectively and enter dense chamber, obtain from the isolated MX in salt chamber in dense chamber.

The bipolar membrane electrodialysis know-why that the present invention adopts is: bipolar membrane electrodialysis can dissociate water generate H ⁺And OH ^-, in conjunction with anion-exchange membrane and/or cationic exchange membrane, bipolar membrane electrodialysis can generate corresponding bronsted lowry acids and bases bronsted lowry to salt.Fig. 6 is the film stacking structure synoptic diagram of " acid-salt-alkali " three Room bipolar membrane electrodialysis.Wherein A is an anion-exchange membrane, and C is a cationic exchange membrane, and BM is a Bipolar Membrane; " salt " expression salt chamber (feeding processed Methionin from handing over waste liquid), " acid " represents sour chamber, " alkali " expression alkali chamber, " utmost point " expression " utmost point chamber ".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 ⁺(M ⁺Be ammonium ion in the present invention) and negatively charged ion 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.When pending feed liquid contains NH ₄ ⁺And SO ₄ ^2-The time, then obtain H in sour chamber ₂SO ₄, obtain NH in the alkali chamber ₃Bipolar membrane electrodialysis above-mentioned except adopting " acid-salt-alkali " three cell structures (principle as shown in Figure 6), can also adopt " acid-salt " two cell structures (as shown in Figure 7), constitute " acid-salt " two Room bipolar membrane electrodialysis devices, promptly be equivalent to " salt-alkali " two Room of Fig. 6 are merged.

Bipolar membrane electrodialysis is obtained some industrial application in some inorganic processes, as from containing KF and KNO ₃Pickle solution in reclaim HF and HNO ₃, from the sodium sulfate waste liquid of artificial silk factory regeneration NaOH and H ₂SO ₄, regeneration absorbs SO from stack gas ₂Recovery liquid, from ammonium nitrate solution, reclaim NH ₃And HNO ₃, from potassium nitrate solution, reclaim KOH and HNO ₃Relate in the organic process, what report was more at present is to separate to transform from organic acid salt to produce organic acid, typical example is from lactic acid fermentation liquid (Sodium.alpha.-hydroxypropionate) regeneration lactic acid and NaOH (L.Madzingaidzo et al.Process development andoptimization of lactic acid purification using electrodialysis.Journal ofbiotechnology, 2002, and the pH value that NaOH circulation is used to regulate fermentation 96:223～239).Other report as produce Vc, from Sunmorl N 60S, reclaim gluconic acid, generate glycine, produce citric acid and carry out that kilnitamin separates etc. (patent publication No. CN1050015A, CN1031112A etc.) from Citrate trianion from Sodium glycocollate from sodium ascorbate.

Methionin of the present invention is from the treatment process of handing over waste liquid, is to adopt the common electrical osmotic technique to extract Methionin that Methionin produces is recovered as ammonium sulfate, ammonium chloride or ammonium nitrate ammonium sulfate, ammonium chloride or ammonium nitrate from the friendship waste liquid the aqueous solution when fermenting lysine is produced; Or the Methionin that adopts the bipolar membrane electrodialysis technology to extract the Methionin generation when fermenting lysine is produced is regenerated as sulfuric acid, hydrochloric acid or nitric acid and ammonia (NH with ammonium sulfate, ammonium chloride or ammonium nitrate from handing over waste liquid ₃); Or adopting common electrical osmotic technique and bipolar membrane electrodialysis technology to combine, the Methionin that extracts the Methionin generation when fermenting lysine is produced is recovered as ammonium sulfate, ammonium chloride or ammonium nitrate the aqueous solution of ammonium sulfate, ammonium chloride or ammonium nitrate and is regenerated as sulfuric acid, hydrochloric acid or nitric acid and ammonia (NH from handing over waste liquid ₃).

To contain NH ₄ ⁺The Methionin of vitriol, hydrochloride or nitrate from handing over waste liquid to feed in the salt chamber of common electrical dialyzer; Open the common electrical dialyzer Methionin that feeds the salt chamber is handled from the friendship waste liquid, be reduced to needed concentration up to the inorganic acid radical concentration of the Methionin that enters the salt chamber in handing over waste liquid, or NH ₄ ⁺Concentration is reduced to needed concentration, finishes Methionin from the processing of handing over waste liquid; The aqueous solution of ammonium sulfate, ammonium chloride or the ammonium nitrate that obtains reclaiming in the dense chamber of common electrical dialyzer, the Methionin after the salt chamber obtains desalination is from handing over waste liquid.

To contain NH ₄ ⁺The Methionin of vitriol, hydrochloride or nitrate from handing over waste liquid to feed in the salt chamber of three Room bipolar membrane electrodialysis devices, or feed in the salt chamber that " salt-alkali " two Room of two Room bipolar membrane electrodialysis devices merge; Open the bipolar membrane electrodialysis device Methionin that feeds the salt chamber is handled from the friendship waste liquid, be reduced to needed concentration up to the inorganic acid radical concentration of the Methionin that enters the salt chamber in handing over waste liquid, or NH ₄ ⁺Concentration is reduced to needed concentration, finishes Methionin from the processing of handing over waste liquid; Wherein:

Sour chamber at three Room bipolar membrane electrodialysis devices obtains regenerated sulfuric acid, hydrochloric acid or nitric acid, obtains regenerated NH in the alkali chamber ₃, the Methionin after the salt chamber obtains desalination is from handing over waste liquid;

Sour chamber at two Room bipolar membrane electrodialysis devices obtains regenerated sulfuric acid, hydrochloric acid or nitric acid, obtains regenerated NH in the salt chamber that salt-alkali two Room merge ₃, NH ₃Be blown the Methionin of back after the salt chamber obtains desalination from handing over waste liquid.

Ammonium concentration in the aqueous solution of described ammonium sulfate, ammonium chloride or the ammonium nitrate that obtains reclaiming in the dense chamber of common electrical dialyzer is 0.5～5mol/L.

The aqueous solution of described ammonium sulfate, ammonium chloride or the ammonium nitrate that obtains reclaiming in the dense chamber of common electrical dialyzer can be directly or is replenished ammonium sulfate, ammonium chloride or ammonium nitrate when being used for fermentative production Methionin after concentrating.

Described sour chamber or the regenerated vitriolic concentration that obtains of the sour chamber of two Room bipolar membrane electrodialysis devices at three Room bipolar membrane electrodialysis devices is 0.5～2.5mol/L; Described at three Room bipolar membrane electrodialysis devices sour chamber or the concentration of the regenerated hydrochloric acid that obtains of the sour chamber of two Room bipolar membrane electrodialysis devices be 1～5mol/L; Described at three Room bipolar membrane electrodialysis devices sour chamber or the concentration of the regenerated nitric acid that obtains of the sour chamber of two Room bipolar membrane electrodialysis devices be 1～5mol/L.

Described sour chamber or the sour chamber of two Room bipolar membrane electrodialysis devices the regenerated sulfuric acid, hydrochloric acid or the nitric acid that obtain at three Room bipolar membrane electrodialysis devices can be directly or through being used to regulate the pH of the preceding lysine fermentation liquor of cationic exchange coloum after concentrating.

The alkali chamber that is used in three Room bipolar membrane electrodialysis devices obtains regenerated NH ₃(ammoniacal liquor, liquefied ammonia or ammonia) or be used in the salt chamber that salt-alkali two Room of two Room bipolar membrane electrodialysis devices merge and obtain regenerated NH ₃(ammoniacal liquor, liquefied ammonia or ammonia) or the feeding medium during fermentation liquid (liquid glucose during with fermentative production Methionin, or ammonium sulfate solution, or aqueous ammonium chloride solution, or aqueous ammonium nitrate solution) is absorbed in ammoniated liquid glucose (or the ammoniated ammonium sulfate solution that obtains that regenerated ammonia that the alkali chamber of three Room bipolar membrane electrodialysis devices obtains or the regenerated ammonia that obtains obtain in the salt chamber that salt-alkali two Room of two Room bipolar membrane electrodialysis devices merge, or the ammoniated aqueous ammonium chloride solution that obtains, or the ammoniated aqueous ammonium nitrate solution that obtains); (fermenting lysine need be added ammonia and ammonium to add ammonia and/or ammonium to fermented liquid when can be used for fermentative production Methionin, wherein ammonium is added with the form of ammonium sulfate, ammonium chloride or ammonium nitrate), and/or be used for the Methionin of wash-out absorption from the cationic exchange coloum that is adsorbed with Methionin; Wherein: add ammonia (NH to fermented liquid when being used for fermentative production Methionin ₃) and/or ammonium is ammoniacal liquor, liquefied ammonia or ammonia, or with liquid glucose (or ammonium sulfate solution, or aqueous ammonium chloride solution, or aqueous ammonium nitrate solution) absorbs ammoniated liquid glucose (or the ammoniated ammonium sulfate solution that obtains that obtains behind the ammonia, or the ammoniated aqueous ammonium chloride solution that obtains, or the ammoniated aqueous ammonium nitrate solution that obtains); Being ammoniacal liquor or absorbing the ammoniated aqueous ammonium chloride solution that obtains behind the ammonia with the aqueous solution that contains ammonium chloride of ammoniacal liquor preparation or with aqueous ammonium chloride solution of Methionin that is used for wash-out absorption from the cationic exchange coloum that is adsorbed with Methionin.Described ammonia (containing ammonia gas) can through or feed fermentor tank behind the storage tank and add ammonia.

Obtain ammonium sulfate with the common electrical dialyzer from Methionin recovery from handing over waste liquid, after the desalination behind the aqueous solution of ammonium chloride or ammonium nitrate in handing over waste liquid, or with the bipolar membrane electrodialysis device after the desalination after regeneration obtains bronsted lowry acids and bases bronsted lowry from handing over waste liquid from Methionin in handing over waste liquid, or adopt common electrical dialyzer and bipolar membrane electrodialysis device to combine, from Methionin reclaim(ed) sulfuric acid ammonium from handing over waste liquid, ammonium chloride or ammonium nitrate and regeneration obtain mainly containing the various organic matters that lysine fermentation liquor brings after the desalination behind the bronsted lowry acids and bases bronsted lowry in handing over waste liquid, can adopt various ordinary method resource utilizations or improvement, as producing methane.The preferred culturing yeast of the present invention consumes most of organic matter by culturing yeast, obtains can be used as the yeast of feedstuff protein simultaneously.Raffinate behind the culturing yeast can adopt conventional anaerobism, aerobic process to administer.

Methionin is from handing over waste liquid COD generally at 30000～50000mg/L.Wherein assorted amino acid, residual sugar, organic acid and organonitrogen etc. all are the nutrition of yeast growth, can be utilized by yeast in various degree.On the other hand, the price of fodder yeast can reach 3000 yuan/ton, and traditional be 600～700 yuan/ton with Methionin from handing over waste liquid to concentrate the sulphur ammonium compound fertilizer price that makes.Therefore, be fodder yeast with the organic matter transformation of Methionin in handing over waste liquid, be to improve the effective way that fermented waste fluid is administered economy.But the Methionin of traditional processing technology causes inhibition to microbial growth, so organic matter wherein is difficult to carry out bio-transformation from handing over waste liquid sulfur acid ammonium concentration very high.Also there is the scholar to screen the barms of resisting high-concentration ammonium sulfate, but still can't resolve the problem of the ammonium sulfate of raffinate behind the culturing yeast.So present production has to concentrate granulation system composite fertilizer from the friendship waste liquid, energy consumption is big.

The NH that the present invention utilizes the common electrical dialyzer that Methionin is contained in handing over waste liquid ₄ ⁺Vitriol, hydrochloride or after nitrate reclaims, or the N that Methionin is contained in the friendship waste liquid with the bipolar membrane electrodialysis device _H4 ⁺Vitriol, hydrochloride or nitrate be regenerated as bronsted lowry acids and bases bronsted lowry after, or adopt common electrical dialyzer and bipolar membrane electrodialysis device to combine, the NH that Methionin is contained in handing over waste liquid ₄ ⁺Vitriol, hydrochloride or after nitrate reclaims and is regenerated as bronsted lowry acids and bases bronsted lowry, can remove with Methionin from handing over waste liquid to cultivate the high salt inhibition of various valuable bacterial classifications, increase substantially its growth velocity.Valuable bacterial classification generally includes yeast, mould, photosynthetic bacterium etc.

The present invention will be with the Methionin after the desalination that obtains behind common electrical dialyzer reclaim(ed) sulfuric acid ammonium, ammonium chloride or the ammonium nitrate from handing over waste liquid, or ammonium sulfate, ammonium chloride or ammonium nitrate are regenerated as Methionin after the desalination that obtains behind the bronsted lowry acids and bases bronsted lowry from handing over waste liquid with the bipolar membrane electrodialysis device, or adopt common electrical dialyzer and bipolar membrane electrodialysis device to combine, ammonium sulfate, ammonium chloride or ammonium nitrate are reclaimed and are regenerated as Methionin after the desalination that obtains behind the bronsted lowry acids and bases bronsted lowry from handing over waste liquid as culturing yeast.Barms comprises that common can be used to make the barms of feed, as: candida tropicalis, Candida utilis, saccharomyces cidri, geotrichum candidum or yeast saccharomyces cerevisiae etc.Adopt conventional method to cultivate.

Because the Methionin after the desalination is complicated from handing over waste liquid to form, there is certain limitation in the nutritive substance of single culture utilization in handing over waste liquid, so the present invention preferably further by a plurality of barms mixed culture, utilizes the complementarity of its nutritional needs, can subdue COD more.From above-mentioned bacterial classification, optimized the mixed culture of cultivating saccharomyces cidri, candida tropicalis and Candida utilis, but their blending ratio is not limit.

Raffinate behind the culturing yeast can adopt the up to standard or reuse of traditional anaerobic-aerobic technology governance.

Common electrical dialyzer among the present invention is conventional common electrical dialyzer equipment, can adopt conventional working method, comprises constant current, constant voltage or transformation, unsteady flow mode.The organizational form of common electrical dialyzer comprises one section of conventional one-level and multistage multistage organizational form.No matter one section of one-level or multistage multistage organizational form all can be according to the initial liquid of ordinary method water, ammonium sulfate (or ammonium chloride, or the ammonium nitrate) aqueous solution as dense chamber.

Bipolar membrane electrodialysis device among the present invention is conventional bipolar membrane electrodialysis device equipment, can adopt conventional working method, comprises constant current, constant voltage or transformation, unsteady flow mode.The organizational form of bipolar membrane electrodialysis device comprises one section of conventional one-level and multistage multistage organizational form.No matter one section of one-level or multistage multistage organizational form all can be according to ordinary method water, diluted acid (sulfuric acid, hydrochloric acid or nitric acid) the initial liquid as sour chamber.All can be according to ordinary method water, weak ammonia initial liquid as the alkali chamber, thus directly obtain ammoniacal liquor in the alkali chamber; Or be the initial liquid of alkali chamber according to ordinary method with NaOH solution, KOH solution or other strongly basic medium, the ammonia that generates in the alkali chamber is blown out with air or other rare gas element obtain ammonia; The ammonia that blows out can further obtain liquefied ammonia with conventional condensation method liquefaction, or the water absorption obtains ammoniacal liquor, or with liquid glucose (or ammonium sulfate solution, or aqueous ammonium chloride solution, or aqueous ammonium nitrate solution) obtains ammoniated liquid glucose (or ammoniated ammonium sulfate solution behind the absorption ammonia, or ammoniated aqueous ammonium chloride solution, or ammoniated aqueous ammonium nitrate solution), obtain ammoniated aqueous ammonium chloride solution after absorbing ammonia or with aqueous ammonium chloride solution.

The present invention further adopts the filtered liquid (seeing through liquid with what lysine fermentation liquor obtained after with method filtration sterilizations such as membrane filtrations) of lysine fermentation liquor, lysine fermentation liquor, the dialyzate of filtering fermentation liquor (with lysine fermentation liquor during with micro-filtration or ultrafiltration membrance filter, the membrane flux that thalline concentrates after-filtration descends, simultaneously also in order to improve the filtering yield that sees through Methionin in the liquid, need 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 in more than one initial liquid as bipolar membrane electrodialysis device acid chamber; The feed liquid that contains Methionin and regenerated sulfuric acid, hydrochloric acid or nitric acid (liquid is finished in sour chamber) that obtains from sour chamber is when being used for fermentative production Methionin, regulates the pH of the fermented liquid before the cationic exchange coloum after fermentation ends.

The present invention further adopts the initial liquid of the aqueous solution of ammonium sulfate, ammonium chloride or ammonium nitrate as bipolar membrane electrodialysis device alkali chamber, three Room; Additional ammonium sulfate when the aqueous solution that contains ammonium sulfate, ammonium chloride or ammonium nitrate and regenerated ammonia that obtains from the alkali chamber is used for fermentative production Methionin (or ammonium chloride, or ammonium nitrate) and ammonia; The aqueous solution that contains ammonium chloride and regenerated ammonia that obtains from the alkali chamber is used for the Methionin of wash-out absorption from the cationic exchange coloum that is adsorbed with Methionin.

The present invention further will be from the alkali chamber of three Room bipolar membrane electrodialysis devices or the ammonia that blows out of the salt chamber that merges, salt-alkali two Room of two Room bipolar membrane electrodialysis devices, feeding medium during fermentation liquid (liquid glucose during with production Methionin, or ammonium sulfate solution, or aqueous ammonium chloride solution, or aqueous ammonium nitrate solution) absorption obtains ammoniated liquid glucose (or ammoniated ammonium sulfate solution, or ammoniated aqueous ammonium chloride solution, or ammoniated aqueous ammonium nitrate solution), then should ammoniated liquid glucose (or ammoniated ammonium sulfate solution, or ammoniated aqueous ammonium chloride solution, or ammoniated aqueous ammonium nitrate solution), the fermentation stage that returns when producing Methionin uses, add sugar (or add ammonium sulfate, or add ammonium chloride, or add ammonium nitrate) when being used for adding ammonia to fermented liquid.Ammoniated liquid glucose (or ammoniated ammonium sulfate solution, or ammoniated aqueous ammonium chloride solution, add sugar when or ammoniated aqueous ammonium nitrate solution) being used for adding ammonia and (or add ammonium sulfate to fermented liquid, or add ammonium chloride, or add ammonium nitrate) be the method that adopts patent CN200510130636.9; Maybe will contain ammonia gas (can through/without storage tank) directly feeds fermentor tank and replenishes the required ammonia of fermenting lysine.

The utmost point chamber feed liquid of the common electrical dialyzer among the present invention consists of conventional industrial electro dialyzer utmost point chamber commonly used to be formed, as the aqueous solution of sodium-chlor, ammonium chloride, sodium sulfate or other indifferent electrolyte of 0.1～0.5mol/L; 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.

The temperature of each chamber (comprising dense chamber, salt chamber, utmost point chamber) feed liquid adopts the temperature of conventional electrodialysis operation, is no more than 5～50 ℃ scope usually; The flow velocity of feed liquid adopts conventional flow velocity in each chamber (comprising dense chamber, salt chamber, utmost point chamber), 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.

The original volume of dense chamber feed liquid and the volume ratio of salt chamber are as the criterion to reach predetermined cycles of concentration.Wherein, the volume ratio of initial feed liquid in dense chamber and salt chamber feed liquid is 0.1～2:1.

The utmost point chamber feed liquid of the bipolar membrane electrodialysis device among the present invention consists of conventional industrial bipolar membrane electrodialysis device utmost point chamber commonly used to be formed, as the aqueous solution of sodium-chlor, sodium sulfate or other indifferent electrolyte of 0.1～0.5mol/L; 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.

The temperature of each chamber (comprising sour chamber, alkali chamber, salt chamber, utmost point chamber) feed liquid adopts the temperature of conventional electrodialysis operation, is no more than 5～50 ℃ scope usually; The flow velocity of feed liquid adopts conventional flow velocity in each chamber (comprising sour chamber, alkali chamber, salt chamber, utmost point chamber), 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.

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.Wherein, the volume ratio of initial feed liquid in sour chamber and salt chamber feed liquid is 0.1～2:1; The volume ratio of initial feed liquid in alkali chamber and salt chamber feed liquid is 0.05～2:1.

In blowing the ammonia operation, the pH value with increasing or reduce the way adjusting alkali chamber of air flow that is: increases air flow when the pH of alkali chamber value is higher than the pH value of setting, reduce air flow when the pH of alkali chamber value is lower than the pH value of setting, thereby keeps the pH of alkali chamber.It is certain numerical value more than 9 that the pH value of alkali chamber maintains pH.Adopt conventional pH control device.

Except above-mentioned " acid-salt-alkali " three Room bipolar membrane electrodialysis devices (as shown in Figure 6), can adopt " acid-salt " two Room bipolar membrane electrodialysis devices (as shown in Figure 7), promptly be equivalent to " salt-alkali " two Room of Fig. 6 are merged, directly from the salt chamber, ammonia blown out and obtain ammonia with air or other rare gas element, or further the ammonia that blows out is obtained liquefied ammonia with conventional condensation method liquefaction, maybe the further water absorption of the ammonia that blows out is obtained ammoniacal liquor.The method of pH control of the circulation means of ammonia and salt chamber is with above-mentioned " acid-salt-alkali " three Room bipolar membrane electrodialysis.

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

Commercially available cationic exchange membrane has much at present, for example: the Neosebta CL-2.5T of day Bender mountain Cao Da company production, Neosebta CLS-2.5T, the Aciplex CK-1 that Japan company of Asahi Chemical Industry produces, Aciplex CK-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 Nepton CR61AZL183 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, FumasepFKE, 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 company limited 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.

Commercially available anion-exchange membrane has much at present, for example: the Neosebta AV-4T of day Bender mountain Cao Da company production, Neosebta AFS-4T, DFM, the AciplexCA-1 that Japan company of Asahi Chemical Industry produces, Aciplex CA-3, the Selemion AMV that Japan AGC company produces, Selemion ASV, 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 Nepton AR111BZL183 that Ion America Inc. (Ionics) produces, Nepton AR111BZL065, the Fumasep FTAM that U.S. good fortune equine skill company (Fumatech) produces, Fumasep FAB, Fumasep FAA, Fumasep FAP, Fumasep FAB-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 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 produced of Ministry of Nuclear Industry Beijing five.

Commercially available Bipolar Membrane has at present: the Neosebta BP-1 of day Bender mountain Cao Da company production or the Fumasep FBM that U.S.'s good fortune equine skill is produced.

Add degerming, remove the albumen step

Fermentative Production Methionin has preceding degerming, i.e. degerming before last cationic exchange coloum to the processing of thalline at present; Back degerming is also arranged, and the extraction Methionin that promptly carries disease germs all the time, thalline enter Methionin from handing over waste liquid.In recent years, because membrane filtration technique is tending towards ripe, part enterprise begins to adopt membrane filtration degerming before cationic exchange coloum on the fermented liquid, and first degerming can improve the capacity of ion exchange resin absorption Methionin, the life-span of prolongation ion exchange resin.

The inventor finds, with the common electrical dialyzer from Methionin from handing over waste liquid when reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, or with the bipolar membrane electrodialysis device from Methionin from handing over waste liquid during the regeneration soda acid, or combine with common electrical dialyzer and bipolar membrane electrodialysis device, from Methionin from handing over waste liquid when reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate and regeneration soda acid, earlier with Methionin from hand over the waste liquid degerming, remove albumen can prolong common electrical dialyzer and/or bipolar membrane electrodialysis device operational cycle, cut down the consumption of energy.Reason is that thalline and foreign protein can form film and pollute.Therefore, the present invention is at reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, and/or the acid-alkali regeneration step adds Methionin before from the degerming of handing over waste liquid, except that the albumen step.

Conventional means is adopted in degerming, and 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.

Remove albumen and adopt ultrafiltration.Can adopt molecular weight cut-off is the ultra-filtration membrane of 1K, 3K, 6K or 10K.

Add and purify the decalcification step

The inventor finds, with the common electrical dialysis from Methionin from handing over waste liquid when reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, the high-valence cationic of Methionin in handing over waste liquid mainly is calcium, magnesium ion, can form membrane contaminant in the salt chamber side of cationic exchange membrane and the dense chamber side of anion-exchange membrane; With bipolar membrane electrodialysis from Methionin from handing over waste liquid during the regeneration soda acid, the high-valence cationic of Methionin in handing over waste liquid mainly is that calcium, magnesium ion can move and enter the alkali chamber, and forms membrane contaminant on cationic exchange membrane and Bipolar Membrane; When adopting " acid-salt " two Room bipolar membrane electrodialysis device (Fig. 7) to carry out acid-alkali regeneration, calcium, magnesium ion also can form membrane contaminant on Bipolar Membrane.Film pollutes and can increase resistance and energy consumption, increases the cleaning burden of electrodialyzer.Therefore, the present invention is at reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, and/or the acid-alkali regeneration step adds Methionin before from the decalcification magnesium step of handing over waste liquid.

Decalcification magnesium adopts the method for conventional cationic exchange, or adds the method that oxalic acid forms oxalate precipitation.The ion exchange resin that base exchange method of the present invention removes calcium, magnesium ion in handing over waste liquid can adopt storng-acid cation exchange resin, weakly acidic cation-exchange resin and chelating ion exchange resin.

Described storng-acid cation exchange resin is commercially available 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 company limited produces, and Chinese Zhengguang Resin Co., Ltd. produce 001 * 7, D001.

Described weakly acidic cation-exchange resin is commercially available weakly acidic 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.

Described chelating ion exchange resin is commercially available 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 the preferred Chinese Chemical Plant of Nankai Univ. of the present invention produces, or a kind of among the chelating ion exchange resin D402 that produces of Chinese Jiangsu Su Qing engineering of water treatment Group Co.,Ltd.

The operational condition that adds oxalic acid decalcification, magnesium ion of the present invention is as follows: oxalic acid solution is 0.01mol/L～5mol/L in the concentration in handing over waste liquid; Or the add-on of oxalic acid is 0.1～5 times of total moles of calcium magnesium in handing over waste liquid.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 forms such as centrifugal, filtration.

Add concentrated step

The inventor finds, with the common electrical dialyzer from Methionin reclaim(ed) sulfuric acid ammonium from handing over waste liquid, before ammonium chloride or the ammonium nitrate, or with the bipolar membrane electrodialysis device from Methionin from handing over waste liquid before the regeneration soda acid, or combine with common electrical dialyzer and bipolar membrane electrodialysis device, from Methionin reclaim(ed) sulfuric acid ammonium from handing over waste liquid, before ammonium chloride or ammonium nitrate and the regeneration soda acid, to can improve the ammonium sulfate of recovery from handing over waste liquid to concentrate, the concentration of ammonium chloride or ammonium nitrate and/or regenerated vitriolic concentration reduce the reclaim(ed) sulfuric acid ammonium on the whole, the energy consumption of ammonium chloride or ammonium nitrate and/or regeneration soda acid process.

Therefore, the present invention is at reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, and/or the acid-alkali regeneration step adds Methionin before from the enrichment step of handing over waste liquid.Can adopt conventional means such as evaporation, multiple-effect evaporation or membrane concentration.Can be with Methionin from handing over waste liquid to be concentrated into 1/6～1 of original volume.

Methionin is applicable to ammonium sulfate, ammonium chloride or ammonium nitrate from the treatment process of handing over waste liquid and replenishes ammonium ion to lysine fermentation process in the fermentative Production Methionin of the present invention, simultaneously, regulate the extraction process that goes up the preceding fermented liquid pH (being the acidifying of Fig. 1) of cationic exchange coloum with sulfuric acid, hydrochloric acid or nitric acid.

Methionin from the benefit of the treatment process of handing over waste liquid is in the fermentative Production Methionin of the present invention: 1. the inorganic salt in the waste liquid are reclaimed and/or are regenerated as bronsted lowry acids and bases bronsted lowry and realize closed cycle, thereby reduce supplies consumption significantly; 2. avoid producing ammonium sulfate composite fertilizer, more energy-conservation than the concentrating spent liquor system ammonium sulfate composite fertilizer of traditional technology; 3. with the organic matter transformation in the waste liquid Yeast protein feed (price surpasses 3000 yuan/ton, and composite fertilizer's price about 600 yuan/ton) of high value.Methionin has been removed high salt and has been suppressed after handing over the waste liquid desalination, the zymic speed of growth can improve greatly, can realize organic resource utilization and high-valued; 4. compare with traditional technology, do not reduce the total recovery of Methionin; 5. remove the bottleneck of waste liquid downstream biological treating, make the present sophisticated biotechnology governance for reaching standard of raffinate, fundamentally solve the pollution problem that the high bisulfate waste liquor of Methionin brings.

From handing over waste liquid culturing yeast single culture, COD can be reduced to 3000～8000mg/L from 30000～50000mg/L with the Methionin after the desalination, the yeast productive rate can reach 20g/L days, far above the speed of growth of directly using the waste liquid culturing yeast.

When handing over waste liquid to cultivate the mixture of three primary yeasts, the biomass that obtains does not almost have lag period all greater than single culture with the Methionin after the desalination, and the space-time yield of logarithmic phase can reach 1g/Lh, and COD can reduce to 3000～7000mg/L from 40000mg/L.

Description of drawings

Fig. 1. the traditional processing technology schematic flow sheet of Methionin.

Fig. 2. fermentation of the present invention is added ammonium sulfate and ammonia, is used the Methionin of sulfuric acid acidation fermented liquid from handing over the process for treating waste liquor synoptic diagram.

Fig. 3. fermentation of the present invention is added ammonium chloride and ammonia, is used the Methionin of hcl acidifying fermented liquid from handing over the process for treating waste liquor synoptic diagram.

Fig. 4. fermentation of the present invention is added ammonium nitrate and ammonia, is used the Methionin of nitric acid acidifying fermentation liquid from handing over the process for treating waste liquor synoptic diagram.

Fig. 5. the film stacking structure in the common electrical dialyzer is arranged synoptic diagram; Wherein:

A is an anion-exchange membrane, and C is a cationic exchange membrane; " salt " expression salt chamber, " dense " expression concentration compartments, " utmost point " expression " utmost point chamber "; M is the positively charged ion of salt, and X is the acid radical anion of salt.

Fig. 6. the film stacking structure in " acid-salt-alkali " three Room bipolar membrane electrodialysis devices is arranged synoptic diagram; Wherein:

A is an anion-exchange membrane, and C is a cationic exchange membrane, and BM is a Bipolar Membrane; " salt " expression salt chamber, " acid " represents sour chamber, " alkali " expression alkali chamber; M is the positively charged ion of salt, and X is the acid radical anion of salt.

Fig. 7. film stacking structure is arranged synoptic diagram in " acid-salt " two Room bipolar membrane electrodialysis devices; Wherein:

A is an anion-exchange membrane, and BM is a Bipolar Membrane; " salt " expression salt chamber, " acid " represents sour chamber; M is the positively charged ion of salt, and X is the acid radical anion of salt.

Embodiment

Embodiment 1

The common electrical dialyzer is the common electrical dialyzer of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of ion-exchange membrane is 210mm * 62mm, uses JAM-10 type anion-exchange membrane and JCM-1 type cationic exchange membrane.Anion-exchange membrane, cationic exchange membrane are formed 5 pairs of two compartment film stacking structure (as Fig. 5) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made negative plate.Dividing plate and filter are polypropylene material, and dividing plate is a no widely different road dividing plate, and filter is the mesh grid type.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 53000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed in the salt chamber of common electrical dialyzer from friendship waste liquid 3.0L; The initial liquid in dense chamber is the ammonium sulfate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 2.7mol/L of the ammonium ion) aqueous solution that concentration is about 1.35mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 50100mg/L of COD after measured, and BOD is 26200mg/L, reducing sugar 5g/L, and the pH value is about 3.1.

Embodiment 2

The common electrical dialyzer is with embodiment 1.

See also Fig. 3.The ammonium chloride that contains 48g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 52000mg/L of COD are fed in the salt chamber of common electrical dialyzer from friendship waste liquid 3.0L; The initial liquid in dense chamber is the aqueous ammonium chloride solution of 3.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 3.09 liters of the aqueous ammonium chloride solution that concentration is about 0.9mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 49200mg/L of COD after measured, and BOD is 25200mg/L, reducing sugar 5g/L, and the pH value is about 3.3.

Embodiment 3

The common electrical dialyzer is with embodiment 1.

See also Fig. 4.The ammonium nitrate that contains 72g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 54000mg/L of COD are fed in the salt chamber of common electrical dialyzer from friendship waste liquid 6.0L; The initial liquid in dense chamber is the aqueous ammonium nitrate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.08 liters of the aqueous ammonium nitrate solution that concentration is about 5.0mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 50090mg/L of COD after measured, and BOD is 27100mg/L, reducing sugar 5g/L, and the pH value is about 3.1.

Embodiment 4

The common electrical dialyzer is with embodiment 1.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 53000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed in the salt chamber of common electrical dialyzer from friendship waste liquid 5.0L; The initial liquid in dense chamber is the ammonium sulfate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 4.4mol/L of the ammonium ion) aqueous solution that concentration is about 2.2mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 51000mg/L of COD after measured, and BOD is 25400mg/L, reducing sugar 5g/L, and the pH value is about 3.2.

Embodiment 5

The common electrical dialyzer is with embodiment 1.

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 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 2.7mol/L of the ammonium ion) aqueous solution that concentration is about 1.35mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 49700mg/L of COD after measured, and BOD is 25900mg/L, reducing sugar 5g/L, and the pH value is about 3.2.

The ammonium sulfate solution that obtains in the dense chamber is concentrated 2 times, be used for another batch fermenting lysine add ammonium sulfate, effect with prepare the ammonium sulfate solution that obtains with commodity ammonium sulfate and do not have marked difference.

Embodiment 6

The common electrical dialyzer is with embodiment 1.

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 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 3.09 liters of the aqueous ammonium chloride solution that concentration is about 0.9mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 49080mg/L of COD after measured, and BOD is 26080mg/L, reducing sugar 5g/L, and the pH value is about 3.3.

The aqueous ammonium chloride solution that obtains in the dense chamber is concentrated 6 times, be used for another batch fermenting lysine add ammonium chloride, effect with prepare the aqueous ammonium chloride solution that obtains with commodity ammonium chloride and do not have marked difference.

Embodiment 7

The common electrical dialyzer is with embodiment 1.

See also Fig. 4.The ammonium nitrate that contains 72g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 54000mg/L of COD are fed in the salt chamber of common electrical dialyzer from friendship waste liquid 5.0L; The initial liquid in dense chamber is the aqueous ammonium nitrate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.08 liters of the aqueous ammonium nitrate solution that concentration is about 4.7mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 51600mg/L of COD after measured, and BOD is 27800mg/L, reducing sugar 5g/L, and the pH value is about 3.1.

With the aqueous ammonium nitrate solution that obtains in the dense chamber, be used for another batch fermenting lysine add ammonium nitrate, effect with prepare the aqueous ammonium nitrate solution that obtains with commodity ammonium nitrate and do not have marked difference.

Embodiment 8

The common electrical dialyzer is with embodiment 1.

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 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 4.4mol/L of the ammonium ion) aqueous solution that concentration is about 2.2mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 50500mg/L of COD after measured, and BOD is 25400mg/L, reducing sugar 5g/L, and the pH value is about 3.2.

The ammonium sulfate solution that obtains in the dense chamber is concentrated 1.3 times, be used for another batch fermenting lysine add ammonium sulfate, effect with prepare the ammonium sulfate solution that obtains with commodity ammonium sulfate and do not have marked difference.

Embodiment 9

See also Fig. 2.

Common electrical dialyzer reclaim(ed) sulfuric acid ammonium: the common electrical dialyzer is the common electrical dialyzer of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of ion-exchange membrane is 210mm * 62mm, uses JAM-10 type anion-exchange membrane and JCM-1 type cationic exchange membrane.Anion-exchange membrane, cationic exchange membrane are formed 5 pairs of two compartment film stacking structure (as Fig. 5) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made negative plate.Dividing plate and filter are polypropylene material, and dividing plate is a no widely different road dividing plate, and filter is the mesh grid type.

The Methionin that contains 60g/L ammonium sulfate, the about 53000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed in the salt chamber of common electrical dialyzer from friendship waste liquid 3.0L; The initial liquid in dense chamber is the ammonium sulfate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 30 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 1.4mol/L of the ammonium ion) aqueous solution that concentration is about 0.7mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 50100mg/L of COD after measured, and BOD is 27200mg/L, reducing sugar 5g/L, and the pH value is about 3.3, the about 0.22mol/L of sulfur acid ammonium.

Bipolar membrane electrodialysis black sulfuric acid and ammonia: the bipolar membrane electrodialysis device is three Room bipolar membrane electrodialysis devices of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of 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 are formed 5 pairs of three compartment film stacking structure (as Fig. 6) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made negative plate.Dividing plate and filter are polypropylene material, and dividing plate is a no widely different road dividing plate, and filter is the mesh grid type.

The waste liquid 3.0L that the salt chamber of common electrical dialyzer is obtained feeds the salt chamber of three Room bipolar membrane electrodialysis devices; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L0.05mol/L, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of alkali chamber blows out regenerated ammonia with air, air-blowing quantity is 1 liter/minute.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 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.04 liters of the sulfuric acid that concentration is about 0.64mol/L.Absorb and to obtain mass concentration in the container and be about about 0.5 liter of 4% ammoniacal liquor.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 49900mg/L of COD after measured, and BOD is 26400mg/L, reducing sugar 4g/L, and the pH value is about 3.1.

Embodiment 10

See also Fig. 2.

Bipolar membrane electrodialysis black sulfuric acid and ammonia: the bipolar membrane electrodialysis device is two Room bipolar membrane electrodialysis devices of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of ion-exchange membrane 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. 7) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made negative plate.Dividing plate and filter are polypropylene material, and dividing plate is a no widely different road dividing plate, and filter is the mesh grid type.

The Methionin that contains 60g/L ammonium sulfate, the about 53000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of " salt-alkali " two Room merging of two Room bipolar membrane electrodialysis devices from friendship waste liquid 3.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L 0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of salt chamber blows out regenerated ammonia with air, air-blowing quantity is 0.5 liter/minute, and the gas that blows out contains the ammonia molar fraction after measured and is about 21%.The ammonia that blows out D/W with 0.5 liter of 400g/L in another container absorbs.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 32 μ S/cm, stop two Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.02 liters of the sulfuric acid that concentration is about 0.69mol/L.Absorb and to obtain the ammonia mass concentration in the container and be about about 0.5 liter of 4.5% liquid glucose.The waste liquid that obtains in the salt chamber of two Room bipolar membrane electrodialysis devices is the about 51200mg/L of COD after measured, and BOD is 26300mg/L, reducing sugar 4.9g/L, and the pH value is about 8.6, the about 0.22mol/L of sulfur acid ammonium.

Common electrical dialyzer reclaim(ed) sulfuric acid ammonium: the common electrical dialyzer is with embodiment 9.

The waste liquid 3.0L that the salt chamber of two Room bipolar membrane electrodialysis devices is obtained feeds in the salt chamber of common electrical dialyzer; The initial liquid in dense chamber is the ammonium sulfate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.04 liters of ammonium sulfate (the about 1.3mol/L of the ammonium ion) aqueous solution that concentration is about 0.65mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 50100mg/L of COD after measured, and BOD is 26200mg/L, reducing sugar 4g/L, and the pH value is about 8.1.

Embodiment 13

See also Fig. 2.

The Methionin that contains 60g/L ammonium sulfate, the about 53000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed in the salt chamber of common electrical dialyzer from friendship waste liquid 6.0L; The initial liquid in dense chamber is the ammonium sulfate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 19 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 4.06mol/L of the ammonium ion) aqueous solution that concentration is about 2.03mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 50300mg/L of COD after measured, and BOD is 26200mg/L, reducing sugar 5g/L, and the pH value is about 3.3, the about 0.11mol/L of sulfur acid ammonium.

Bipolar membrane electrodialysis black sulfuric acid and ammonia: the bipolar membrane electrodialysis device is with embodiment 9.

The waste liquid 6.0L that the salt chamber of common electrical dialyzer is obtained feeds the salt chamber of three Room bipolar membrane electrodialysis devices; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 0.3L0.05mol/L, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of alkali chamber blows out regenerated ammonia with air, air-blowing quantity is 1 liter/minute.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 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 0.3 liter of the sulfuric acid that concentration is about 2.2mol/L.Absorb about 0.5 liter of the ammoniacal liquor that obtains mass concentration about 4.5% in the container.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 49700mg/L of COD after measured, and BOD is 25300mg/L, reducing sugar 4g/L, and the pH value is about 3.1.

The pH regulator that the sulfuric acid that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 141g/L of Methionin) of another batch, its pH is adjusted to 3.2 from 6.9, consume about 0.076 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.Be about 4.5% ammoniacal liquor and add the pH regulator that liquefied ammonia to ammonia mass concentration 20% is used for the fermenting lysine of another batch absorbing the mass concentration that obtains in the container, effect with dilute the strong aqua that obtains with commodity liquefied ammonia and do not have marked difference.Be about 4.5% ammoniacal liquor to add liquefied ammonia and ammonium chloride to the mass concentration of ammonia mass concentration 15%, ammonium chloride be 20% absorbing the mass concentration that obtains in the container, be mixed with elutriant, be used for another batch absorption the wash-out of ion exchange column of Methionin, obtain containing the liquid of freeing that Methionin is 152g/L, effect is suitable with the elute effect of the elutriant that obtains with the preparation of commodity liquefied ammonia.

Embodiment 14

See also Fig. 2.

Bipolar membrane electrodialysis black sulfuric acid and ammonia: the bipolar membrane electrodialysis device is with embodiment 12.

The Methionin that contains 60g/L ammonium sulfate, the about 53000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of " salt-alkali " two Room merging of two Room bipolar membrane electrodialysis devices from friendship waste liquid 6.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of salt chamber blows out regenerated ammonia with air, air-blowing quantity is 0.5 liter/minute, and the gas that blows out contains ammonia molar fraction about 20% after measured.The ammonia that blows out D/W with 0.5 liter of 400g/L in another container absorbs.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 22 μ S/cm, stop two Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.05 liters of the sulfuric acid that concentration is about 0.67mol/L.Absorb obtain in the container that the ammonia mass concentration is about 4.6%, about 0.5 liter of the aqueous solution of glucose 400g/L.The waste liquid that obtains in the salt chamber of two Room bipolar membrane electrodialysis devices is the about 51800mg/L of COD after measured, and BOD is 26400mg/L, reducing sugar 5g/L, and the pH value is about 8.6, the about 0.34mol/L of sulfur acid ammonium.

The pH regulator that the sulfuric acid that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 145g/L of Methionin) of another batch, its pH is adjusted to 3.2 from 7.0, consume about 0.26 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The ammonia mass concentration that obtains in the container is about 4.6% with absorbing, to add liquefied ammonia to ammonia mass concentration be 15% to the aqueous solution of glucose 400g/L, the pH regulator sugar consumption of afterfermentation simultaneously that is used for the fermenting lysine of another batch, adopt the method for patent CN200510130636.9, effect does not have marked difference with the feed supplement liquid that obtains with the preparation of commodity liquefied ammonia.

The waste liquid 6.0L that the salt chamber of two Room bipolar membrane electrodialysis devices is obtained feeds in the salt chamber of common electrical dialyzer; The initial liquid in dense chamber is the ammonium sulfate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 3.9mol/L of the ammonium ion) aqueous solution that concentration is about 1.95mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 50100mg/L of COD after measured, and BOD is 25200mg/L, reducing sugar 4g/L, and the pH value is about 8.3.

Embodiment 17

Degerming, remove albumen: the Methionin that contains 60g/L ammonium sulfate, the about 53000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. from the 0.2 μ m microfiltration membrane and the filtration of 3K hyperfiltration membrane assembly of handing over waste liquid through Tianjin MoTian Membrane Engineering Technology Co., Ltd, is obtained about 10 liters of clear liquid.

With the above-mentioned sulfur acid ammonium that obtains from handing over the waste liquid clear liquid by being filled with 6.0L (resin floor height 1000mm * internal diameter 90mm) H ⁺The ion exchange column of type D072 Zeo-karb makes calcium ions and magnesium ions in handing over waste liquid by H ⁺Exchange absorption.The upper prop flow be 2 column volumes/hour, at the bottom of post, collect about 8L contain the 70mg/L calcium ions and magnesium ions from handing over waste liquid.

See also Fig. 2.

With the sulfur acid ammonium of the above-mentioned decalcification magnesium that obtains from handing over waste liquid 6.0L to feed in the salt chamber of common electrical dialyzer; The initial liquid in dense chamber is the ammonium sulfate solution of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 19 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 4.06mol/L of the ammonium ion) aqueous solution that concentration is about 2.03mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 30300mg/L of COD after measured, and BOD is 16200mg/L, reducing sugar 4.5g/L, and the pH value is about 3.3, the about 0.11mol/L of sulfur acid ammonium.

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 regenerated ammonia with air, air-blowing quantity is 1 liter/minute.The ammonia that blows out ammonium sulfate solution water with 0.15 liter of 280g/L in another container 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 three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 0.3 liter of the sulfuric acid that concentration is about 2.2mol/L.Absorb obtain in the container that the ammonia mass concentration is about 15%, about 0.5 liter of the aqueous solution of the about 280g/L of ammonium sulfate.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 29700mg/L of COD after measured, and BOD is 15300mg/L, reducing sugar 4g/L, and the pH value is about 3.1.

The pH regulator that the sulfuric acid that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 141g/L of Methionin) of another batch, its pH is adjusted to 3.2 from 6.9, consume about 0.076 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The pH regulator of the fermenting lysine that the ammonia mass concentration that obtains in the container is about 15% with absorbing, the aqueous solution of the about 280g/L of ammonium sulfate is used for another batch and add ammonium sulfate, effect with prepare the feed supplement liquid that obtains with commodity liquefied ammonia and do not have marked difference.

Culturing yeast: the yeast that uses is saccharomyces cidri (Saccharomyces cerevisiae, the As2.374 of China common micro-organisms DSMZ), Candida utilis (Candida utilis, As2.281) and candida tropicalis (Candida tropicalis, As2.637).

The seed culture medium of three primary yeasts all is the YPD substratum: glucose 20g/L, peptone 10g/L, yeast powder 10g/L, potassium primary phosphate 2g/L, ammonium sulfate 5g/L, sal epsom 0.1g/L.Transferring the medium pH value with NaOH is about 6.Three primary yeast seeds are inserted seed culture medium respectively, and 300 rev/mins of shaking speed were cultivated 24 hours for 28 ℃, obtained the kind liquid of three primary yeasts.

The about 1.5L of waste liquid that the salt chamber of three Room bipolar membrane electrodialysis devices is obtained packs in the 2L fermentor tank, without sterilization.Insert above-mentioned three all liquid by 5% inoculum size respectively.Culture temperature is controlled at 28 ± 0.5 ℃, and 200 rev/mins of mixing speed were cultivated 12 hours, and dry cell weight reaches 14g/L.The COD of centrifugal gained supernatant liquor reduces to 3100mg/L.

Embodiment 18

Degerming, remove albumen: the Methionin of the ammonium chloride that contains 48g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the about 52000mg/L of COD from the 0.2 μ m microfiltration membrane and the filtration of 6K hyperfiltration membrane assembly of handing over waste liquid through Tianjin MoTian Membrane Engineering Technology Co., Ltd, is obtained about 10 liters of clear liquid.

With above-mentioned obtain contain ammonium chloride from handing over the waste liquid clear liquid by being filled with the adsorption column of 3L (resin floor height 500mm * internal diameter 90mm) D402 huge legendary turtle mould assembly ion exchange resin, the calcium ions and magnesium ions in handing over waste liquid is adsorbed.The upper prop flow be 1.5 column volumes/hour, at the bottom of post, collect about 8L contain the 60mg/L calcium ions and magnesium ions from handing over waste liquid.

See also Fig. 2.

The Methionin of the above-mentioned sulfur acid ammonium that obtains is fed the salt chamber of " salt-alkali " two Room merging of two Room bipolar membrane electrodialysis devices from the clear liquid 6.0L that hands over waste liquid; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of salt chamber blows out regenerated ammonia with air, air-blowing quantity is 0.5 liter/minute, and the gas that blows out contains ammonia molar fraction about 20% after measured.The ammonia that blows out aqueous ammonium chloride solution water with 0.25 liter of 140g/L in another container absorbs.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 22 μ S/cm, stop two Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.05 liters of the sulfuric acid that concentration is about 0.67mol/L.Absorb obtain in the container that the ammonia mass concentration is about 9%, 0.25 liter of the aqueous solution of the about 140g/L of ammonium chloride.The waste liquid that obtains in the salt chamber of two Room bipolar membrane electrodialysis devices is the about 27800mg/L of COD after measured, and BOD is 14400mg/L, reducing sugar 4.5g/L, and the pH value is about 8.6, the about 0.34mol/L of sulfur acid ammonium.

The pH regulator that the sulfuric acid that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 145g/L of Methionin) of another batch, its pH is adjusted to 3.2 from 7.0, consume about 0.26 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The absorption that the ammonia mass concentration that obtains in the container is about 9% with absorbing, the aqueous solution of the about 140g/L of ammonium chloride is used for another batch the wash-out of ion exchange column of Methionin, obtain containing the liquid of freeing that Methionin is 95g/L, effect is suitable with the elute effect of the elutriant that obtains with the preparation of commodity liquefied ammonia.

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 5 μ S/cm, stop the common electrical dialysis operation.In dense chamber, obtain about 1.05 liters of ammonium sulfate (the about 3.9mol/L of the ammonium ion) aqueous solution that concentration is about 1.95mol/L.The waste liquid that obtains in the salt chamber of common electrical dialyzer is the about 26100mg/L of COD after measured, and BOD is 13200mg/L, reducing sugar 4g/L, and the pH value is about 8.3.

Embodiment 21

The bipolar membrane electrodialysis device is three Room bipolar membrane electrodialysis devices of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of 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 are formed 5 pairs of three compartment film stacking structure (as Fig. 6) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made negative plate.Dividing plate and filter are polypropylene material, and dividing plate is a no widely different road dividing plate, and filter is the mesh grid type.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 52000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 3.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L0.05mol/L, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of alkali chamber blows out regenerated ammonia with air, air-blowing quantity is 1 liter/minute.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 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.05 liters of the sulfuric acid that concentration is about 1.35mol/L.Absorb and to obtain mass concentration in the container and be about about 0.5 liter of 9% ammoniacal liquor.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 50100mg/L of COD after measured, and BOD is 27400mg/L, reducing sugar 5g/L, and the pH value is about 3.3.

Embodiment 22

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 3.The ammonium chloride that contains 48g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 51000mg/L of COD are fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 3.0L; The initial liquid in acid chamber is the dilute hydrochloric acid solution of 1.0L0.05mol/L, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of alkali chamber blows out regenerated ammonia 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.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 three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.09 liters of the hydrochloric acid that concentration is about 2.7mol/L.In the receiving bottle of the refrigerator inner coil the other end, obtain about 42 gram liquefied ammonia.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 49000mg/L of COD after measured, and BOD is 26600mg/L, reducing sugar 5g/L, and the pH value is about 3.1.

Embodiment 23

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 4.The ammonium nitrate that contains 72g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 53000mg/L of COD are fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 3.0L; Acid chamber initial liquid is the dilute nitric acid solution of 1.0L0.05mol/L, and the initial liquid in alkali chamber is 0.5% ammoniacal liquor for the 0.5L mass concentration, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.08 liters of the nitric acid that concentration is about 2.8mol/L.Obtain about 0.5 liter of the ammoniacal liquor of mass concentration about 9% in the alkali chamber.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 50050mg/L of COD after measured, and BOD is 27400mg/L, reducing sugar 5g/L, and the pH value is about 3.3.

Embodiment 24

The bipolar membrane electrodialysis device is two Room bipolar membrane electrodialysis devices of one section one-level, separate unit independent operating, and the liquid flow path direction in the adjacent compartments adopts and be streamed.The area of ion-exchange membrane 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. 7) repeated arrangement.Use titanium to be coated with ruthenium electrode and make positive plate, stainless steel electrode is made negative plate.Dividing plate and filter are polypropylene material, and dividing plate is a no widely different road dividing plate, and filter is the mesh grid type.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 52000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of " salt-alkali " two Room merging of two Room bipolar membrane electrodialysis devices from friendship waste liquid 3.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of salt chamber blows out regenerated ammonia with air, air-blowing quantity is 0.5 liter/minute, and the gas that blows out contains the ammonia molar fraction after measured and is about 21%.The ammonia that blows out D/W with 0.5 liter of 400g/L in another container 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 two Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.03 liters of the sulfuric acid that concentration is about 1.4mol/L.Absorb and to obtain the ammonia mass concentration in the container and be about about 0.5 liter of 9% liquid glucose.The waste liquid that obtains in the salt chamber of two Room bipolar membrane electrodialysis devices is the about 51300mg/L of COD after measured, and BOD is 26800mg/L, reducing sugar 5g/L, and the pH value is about 8.6.

Embodiment 25

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 52000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 5.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L0.05mol/L, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of alkali chamber blows out regenerated ammonia with air, air-blowing quantity is 1 liter/minute.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 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.01 liters of the sulfuric acid that concentration is about 2.2mol/L.Absorb about 0.5 liter of the ammoniacal liquor that obtains mass concentration about 15% in the container.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 50500mg/L of COD after measured, and BOD is 27300mg/L, reducing sugar 5g/L, and the pH value is about 3.3.

The sulfuric acid that obtains in the sour chamber is used for the pH regulator of the 1L lysine fermentation liquor (containing the about 140g/L of Methionin) of another batch, its pH is adjusted to 3.3 from 6.8, consume about 0.075 liter of sulfuric acid, last H ⁺The Methionin adsorption rate of type 732 resin columns and conventional ion exchange absorption do not have marked difference.Be about the pH regulator that 15% ammoniacal liquor is used for the fermenting lysine of another batch with absorbing the mass concentration that obtains in the container, effect with dilute the strong aqua that obtains with commodity liquefied ammonia and do not have marked difference.Be about 15% ammoniacal liquor to add ammonium chloride be 20% to the mass concentration of ammonium chloride absorbing the mass concentration that obtains in the container, be mixed with elutriant, be used for another batch absorption the wash-out of ion exchange column of Methionin, obtain containing the liquid of freeing that Methionin is 150g/L, effect is suitable with the elute effect of the elutriant that obtains with the preparation of commodity liquefied ammonia.

Embodiment 26

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 3.The ammonium chloride that contains 48g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 51000mg/L of COD are fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 5.0L; The initial liquid in acid chamber is the dilute hydrochloric acid solution of 1.0L0.05mol/L, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of alkali chamber blows out regenerated ammonia with air, air-blowing quantity is 1 liter/minute.The ammonia that blows out from the alkali chamber feeds the stainless steel coiled pipe that places in-60 ℃ of refrigerators.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 three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.08 liters of the hydrochloric acid that concentration is about 4.5mol/L.In the receiving bottle of the refrigerator inner coil the other end, obtain about 70 gram liquefied ammonia.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 49700mg/L of COD after measured, and BOD is 24600mg/L, reducing sugar 5g/L, and the pH value is about 3.1.

The pH regulator that the hydrochloric acid that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 140g/L of Methionin) of another batch, its pH is adjusted to 3.4 from 6.9, consume about 0.071 liter of hydrochloric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The liquefied ammonia dilution that condensation is obtained is about the pH regulator that 25% ammoniacal liquor is used for the fermenting lysine of another batch for mass concentration, effect with dilute the strong aqua that obtains with commodity liquefied ammonia and do not have marked difference.The liquefied ammonia dilution that condensation is obtained is about 18% ammoniacal liquor for mass concentration, be used for another batch absorption the wash-out of ion exchange column of Methionin, obtain containing the liquid of freeing that Methionin is 143g/L, effect is suitable with the elute effect of the elutriant that obtains with the preparation of commodity liquefied ammonia.

Embodiment 27

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 4.The ammonium nitrate that contains 72g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 53000mg/L of COD are fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 5.0L; Acid chamber initial liquid is the dilute nitric acid solution of 1.0L0.05mol/L, and the initial liquid in alkali chamber is 0.5% ammoniacal liquor for the 0.5L mass concentration, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.03 liters of the nitric acid that concentration is about 4.6mol/L.Obtain about 0.5 liter of the ammoniacal liquor of mass concentration about 15% in the alkali chamber.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 51000mg/L of COD after measured, and BOD is 27500mg/L, reducing sugar 5g/L, and the pH value is about 3.2.

The pH regulator that the nitric acid that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 140g/L of Methionin) of another batch, its pH is adjusted to 3.5 from 7.0, consume about 0.072 liter of nitric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The ammoniacal liquor of the mass concentration about 15% that will obtain in the alkali chamber is used for the pH regulator of the fermenting lysine of another batch, and effect does not have marked difference with the strong aqua that obtains with the dilution of commodity liquefied ammonia.It is 20% to the mass concentration of ammonium chloride that the ammoniacal liquor of the mass concentration about 15% that will obtain in the alkali chamber is added ammonium chloride, be mixed with elutriant, be used for another batch absorption the wash-out of ion exchange column of Methionin, obtain containing the liquid of freeing that Methionin is 150g/L, effect is suitable with the elute effect of the elutriant that obtains with the preparation of commodity liquefied ammonia.

Embodiment 28

The bipolar membrane electrodialysis device is with embodiment 24.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 52000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of " salt-alkali " two Room merging of two Room bipolar membrane electrodialysis devices from friendship waste liquid 5.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.0L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of salt chamber blows out regenerated ammonia with air, air-blowing quantity is 0.5 liter/minute, and the gas that blows out contains ammonia molar fraction about 20% after measured.The ammonia that blows out D/W with 1.5 liters of 400g/L in another container 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 two Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.05 liters of the sulfuric acid that concentration is about 2.2mol/L.Absorb obtain in the container that the ammonia mass concentration is about 5%, about 1.5 liters of the aqueous solution of glucose 400g/L.The waste liquid that obtains in the salt chamber of two Room bipolar membrane electrodialysis devices is the about 51800mg/L of COD after measured, and BOD is 26400mg/L, reducing sugar 5g/L, and the pH value is about 8.6.

The pH regulator that the sulfuric acid that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 145g/L of Methionin) of another batch, its pH is adjusted to 3.3 from 6.9, consume about 0.079 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The ammonia mass concentration that obtains in the container is about 5% with absorbing, the aqueous solution of glucose 400g/L is added liquefied ammonia to ammonia mass concentration about 15%, the pH regulator sugar consumption of afterfermentation simultaneously that is used for the fermenting lysine of another batch, adopt the method for patent CN200510130636.9, effect does not have marked difference with the feed supplement liquid that obtains with the preparation of commodity liquefied ammonia.

Embodiment 29

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 52000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 2.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.5L0.05mol/L, and the initial liquid in alkali chamber is the ammonium sulfate solution of 0.2 liter of 280g/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.57 liters of the sulfuric acid that concentration is about 0.55mol/L.Obtain in the alkali chamber that the ammonia mass concentration is about 15%, about 0.2 liter of the aqueous solution of the about 280g/L of ammonium sulfate.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 49800mg/L of COD after measured, and BOD is 24980mg/L, reducing sugar 5g/L, and the pH value is about 3.4.

With 4 times of the sulphuric acid concentration that obtain in the sour chamber, be used for the pH regulator of the 1L lysine fermentation liquor (containing the about 142g/L of Methionin) of another batch, its pH is adjusted to 3.3 from 6.9, consume about 0.074 liter of sulfuric acid, last H ⁺The Methionin adsorption rate of type 732 resin columns and conventional ion exchange absorption do not have marked difference.With the pH regulator of the fermenting lysine that the ammonia mass concentration that obtains in the alkali chamber is about 15%, the aqueous solution of the about 280g/L of ammonium sulfate is used for another batch with add ammonium sulfate, effect with prepare the feed supplement liquid that obtains with commodity liquefied ammonia and do not have marked difference.

Embodiment 30

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 3.The ammonium chloride that contains 48g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 51000mg/L of COD are fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 2.0L; The initial liquid in acid chamber is the dilute hydrochloric acid solution of 1.5L0.05mol/L, and the initial liquid in alkali chamber is the aqueous ammonium chloride solution of 0.2 liter of 230g/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.58 liters of the hydrochloric acid that concentration is about 1.08mol/L.Obtain in the alkali chamber that the ammonia mass concentration is about 15%, about 0.2 liter of the aqueous solution of the about 230g/L of ammonium chloride.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 49900mg/L of COD after measured, and BOD is 24700mg/L, reducing sugar 5g/L, and the pH value is about 3.0.

The hydrochloric acid that obtains in the sour chamber is concentrated 4 times, the pH regulator that is used for the 1L lysine fermentation liquor (containing the about 139g/L of Methionin) of another batch, its pH is adjusted to 3.4 from 6.9, consume about 0.072 liter of hydrochloric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The pH regulator of the fermenting lysine that the ammonia mass concentration is about 15% with obtaining in the alkali chamber, the aqueous solution of the about 230g/L of ammonium chloride is used for another batch and add ammonium chloride, effect with prepare the feed supplement liquid that obtains with commodity liquefied ammonia and do not have marked difference.

Embodiment 31

The bipolar membrane electrodialysis device is with embodiment 21.

See also Fig. 4.The ammonium nitrate that contains 72g/L of Chinese Ningxia Yipin Biological Engineering Co., Ltd., the Methionin of the about 53000mg/L of COD are fed the salt chamber of three Room bipolar membrane electrodialysis devices from friendship waste liquid 2.0L; The initial liquid in acid chamber is the dilute nitric acid solution of 1.5L0.05mol/L, and the initial liquid in alkali chamber is the aqueous ammonium chloride solution of 0.2 liter of 200g/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Measure the electric conductivity value of feed liquid in the salt chamber every 10 minutes, when electric conductivity value drops to 5 μ S/cm, stop three Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.53 liters of the nitric acid that concentration is about 1.12mol/L.Obtain in the alkali chamber that the ammonia mass concentration is about 15%, about 0.2 liter of the aqueous solution of the about 200g/L of ammonium chloride.The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 51300mg/L of COD after measured, and BOD is 27200mg/L, reducing sugar 5g/L, and the pH value is about 3.1.

The nitric acid that obtains in the sour chamber is concentrated 4 times, the pH regulator that is used for the 1L lysine fermentation liquor (containing the about 142g/L of Methionin) of another batch, its pH is adjusted to 3.5 from 6.9, consume about 0.070 liter of nitric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.

With the ammonia mass concentration that obtains in the alkali chamber be about 15%, the aqueous solution of the about 200g/L of ammonium chloride, be used for another batch absorption the wash-out of ion exchange column of Methionin, obtain containing the liquid of freeing that Methionin is 151g/L, effect is suitable with the elute effect of the elutriant that obtains with the preparation of commodity liquefied ammonia.

Embodiment 32

The bipolar membrane electrodialysis device is with embodiment 24.

See also Fig. 2.The Methionin that contains 60g/L ammonium sulfate, the about 52000mg/L of COD of Chinese Ningxia Yipin Biological Engineering Co., Ltd. is fed the salt chamber of " salt-alkali " two Room merging of two Room bipolar membrane electrodialysis devices from friendship waste liquid 2.0L; The initial liquid in acid chamber is the dilution heat of sulfuric acid of 1.5L0.05mol/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.

Control current density 30mA/cm in the operating process ², liquid-flow linear velocity 3cm/s in each compartment, 30 ℃ of each chamber feed temperatures.Bubbling air in the material cylinder of salt chamber blows out regenerated ammonia with air, air-blowing quantity is 0.5 liter/minute, and the gas that blows out contains ammonia molar fraction about 20% after measured.The ammonia that blows out aqueous ammonium nitrate solution with 0.2 liter of 340g/L in another container 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 two Room bipolar membrane electrodialysis operations.In sour chamber, obtain about 1.55 liters of the sulfuric acid that concentration is about 0.56mol/L.Obtain in absorbing container that the ammonia mass concentration is about 15%, about 0.2 liter of the aqueous solution of the about 340g/L of ammonium nitrate.The waste liquid that obtains in the salt chamber of two Room bipolar membrane electrodialysis devices is the about 51300mg/L of COD after measured, and BOD is 26200mg/L, reducing sugar 5g/L, and the pH value is about 8.8.

With 4 times of the sulphuric acid concentration that obtain in the sour chamber, the pH regulator that is used for the 1L lysine fermentation liquor (containing the about 144g/L of Methionin) of another batch, its pH is adjusted to 3.3 from 6.9, consume about 0.077 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.The ammonia mass concentration that obtains in the container is about 15% with absorbing, the aqueous solution of the about 340g/L of ammonium nitrate is used for the additional simultaneously ammonium nitrate of pH regulator of the fermenting lysine of another batch, adopt the method for patent CN200510130636.9, effect does not have marked difference with the feed supplement liquid that obtains with the preparation of commodity liquefied ammonia.

Embodiment 33

Used Methionin is from handing over waste liquid with embodiment 21.

Degerming, remove albumen: Methionin is filtered from 0.2 μ m microfiltration membrane and the 1K hyperfiltration membrane assembly of handing over waste liquid through Tianjin MoTian Membrane Engineering Technology Co., Ltd, obtain about 2.5 liters of clear liquid.

See also Fig. 2.

Bipolar membrane electrodialysis is from handing over the spent solution regeneration soda acid: the bipolar membrane electrodialysis device is with embodiment 21.With the above-mentioned sulfur acid ammonium that obtains from handing over waste liquid clear liquid 2L to feed the salt chamber of three Room bipolar membrane electrodialysis devices; The initial liquid in acid chamber is the lysine fermentation liquor of 0.5L degerming, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.The operation of bipolar membrane electrodialysis device is with embodiment 21.When dropping to 5 μ S/cm, electric conductivity value stops three Room bipolar membrane electrodialysis operations.In sour chamber, obtain containing about 0.6 liter of the solution of the about 140g/L of Methionin, the about 1.6mol/L of sulfur acid; Absorb and to obtain mass concentration in the container and be about about 0.5 liter of 6% ammoniacal liquor; The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 33500mg/L of COD after measured, and BOD is 17400mg/L, reducing sugar 4.7g/L, and the pH value is about 3.2.The energy loss-rate embodiment 21 of bipolar membrane electrodialysis regeneration unit mass ammonium sulfate reduces by 14%.

The about 900mL of waste liquid of the salt chamber after bipolar membrane electrodialysis handled packs in the 2L fermentor tank, without sterilization.Insert above-mentioned three all liquid by 5% inoculum size respectively.Culture temperature is controlled at 28 ± 0.5 ℃, and 180 rev/mins of mixing speed were cultivated 12 hours, and dry cell weight reaches 15g/L.The COD of centrifugal gained supernatant liquor reduces to 4800mg/L.

Embodiment 34

Used Methionin is from handing over waste liquid with embodiment 21.

Degerming, remove albumen: Methionin is filtered from 0.2 μ m microfiltration membrane and the 3K hyperfiltration membrane assembly of handing over waste liquid through Tianjin MoTian Membrane Engineering Technology Co., Ltd, obtain about 2.5 liters of clear liquid.

With the above-mentioned sulfur acid ammonium that obtains from handing over the waste liquid clear liquid by being filled with 1.5L (resin floor height 1000mm * internal diameter 45mm) H ⁺The ion exchange column of type D072 Zeo-karb makes calcium ions and magnesium ions in handing over waste liquid by H ⁺Exchange absorption.The upper prop flow be 2 column volumes/hour, at the bottom of post, collect about 2.2L contain the 70mg/L calcium ions and magnesium ions from handing over waste liquid.

See also Fig. 2.

Bipolar membrane electrodialysis is from handing over the spent solution regeneration soda acid: the bipolar membrane electrodialysis device is with embodiment 21.With the sulfur acid ammonium of the above-mentioned decalcification magnesium that obtains from handing over waste liquid 2L to feed the salt chamber of three Room bipolar membrane electrodialysis devices; The initial liquid in acid chamber is the dilution fermented liquid that contain Methionin about 30g/L of 0.5L with the lysine fermentation liquor thin up of degerming, and the initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.The operation of bipolar membrane electrodialysis device is with embodiment 21.When dropping to 5 μ S/cm, electric conductivity value stops three Room bipolar membrane electrodialysis operations.In sour chamber, obtain containing about 0.6 liter of the solution of the about 30g/L of Methionin, the about 1.6mol/L of sulfur acid; Absorb and to obtain mass concentration in the container and be about about 0.5 liter of 6% ammoniacal liquor; The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 33100mg/L of COD after measured, and BOD is 17030mg/L, reducing sugar 4.7g/L, and the pH value is about 3.0.The energy loss-rate embodiment 21 of bipolar membrane electrodialysis regeneration unit mass ammonium sulfate reduces by 16%.

The pH regulator that the sulfur acid solution that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 140g/L of Methionin) of another batch, its pH is adjusted to 3.3 from 6.9, consume about 0.055 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.

Embodiment 35

Used Methionin is from handing over waste liquid with embodiment 21.

Degerming, remove albumen: Methionin is filtered from 0.2 μ m microfiltration membrane and the 6K hyperfiltration membrane assembly of handing over waste liquid through Tianjin MoTian Membrane Engineering Technology Co., Ltd, obtain about 2.5 liters of clear liquid.

With the above-mentioned sulfur acid ammonium that obtains from handing over the waste liquid clear liquid by being filled with the adsorption column of 0.75L (resin floor height 500mm * internal diameter 45mm) D402 huge legendary turtle mould assembly ion exchange resin, the calcium ions and magnesium ions in handing over waste liquid is adsorbed.The upper prop flow be 1.5 column volumes/hour, at the bottom of post, collect about 2.2L contain the 60mg/L calcium ions and magnesium ions from handing over waste liquid.

See also Fig. 2.

Bipolar membrane electrodialysis is from handing over the spent solution regeneration soda acid: the bipolar membrane electrodialysis device is with embodiment 21.With the sulfur acid ammonium of the above-mentioned decalcification magnesium that obtains from handing over waste liquid 2L to feed the salt chamber of three Room bipolar membrane electrodialysis devices; The initial liquid in acid chamber is the dilution fermented liquid that contain Methionin about 60g/L of 0.5L with the lysine fermentation liquor thin up, and the initial liquid in alkali chamber is the aqueous ammonium chloride solution of 0.2 liter of 200g/L, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.The operation of bipolar membrane electrodialysis device is with embodiment 21.When dropping to 5 μ S/cm, electric conductivity value stops three Room bipolar membrane electrodialysis operations.In sour chamber, obtain containing about 0.6 liter of the solution of the about 60g/L of Methionin, the about 1.6mol/L of sulfur acid; Indoorly obtain that the ammonia mass concentration is about 15% at alkali, about 0.2 liter of the aqueous solution of the about 200g/L of ammonium chloride; The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 32300mg/L of COD after measured, and BOD is 17060mg/L, reducing sugar 4.6g/L, and the pH value is about 3.0.The energy loss-rate embodiment 21 of bipolar membrane electrodialysis regeneration unit mass ammonium sulfate reduces by 18%.

The sulfur acid solution that obtains in the sour chamber is used for the pH regulator of the 1L lysine fermentation liquor (containing the about 144g/L of Methionin) of another batch, its pH is adjusted to 3.3 from 7.0, consume about 0.057 liter of sulfuric acid, last H ⁺The Methionin adsorption rate of type 732 resin columns and conventional ion exchange absorption do not have marked difference.

With the ammonia mass concentration that obtains in the alkali chamber be about 15%, the aqueous solution of the about 200g/L of ammonium chloride, be used for another batch absorption the wash-out of ion exchange column of Methionin, obtain containing the liquid of freeing that Methionin is 149g/L, effect is suitable with the elute effect of the elutriant that obtains with the preparation of commodity liquefied ammonia.

Embodiment 36

Used Methionin is from handing over waste liquid with embodiment 21.

Degerming, remove albumen: Methionin is filtered from 0.2 μ m microfiltration membrane and the 10K hyperfiltration membrane assembly of handing over waste liquid through Tianjin MoTian Membrane Engineering Technology Co., Ltd, obtain about 2.5 liters of clear liquid.

Concentrate from handing over waste liquid: above-mentioned Methionin is concentrated 2 times from the clear liquid heating of handing over waste liquid.

Decalcification magnesium ion: in above-mentioned spissated clear liquid, add the oxalic acid of 0.05mol/L, mix the back room temperature and placed 4 hours, remove by filter precipitation.Removing post precipitation mensuration is 65mg/L from the calcium ions and magnesium ions concentration of handing over waste liquid.

See also Fig. 2.

Bipolar membrane electrodialysis is from handing over the spent solution regeneration soda acid: the bipolar membrane electrodialysis device is with embodiment 21.With the sulfur acid ammonium of the above-mentioned decalcification magnesium that obtains from handing over waste liquid 1L to feed the salt chamber of three Room bipolar membrane electrodialysis devices; The initial liquid in acid chamber is the dialyzate of 0.5L lysine fermentation liquor membrane filtration, contains the about 100g/L of Methionin; The initial liquid in alkali chamber is the 1L0.05mol/L sodium hydroxide solution, and chamber, the two poles of the earth liquid is the metabisulfite solution of 1L0.25mol/L.The operation of bipolar membrane electrodialysis device is with embodiment 21.When dropping to 8 μ S/cm, electric conductivity value stops three Room bipolar membrane electrodialysis operations.In sour chamber, obtain containing about 0.6 liter of the solution of the about 100g/L of Methionin, the about 1.6mol/L of sulfur acid; Absorb about 0.5 liter of the ammoniacal liquor that obtains mass concentration about 6% in the container; The waste liquid that obtains in the salt chamber of three Room bipolar membrane electrodialysis devices is the about 64500mg/L of COD after measured, and BOD is 34400mg/L, reducing sugar 9.7g/L, and the pH value is about 3.1.The energy loss-rate embodiment 21 of bipolar membrane electrodialysis regeneration unit mass ammonium sulfate reduces by 25%.

The pH regulator that the sulfur acid solution that obtains in the sour chamber is used for the 1L lysine fermentation liquor (containing the about 142g/L of Methionin) of another batch, its pH is adjusted to 3.5 from 6.9, consume about 0.051 liter of sulfuric acid, the Methionin adsorption rate of last H+ type 732 resin columns and conventional ion exchange absorption do not have marked difference.

The about 900mL of waste liquid of the salt chamber after bipolar membrane electrodialysis handled packs in the 2L fermentor tank, without sterilization.Insert above-mentioned three all liquid by 5% inoculum size respectively.Culture temperature is controlled at 28 ± 0.5 ℃, and 180 rev/mins of mixing speed were cultivated 18 hours, and dry cell weight reaches 27g/L.The COD of centrifugal gained supernatant liquor reduces to 7200mg/L.

Claims

In the fermentative Production Methionin from the treatment process of handing over waste liquid, be to adopt the common electrical osmotic technique when fermenting lysine is produced, to extract Methionin that Methionin produces is recovered as ammonium sulfate, ammonium chloride or ammonium nitrate ammonium sulfate, ammonium chloride or ammonium nitrate from the friendship waste liquid the aqueous solution; Or the Methionin that adopts the bipolar membrane electrodialysis technology to extract the Methionin generation when fermenting lysine is produced is regenerated as sulfuric acid, hydrochloric acid or nitric acid and NH3 with ammonium sulfate, ammonium chloride or ammonium nitrate from handing over waste liquid; Or adopting common electrical osmotic technique and bipolar membrane electrodialysis technology to combine, the Methionin that extracts the Methionin generation when fermenting lysine is produced reclaims and is regenerated as sulfuric acid, hydrochloric acid or nitric acid and NH with ammonium sulfate, ammonium chloride or ammonium nitrate from handing over waste liquid ₃It is characterized in that:

To contain NH ₄ ⁺The Methionin of vitriol, hydrochloride or nitrate from handing over waste liquid to feed in the salt chamber of common electrical dialyzer; Open the common electrical dialyzer Methionin that feeds the salt chamber is handled from the friendship waste liquid, be reduced to needed concentration up to the inorganic acid radical concentration of the Methionin that enters the salt chamber in handing over waste liquid, or NH ₄ ⁺Concentration is reduced to needed concentration, finishes Methionin from the processing of handing over waste liquid; Wherein:

The aqueous solution of ammonium sulfate, ammonium chloride or the ammonium nitrate that obtains reclaiming in the dense chamber of common electrical dialyzer, the Methionin after the salt chamber obtains desalination is from handing over waste liquid; Or

To contain NH ₄ ⁺The Methionin of vitriol, hydrochloride or nitrate from handing over waste liquid to feed in the salt chamber of three Room bipolar membrane electrodialysis devices, or feed in the salt chamber that salt-alkali two Room of two Room bipolar membrane electrodialysis devices merge; Open the bipolar membrane electrodialysis device Methionin that feeds the salt chamber is handled from the friendship waste liquid, be reduced to needed concentration up to the inorganic acid radical concentration of the Methionin that enters the salt chamber in handing over waste liquid, or NH ₄ ⁺Concentration is reduced to needed concentration, finishes Methionin from the processing of handing over waste liquid; Wherein:

Sour chamber at three Room bipolar membrane electrodialysis devices obtains regenerated sulfuric acid, hydrochloric acid or nitric acid, obtains regenerated NH in the alkali chamber ₃, the Methionin after the salt chamber obtains desalination is from handing over waste liquid;

Sour chamber at two Room bipolar membrane electrodialysis devices obtains regenerated sulfuric acid, hydrochloric acid or nitric acid, obtains regenerated NH in the salt chamber that salt-alkali two Room merge ₃, NH ₃Be blown the Methionin of back after the salt chamber obtains desalination from handing over waste liquid.
2. method according to claim 1 is characterized in that: the ammonium concentration in the aqueous solution of described ammonium sulfate, ammonium chloride or the ammonium nitrate that obtains reclaiming in the dense chamber of common electrical dialyzer is 0.5～5mol/L; Described sour chamber or the regenerated vitriolic concentration that obtains of the sour chamber of two Room bipolar membrane electrodialysis devices at three Room bipolar membrane electrodialysis devices is 0.5～2.5mol/L; Described at three Room bipolar membrane electrodialysis devices sour chamber or the concentration of the regenerated hydrochloric acid that obtains of the sour chamber of two Room bipolar membrane electrodialysis devices be 1～5mol/L; Described at three Room bipolar membrane electrodialysis devices sour chamber or the concentration of the regenerated nitric acid that obtains of the sour chamber of two Room bipolar membrane electrodialysis devices be 1～5mol/L.
3. method according to claim 1 and 2 is characterized in that: the aqueous solution of described ammonium sulfate, ammonium chloride or the ammonium nitrate that obtains reclaiming in the dense chamber of common electrical dialyzer directly or replenish ammonium sulfate, ammonium chloride or ammonium nitrate when being used for fermentative production Methionin after concentrating;

Described sour chamber or the sour chamber of two Room bipolar membrane electrodialysis devices the regenerated sulfuric acid, hydrochloric acid or the nitric acid that obtain at three Room bipolar membrane electrodialysis devices is directly or through being used to regulate the pH of the preceding lysine fermentation liquor of cationic exchange coloum after concentrating.
4. method according to claim 1 is characterized in that: will obtain regenerated NH in the alkali chamber of three Room bipolar membrane electrodialysis devices ₃, or

Obtain regenerated NH in the salt chamber that will merge in salt-alkali two Room of two Room bipolar membrane electrodialysis devices ₃, or

Feeding medium during fermentation liquid glucose or ammonium sulfate solution or aqueous ammonium chloride solution or aqueous ammonium nitrate solution in the time of will be with fermentative production Methionin, be absorbed in the ammoniated liquid glucose that regenerated ammonia that the alkali chamber of three Room bipolar membrane electrodialysis devices obtains or the regenerated ammonia that obtains obtain in the salt chamber that salt-alkali two Room of two Room bipolar membrane electrodialysis devices merge, or the ammoniated ammonium sulfate solution that obtains, or the ammoniated aqueous ammonium chloride solution that obtains, or the ammoniated aqueous ammonium nitrate solution that obtains;

Add ammonia and/or ammonium to fermented liquid when being used for fermentative production Methionin, and/or be used for the Methionin of wash-out absorption from the cationic exchange coloum that is adsorbed with Methionin; Described NH ₃Be ammoniacal liquor, liquefied ammonia or ammonia.
5. method according to claim 1, it is characterized in that: from handing over waste liquid, reclaim from Methionin with the common electrical dialyzer and obtain ammonium sulfate, after the desalination behind the aqueous solution of ammonium chloride or ammonium nitrate from handing over waste liquid, or with the bipolar membrane electrodialysis device after the desalination after regeneration obtains bronsted lowry acids and bases bronsted lowry from handing over waste liquid from Methionin from handing over waste liquid, or combine with common electrical dialyzer and bipolar membrane electrodialysis device, obtain ammonium sulfate from Methionin recovery from handing over waste liquid, the aqueous solution of ammonium chloride or ammonium nitrate and regeneration obtain after the desalination behind the bronsted lowry acids and bases bronsted lowry from handing over the waste liquid culturing yeast, described culturing yeast is a saccharomyces cidri, the mixed culture of candida tropicalis and Candida utilis.
6. method according to claim 1 is characterized in that: more than one in the diluent of the diluent of the diluent of the filtered liquid of employing lysine fermentation liquor, lysine fermentation liquor, the dialyzate of filtering fermentation liquor or lysine fermentation liquor, the filtered liquid of lysine fermentation liquor, the dialyzate of filtering fermentation liquor are as initial liquid of three Room bipolar membrane electrodialysis devices or bipolar membrane electrodialysis devices acid chamber, two Room;

Adopt ammonium sulfate solution, aqueous ammonium chloride solution or aqueous ammonium nitrate solution initial liquid as bipolar membrane electrodialysis device alkali chamber, three Room.
7. method according to claim 1 is characterized in that: at reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, and/or add before the acid-alkali regeneration step Methionin from the degerming of handing over waste liquid, except that the albumen step.
8. method according to claim 1 is characterized in that: at reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, and/or add Methionin from the enrichment step of handing over waste liquid before the acid-alkali regeneration step.
9. method according to claim 1 is characterized in that: at reclaim(ed) sulfuric acid ammonium, ammonium chloride or ammonium nitrate, and/or add Methionin from the decalcification magnesium step of handing over waste liquid before the acid-alkali regeneration step.