CN102206167A - Method for purifying lysine - Google Patents
Method for purifying lysine Download PDFInfo
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- CN102206167A CN102206167A CN2011100809775A CN201110080977A CN102206167A CN 102206167 A CN102206167 A CN 102206167A CN 2011100809775 A CN2011100809775 A CN 2011100809775A CN 201110080977 A CN201110080977 A CN 201110080977A CN 102206167 A CN102206167 A CN 102206167A
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- methionin
- exchange resin
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Abstract
The invention provides a method for purifying lysine, comprising the following steps of: (1) contacting a lysine-containing solution with a cation exchange resin for carrying out ion exchange to ensure that the lysine is adsorbed onto the cation exchange resin, wherein the pH value of the lysine-containing solution is 3.5-6; (2) eluting the cation exchange resin adsorbed with the lysine in the step (1) with an eluent to ensure that the lysine-containing solution adsorbed onto the cation exchange resin by the eluent is replaced so as to obtain a cleaning solution; (3) eluting the lysine adsorbed onto the cation exchange resin in the step (2) with ammonia water to obtain a lysine eluent; and (4) regenerating resin by contacting the cation exchange resin eluted with the ammonia water in the step (3) with a sulphuric acid solution, and reusing the regenerated cation exchange resin in the step (1). According to the method provided by the invention, the exchange adsorption capacity of the lysine and the cation exchange resin can be greatly improved.
Description
Technical field
The present invention relates to a kind of method of purification of Methionin.
Background technology
Methionin is a kind of in 20 multiple amino acids, is that humans and animals is indispensable and be that people self one of can not 8 kinds of indispensable amino acids of synthetic, is the main component of constitutive protein matter.People's quality of life improve constantly change with foodstuff texture, accelerated the lifting of the consumption requirements total amount of Methionin, now become the important source material of industries such as food, medicine, fodder industry and makeup.
The throughput of world's Methionin in 2000 is 600,000 tons, and output reaches 500,000 tons.In recent years, the production total capacity of global Methionin surpassed 2,000,000 tons/year, surplus the consumption of international Methionin has reached 100 ten thousand tons/year.The Methionin yearly capacity of China rises to 700,000 tons in 2006 by calendar year 2001 50000 tons of less thaies, rises to 800,000 tons by 2007.Nearly 2 years, the increase of production of Methionin is slowed down situation, and 2008 is 400,000 tons.
At present, generally adopt the method for ion-exchange to separate purification Methionin, this method comprises that the pH that adds sulfuric acid adjusting Methionin earlier in lysine fermentation liquor is 1.5-3.0, then with lysine fermentation liquor process metallic membrane or ceramic membrane filter, obtaining Methionin membrane filtration liquid (perhaps flocculates lysine fermentation liquor, filter, fermenting lysine clear liquid behind the thalline is removed), adsorb exchange with ammonium type Zeo-karb then, water washing is with rinsing impurity, with weak ammonia Methionin is carried out wash-out again, the Methionin that elutes is through concentrating, hydrochloric acid is regulated pH, crystallization, obtain 98.5% feed grade lysine hydrochloric acid product salt after the oven dry.
The method of the separation purification Methionin of employing prior art was purified to the solution that contains Methionin after separation for some time, the exchange adsorptive power of Zeo-karb can significantly descend, thereby influenced the efficient of the separation and purification of Methionin greatly, and be unfavorable for the operate continuously of technology, and the purity of the Methionin product that obtains is lower.
Summary of the invention
The method of purification that the objective of the invention is to overcome the problems referred to above of the prior art and a kind of Methionin product purity Methionin higher, that separation and purification efficient is higher is provided.
To achieve these goals, the invention provides a kind of method of purification of Methionin, wherein, this method comprises the steps:
(1) solution that will contain Methionin contacts with Zeo-karb, carries out ion-exchange, and Methionin is adsorbed onto on the described Zeo-karb, and the described pH value that contains the solution of Methionin is 3.5 to 6;
(2) Zeo-karb that is adsorbed with Methionin that obtains with leacheate drip washing step (1) makes the solution that contains Methionin that is not adsorbed on the described Zeo-karb be replaced by leacheate, obtains washings;
(3) with ammoniacal liquor with step (2) be adsorbed onto Methionin wash-out on the described Zeo-karb, obtain the Methionin elutriant;
(4) contact resin regeneration with the Zeo-karb through the ammoniacal liquor wash-out of step (3) with sulphuric acid soln, and the Zeo-karb after will regenerating is reused for step (1).
The present inventor finds, owing to containing some impurity in the solution that contains Methionin, as metal ions such as calcium ion and magnesium ions, these metal ions can be along with accumulating in resin with contacting of Zeo-karb, therefore, after separation and purification for some time, described Zeo-karb will descend to the exchange adsorptive power of Methionin, thereby influences the efficient of separation and purification.And after the present inventor utilizes sulphuric acid soln that eluted resins is regenerated, can remove the foreign ion that is accumulated in the resin at an easy rate, ammonium type Zeo-karb after resolving through ammoniacal liquor can be made the transition simultaneously to being easier to adsorb the hydrogen type cation exchange resin of exchange, further be beneficial to the continuous operation of separation purifying technique, and the purity of the Methionin product that adopts method of the present invention to purify to obtain is higher.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Description of drawings
Fig. 1 is the dissociation curve of Methionin under different pH values;
Fig. 2 carries out the schema of purifying for adopting method of the present invention to Methionin.
Embodiment
According to the present invention, the method for purification of described Methionin comprises the steps:
(1) solution that will contain Methionin contacts with Zeo-karb, carries out ion-exchange, and Methionin is adsorbed onto on the described Zeo-karb, and the described pH value that contains the solution of Methionin is 3.5 to 6, is preferably 3.5-4.5;
(2) Zeo-karb that is adsorbed with Methionin that obtains with leacheate drip washing step (1) makes the solution that contains Methionin that is not adsorbed on the described Zeo-karb be replaced by leacheate, obtains washings;
(3) with ammoniacal liquor with step (2) be adsorbed onto Methionin wash-out on the described Zeo-karb, obtain the Methionin elutriant;
(4) contact resin regeneration with the Zeo-karb through the ammoniacal liquor wash-out of step (3) with sulphuric acid soln, and the Zeo-karb after will regenerating is reused for step (1).
According to the present invention, in the step (4), generally can comprise the temperature of contact and the time that contacts with sulphuric acid soln with the condition that the Zeo-karb through the ammoniacal liquor wash-out of step (3) contacts, the temperature of described contact can be 20-70 ℃, is preferably 30-50 ℃; The time of contact can be 5-60 minute, is preferably 20-45 minute.The consumption of described sulphuric acid soln is not particularly limited, as long as promptly can thinking, the pH of assurance regenerated liquid reached the regenerated requirement about 7, under the preferable case, sulphuric acid soln can be 0.3-1.5 with the weight ratio of the Zeo-karb of process ammoniacal liquor wash-out: 1, be preferably 0.8-1.2: 1; The pH value of described sulphuric acid soln is generally 0.5-3, and described sulphuric acid soln can be for containing the vitriolic aqueous solution.
The present invention is to being not particularly limited sulphuric acid soln with the mode that the Zeo-karb through the ammoniacal liquor wash-out of step (3) contacts, for example, can be for soaking or drip washing, under the preferable case, be the Zeo-karb with the described process of sulphuric acid soln drip washing ammoniacal liquor wash-out for the ease of the mode of operating and be beneficial to the described contact of regeneration, the flow velocity of sulphuric acid soln can be 5-10m/h.
The present inventor finds, adopting the method for the separation purification Methionin of prior art is 1.5-3.0 with the pH value that is generally with sulfuric acid adjusting lysine fermentation liquor, at this moment, Methionin mainly exists with the divalent cation form, and the ion exchange reaction formula of adsorption and desorption is as follows:
2R-H+HLys?H
2 2+→R
2-HLys?H
2+2H
+ (1)
R
2-HLys?H
2+2NH
4 ++2OH
-→2R-NH
4+HLys+2H
2O (2)
Therefore, when regulating the pH value, need consume a large amount of vitriol oils, also need to consume a large amount of ammoniacal liquor during with the ammoniacal liquor wash-out.And water carries out the impurities removal washing to the resin that is adsorbed with Methionin and the time can produce a large amount of waste water again, increased the burden of environmental protection, and caused the waste of resource.And, the concentration of the Methionin elutriant that the method for employing prior art obtains is lower, its concentration generally is lower than 14% (w/v), further carry dense a large amount of steam that needs to consume, and percent crystallization in massecuite is very low when making the lysine hydrochloride finished product, cause the crystalline mother solution turn-head-rate higher, increased production cost.
Therefore, the preferably feasible pH value that contains the solution of Methionin of the present invention is 3.5 to 6, more preferably 3.5-4.5.At this moment, Methionin mainly exists with the monovalent cation form, and the ion exchange reaction formula of adsorption and desorption is as follows:
R-H+HLys?H
+→R-HLys?H+H
+ (3)
R-HLys?H+NH
4 ++OH
-→R-NH
4+HLys+H
2O (4)
The dissociation curve of Methionin under different pH values as shown in Figure 1, the dissociation constant of Methionin is respectively pK
1=2.18, pK
2=8.95, and pK
3=10.53, the disassociation under different pH values is as follows:
From the contrast of formula (1) and formula (3) and formula (2) and formula (4) as can be seen, the pH value of the solution that contains Methionin of preferred controlled step (1) is 3.5 to 6,3.5-4.5 more preferably, Methionin mainly exists with the monovalent cation form, at this moment, a Zeo-karb promptly can exchange Methionin of absorption, and in the prior art, the pH value of lysine fermentation liquor is 1.5-3, this moment, Methionin mainly existed with the divalent cation form, and at this moment, two Zeo-karbs could exchange Methionin of absorption, therefore, according to the exchange adsorptive capacity that preferred embodiment can improve itself and Zeo-karb greatly of the present invention; The present inventor is surprised to find that the adsorptive power between Methionin and the resin particle is not weakened yet simultaneously, and particularly when the pH of the solution that contains Methionin value was preferably 3.5-4.5, resin was stronger to the adsorptive power of Methionin.In addition, separate the Methionin of purification equivalent, sulfuric acid and ammonia volume obviously reduce, and therefore, have reduced supplementary product onsumption effectively.The concentration of the Methionin elutriant that obtains is higher also higher, therefore, in concentration process, can effectively reduce Methionin and carry dense steam consumption, and the purity of collecting the lysine solution obtain can reach more than the 92 weight %.
Under the preferable case, the described leacheate of step (2) is the Methionin elutriant that step (3) obtains; In the step (1), the described solution that contains Methionin for the pH value less than 3.5, the fermenting lysine clear liquid that is preferably 2-3 and step (2) obtain washings and mix and obtain.
In the method for the invention, consumption for conserve water, effectively despumation also improves the purity of the Methionin elutriant that finally obtains, this method comprises that also the Methionin elutriant with the remainder except being used for concentrated and crystalline part Methionin elutriant returns step (2), be used for the Zeo-karb that is adsorbed with Methionin that drip washing step (1) obtains as leacheate, make the solution that contains Methionin that is not adsorbed on the described Zeo-karb be replaced by described leacheate, and obtain washings, and this washings is used for mixing the solution that obtains containing Methionin with the pH value of step (1) less than 4 fermenting lysine clear liquid, carry out ion-exchange.The washings that step (2) is obtained is used to dispose pH value 3.5 to 6, be preferably the solution that contains Methionin of 3.5-4.5, on the one hand, can effectively the Methionin in the washings that is not adsorbed be carried out again ion-exchange absorption handles, and improved the concentration of the Methionin elutriant that finally obtains, can also be used to regulate the described pH value that contains the solution of Methionin on the other hand, make it satisfy the requirement of pH value 3.5 to 6.In addition, higher its percent crystallization in massecuite of Methionin elutriant of concentration is also high, therefore, also is of value to the percent crystallization in massecuite that improves the amino acid elutriant, has reduced the turn-head-rate of mother liquor simultaneously.Because the Methionin elutriant that step (3) is obtained as the washings that resin is washed impurities removal, has replaced the big water gaging of available technology adopting that the resin after adsorbing is carried out rinsing, and has significantly reduced the generation of waste water, has reduced the pressure of environmental protection.
Be used for concentrating and crystalline Methionin elutriant and adjustable extent broad as the weight ratio of the Methionin elutriant that is used for the Zeo-karb that is adsorbed with Methionin that drip washing step (1) obtains of leacheate, as long as guarantee to can be used in abundant drip washing, and satisfy washings and pH value are got final product less than the requirement that 3.5 lysine fermentation liquor mixes the pH value satisfied 3.5 to 6 of the solution that contains Methionin that obtains as the Methionin elutriant that is used for the Zeo-karb that is adsorbed with Methionin that drip washing step (1) obtains of leacheate.Theoretically, not to be adsorbed to the amount of Methionin elutriant of the fermenting lysine clear liquid on the described Zeo-karb big more as the drip washing that is used for of leacheate, the content of Methionin is just high more in the Methionin elutriant that obtains at last, but not to be adsorbed to the amount of Methionin elutriant of the fermenting lysine clear liquid on the described Zeo-karb big as the drip washing that is used for of leacheate, the amount that means the Methionin elutriant that is used for condensing crystal has just diminished, therefore, can cause the reduction of output, so should take all factors into consideration the quality and the output of Methionin elutriant, and can be identified for according to the pH value of the concentration of the Methionin elutriant that elutes and the solution that contains Methionin to be regulated the Zeo-karb that is adsorbed with Methionin that drip washing step (1) obtains with displacement be not adsorbed to fermenting lysine clear liquid on the resin the weight of Methionin elutriant.Under the preferable case, be used for concentrating and crystalline Methionin elutriant is 1 with weight ratio as the Methionin elutriant that is used for the Zeo-karb that is adsorbed with Methionin that drip washing step (1) obtains of leacheate: 0.1-1, more preferably 1: 0.2-0.6; That is, the Methionin elutriant that is used for the Zeo-karb that is adsorbed with Methionin that drip washing step (1) obtains is preferably half of Methionin elutriant gross weight at most, promptly can satisfy above-mentioned requirements.
According to the present invention, for conserve water resource in suitability for industrialized production better, before this method also is included in the Zeo-karb through the ammoniacal liquor wash-out of step (3) is regenerated, to be adsorbed onto Methionin eluted resins on the Zeo-karb with water wash step (3) with ammoniacal liquor, and in resin bubbling air, water is discharged.The consumption of drip washing institute water will be as long as assurance will remain in the abundant flush away of ammoniacal liquor (pH value that it is generally acknowledged effusive wash water from resin column is clean less than 9.0) in the resin, because before carrying out analyzing step with ammoniacal liquor, the Methionin elutriant as leacheate of having used step (3) to obtain carried out an impurities removal to resin, therefore, in this water-washing step, can suitably reduce the consumption of water.Generally, the consumption of water is the water consumption of a resin column volume in this step.Bubbling air can blow out the wash water that is dissolved with ammonia that remains in the resin and utilize again in resin, has further saved water consumption, and wherein, the pressure of bubbling air generally can be 0.03-0.09MPa.
According to the present invention, in step (1), the fermenting lysine clear liquid is contacted with Zeo-karb continuously, carry out ion-exchange, the condition that Methionin is adsorbed onto on the described Zeo-karb can be the exchange adsorption conditions of routine, for example, the condition of described contact can comprise that the temperature of contact is 20-70 ℃, is preferably 30-50 ℃.Describedly contain the solution of Methionin and the weight ratio of Zeo-karb is generally thought 0.75-5: 1, be preferably 1-3: 1.
In step (2), with ammoniacal liquor the condition that is adsorbed onto the Methionin wash-out on the described hydrogen type cation exchange resin of step (1) also can be the elution requirement of routine, for example, the temperature that can comprise leacheate that comprises of described wash-out can be 20-70 ℃, is preferably 30-50 ℃; Described leacheate generally can be 0.25-1.5 with the weight ratio that is adsorbed with the Zeo-karb of Methionin: 1, be preferably 0.5-1: 1.
In the step (3), the condition that will be adsorbed onto the Methionin wash-out on the described Zeo-karb with ammoniacal liquor also can be the condition of routine, for example, can comprise that the temperature of wash-out is 30-70 ℃, is preferably 40-60 ℃; The concentration of ammoniacal liquor can be 2-10 weight %; Ammoniacal liquor generally can be 0.45-4.5 with the weight ratio that is adsorbed with the Zeo-karb of Methionin: 1, be preferably 0.8-2.5: and 1,0.8-1.5 more preferably: 1.
According to the present invention, the preparation method of described fermenting lysine clear liquid is conventionally known to one of skill in the art, for example, lysine fermentation liquor can be carried out membrane filtration, and obtain Methionin membrane filtration liquid, perhaps lysine fermentation liquor is flocculated, filters, the Methionin clear liquid behind the thalline that is removed, concrete operation method and condition can be carried out according to the method and the condition of routine, here repeat no more.
According to the present invention, as long as the concentration of Methionin satisfies the requirement of its pH value in the described solution that contains Methionin, generally, the quality volumetric concentration of Methionin is 7-17g/100ml in the described solution that contains Methionin.
According to the present invention, the quality complete exchange capacity of the Zeo-karb in the step (1) is 〉=4mmol/g to be preferably 4.5-8mmol/g; The volume complete exchange capacity is 〉=2mmol/ml, is preferably 2.05-5mmol/ml.
In the present invention, described quality complete exchange capacity or volume complete exchange capacity are meant the mole number according to the ion-exchange group that ion exchange resin contained of the unit mass of the working conditions of industry mark regulation and test determines or unit volume.For example, the measuring method of described quality complete exchange capacity comprises: get this hydrogen type cation exchange resin, spending normal saline washing is about 6.0 to pH, and the vacuum filtration of usefulness 5kPa 10 minutes is drained, and detects its moisture content with KETT.Accurately take by weighing resin after 50.0g should drain with analytical balance, at normal temperatures, the NaOH that this resin is put into the 0.5mol/L of 500ml soaks, and intermittently stirs and soaks 48 hours.Get its supernatant liquor, with the HCl titration of 0.2mol/L to pH7.0, according to the dilute hydrochloric acid volume number that consumes, promptly can be regarded as its mass exchange capacity.Measure the volume of this 50.0g resin after draining with graduated cylinder, can obtain the volume complete exchange capacity through conversion.
Among the present invention, the quantity of ion-exchange group is meant the quantity that can carry out the ion-exchange group of ion-exchange, and can obtain according to the quality complete exchange capacity of ion exchange resin or the quality or the volume calculation of volume complete exchange capacity and resin, for example, can calculate by following formula:
The volume (the perhaps quality of ion exchange resin) of the volume complete exchange capacity of the quantity of ion-exchange group (mole)=ion exchange resin (perhaps quality complete exchange capacity) * ion exchange resin.
In the present invention, described Zeo-karb can be hydrogen type cation exchange resin, also can be ammonium type Zeo-karb, also can be the hybrid resin of hydrogen type cation exchange resin and ammonium type Zeo-karb, as long as can exchange with the Methionin generation ionic adsorption in the solution that contains Methionin.If the hybrid resin of hydrogen type cation exchange resin and ammonium type Zeo-karb, take all factors into consideration the cost and the adsorptive capacity of supplementary material, the mol ratio of the ion-exchange group of the ion-exchange group of hydrogen type cation exchange resin and ammonium type Zeo-karb can be preferably 2-5: 1 for more than or equal to 1: 1.If consider adsorption effect merely, more preferably all be hydrogen type cation exchange resin.
Generally, the method that is converted to hydrogen type cation exchange resin near small part ammonium type Zeo-karb can be the resin (more preferably passing through the drip washing of water again) with acid soak process ammoniacal liquor wash-out, the condition optimization of transition makes transition for being preferably more than for the mol ratio of the ion-exchange group of the ammonium type Zeo-karb of hydrogen type cation exchange resin the ion-exchange group of hydrogen type cation exchange resin and transition or equaling 1: 1, more preferably 2-5: 1 gets final product.If consider adsorption effect merely, more preferably all be hydrogen type cation exchange resin transition.Generally speaking, described transition, condition comprised through the resin (more preferably passing through the drip washing of water again) of ammoniacal liquor wash-out and the usage ratio of acid, can be according to the exchange capacity and the resin demand of Zeo-karb, calculate the sum of the ion-exchange group of Zeo-karb, again according to the ratio of waiting to make the transition into the mole number of the ion-exchange group of the Zeo-karb of Hydrogen and ammonium type Zeo-karb, calculate the consumption of acid, thereby guarantee that it is Hydrogen that sour consumption just in time makes volume required ion exchange resin conversion.Generally speaking, Suan mass percent concentration can be 2-10 weight %.Can be 20-70 ℃ with acid to the temperature that resin soaks, the time of immersion can be 5-60min.Described acid can be selected from one or more in the inorganic acids such as sulfuric acid, hydrochloric acid and sulfonic acid.
Because hydrogen type cation exchange resin can obtain by ammonium type Zeo-karb is made the transition, therefore the quality complete exchange capacity or the volume complete exchange capacity of described hydrogen type cation exchange resin can be identical with described ammonium type Zeo-karb, therefore, the quality complete exchange capacity of Zeo-karb described in the present invention is 〉=4mmol/g to be preferably 4.5-8mmol/g; The volume complete exchange capacity is preferably 2.05-5mmol/ml for 〉=2mmol/ml.
The present invention is not particularly limited the content of described ion exchange resin, can carry out appropriate selection according to the mol ratio and the exchange capacity of the ion-exchange group in ion-exchange group in the hydrogen type cation exchange resin or the ammonium type Zeo-karb.
Zeo-karb of the present invention is preferably storng-acid cation exchange resin, and described storng-acid cation exchange resin can be gel-type ion-exchange resin and/or macroreticular ion exchange resin.
The present invention is not particularly limited for the matrix resin of described macroreticular ion exchange resin and gel-type ion-exchange resin.Preferably, described macroreticular ion exchange resin is the polystyrene macroreticular ion exchange resin, and described gel-type ion-exchange resin is the polystyrene gel-type ion-exchange resin, and described weakly acidic cation-exchange resin is an acrylic acid series ion exchange resin.For example, the matrix resin of described macroporous type styrene ion exchange resin and polystyrene gel-type ion-exchange resin can be respectively styrene-divinylbenzene copolymer, and the degree of crosslinking of this multipolymer can be 4-8 mole %.
For example, can be the mixture of any one or they in the following resin: product grade is 001 * 4 polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 4H polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 7 polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 7H polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 7FC polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 7MB polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 8 polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 8FC polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 8MB polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 10 polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 10H polystyrene gel-type strongly acidic cation exchange resin, product grade is 001 * 16 polystyrene gel-type strongly acidic cation exchange resin, product grade is a SQ-66 polystyrene gel-type strongly acidic cation exchange resin, product grade is a SQ-68 polystyrene gel-type strongly acidic cation exchange resin, product grade is a SQ-607 polystyrene gel-type strongly acidic cation exchange resin, product grade is a D001 polystyrene macroporous type storng-acid cation exchange resin, product grade is a D001H polystyrene macroporous type storng-acid cation exchange resin, product grade is a D001FC polystyrene macroporous type storng-acid cation exchange resin, product grade is a D001MB polystyrene macroporous type storng-acid cation exchange resin, product grade is a SQD-61 polystyrene macroporous type storng-acid cation exchange resin, product grade is a SQD-65 polystyrene macroporous type storng-acid cation exchange resin, product grade is a SQD-67 polystyrene macroporous type strong-acid cation-exchange resin, product grade is the resin dedicated polystyrene gel-type strongly acidic cation exchange resin of WA-2 amino acid.More than listed various Zeo-karbs all be available commercially.
According to the present invention, the rate of small round spheres of described Zeo-karb is not particularly limited.From the angle of the physical strength of further raising ion exchange resin, the rate of small round spheres of described Zeo-karb is preferably more than 95%.Among the present invention, the coefficient of uniformity of described Zeo-karb can be 1.05-1.6, is preferably 1.05-1.4.Among the present invention, described rate of small round spheres is meant that resin is the percentage that the spherical particle number accounts for total number of particles; Described coefficient of uniformity is meant can be by the sieve diameter of 60% volume of resins and the ratio of the sieve diameter of the resin that can pass through 10% volume.
Among the present invention, the ion-exchange group of described Zeo-karb can suitably be selected according to concrete working conditions, is not particularly limited.
Particularly, the ion-exchange group of described hydrogen type cation exchange resin can be-SO
3The H group, the ion-exchange group of described ammonium type Zeo-karb can be-SO
3NH
4Group.Above-mentioned ion exchange resin can be commercially available, also can be with Hydrogen or the sodium type Zeo-karb that is commercially available, obtain ammonium type Zeo-karb transition with weak ammonia.
According to a preferred embodiment of the present invention, as shown in Figure 2, described Zeo-karb is the placed in-line cation exchange resin column groups of many groups, the purification process of described Methionin comprises that making the solution that contains Methionin carry out ion-exchange chromatography with many groups cation exchange resin column set of contact separates, every group of cation exchange resin column group passed through adsorption zone 1, trash zone 2 successively and circularly, resolved district 3 and breeding blanket 15, so that the cation exchange resin column group exchanges absorption, impurities removal, parsing and regeneration successively and circularly:
(1) at least two group cation exchange resin column group is in adsorption zone 1 simultaneously, at adsorption zone 1, the solution 5 that contains Methionin is introduced from the upper end along the cation exchange resin column group that is in adsorption zone 1 first place of cation exchange resin column group travel direction, flow through successively to be in and respectively organize the cation exchange resin column group in this adsorption zone 1, and flow out and the absorption raffinate that obtains after resin contacts from the lower end that is in adsorption zone 1 omega-cation exchange resin column group; Be introduced into the exchange capacity that Methionin in the solution that contains Methionin of described the first cation exchange resin column group and the exchange of the active group in this group resin column absorption reach resin, exchange stops, and the cation exchange resin column group that this absorption is saturated moves into trash zone 2; The described solution that contains Methionin 5 for the pH value less than 3.5, the fermenting lysine clear liquid that is preferably 2-3 mixes the mixture that obtains with washings 6;
(2) at least two group cation exchange resin column groups are in trash zone 2 simultaneously, at trash zone 2, leacheate is introduced from the upper end along the resin column group that is in trash zone 2 first places of cation exchange resin column group travel direction, each group in this row's impurity range of drip washing 2 is adsorbed with the cation exchange resin column group of Methionin successively, and flows out the washings 6 after the drip washing from the lower end that is in trash zone 2 omega-cation exchange resin column groups; And the cation exchange resin column group after this drip washing move into resolved district 3, and the washings after the described drip washing 6 is returned adsorption zone 1 be used to prepare the solution 5 that contains Methionin; Described leacheate is a Methionin elutriant 7;
(3) at least two group cation exchange resin column groups are in simultaneously resolves district 3, resolving district 3, with ammoniacal liquor 8 from the upper end of resolving the resin column group of 3 first places, district along being in of cation exchange resin column group travel direction introduce and this parsings district 3 that flows through successively in respectively organize the cation exchange resin column group, and resolve the lower end outflow Methionin elutriant 7 of distinguishing 3 omega-cation exchange resin column groups from being in; And the cation exchange resin column group after will resolving moves into breeding blanket 15, and part Methionin elutriant 7 is returned trash zone 2 as leacheate;
(4) at least two group cation exchange resin column groups are in breeding blanket 15 simultaneously, in the breeding blanket 15, with sulphuric acid soln 10 from introduce along the upper end of the resin column group that is in 15 first places, breeding blanket of cation exchange resin column group travel direction and this breeding blanket 15 of flowing through successively in respectively organize the cation exchange resin column group, and flow out regeneration back waste liquid 11 from the lower end that is in breeding blanket 15 omega-cation exchange resin column groups; And the cation exchange resin column group after will regenerating moves into adsorption zone 1.
Wherein, the number of the resin column in the number of the described resin column group that is in adsorption zone, trash zone, parsing district and breeding blanket and the every group of resin column group can be selected according to actual needs, under the preferable case, the described number that is in the resin column group in adsorption zone, trash zone and parsing district is 3-8, and every group of cation exchange resin column group comprises 1-6 cation exchange resin column in parallel.
Under the preferable case, as shown in Figure 2, this method also was included in before moving into breeding blanket 15 through the resin column group of resolving and moves into washing section 4 successively, at washing section 4, water 9 from introduce along the upper end that will be adsorbed onto the Methionin eluted resins post group on the Zeo-karb that is in washing section 4 first places of cation exchange resin column group travel direction and this washing section 4 of flowing through successively in respectively organize the cation exchange resin column group, and from being in outflow washing back, the lower end waste liquid of washing section 4 omega-cation exchange resin column groups, and in resin bubbling air, water is discharged; And the cation exchange resin column group after will washing moves into breeding blanket 15.
In addition, under the preferable case, the described number that is in the resin column group of washing section also can be 3-8, and every group of cation exchange resin column group preferably includes 1-6 cation exchange resin column in parallel.
To further describe in detail the present invention by specific embodiment below.
What adopt among the following embodiment 1-5 is the continous way ion exchange system, model L100-139, (resin column of per two parallel connections is one group of cation exchange resin column group to 20 cation exchange resin columns, have ten groups of described cation exchange resin column groups, described ten groups of cation exchange resin column group series connection), the specification of single post is Ф 35 * 1000mm, the tetrafluoroethylene material, and U.S. CALGAN CARBON CORP produces.Among the embodiment 1-4 in every resin column the amount of fill of resin be 600 grams.
Used resin is a storng-acid cation exchange resin in following enforcement, this resin model is that WA-2 amino acid is resin dedicated, the quality complete exchange capacity is 5.5mmol/g, resinous type is the gel type cation exchange resin, being purchased producer is Anhui Wan Dong chemical industry company limited, coefficient of uniformity is 1.3, and rate of small round spheres is 96%.
The purity of lysine fermentation liquor described in the following embodiment/Methionin elutriant is meant the ratio of the dry matter content of the content of Methionin in lysine fermentation liquor/Methionin elutriant and lysine fermentation liquor/Methionin elutriant, wherein, the content of Methionin is measured by ninhydrin method, and the dry matter content of lysine fermentation liquor/Methionin elutriant is measured by baking oven.
Present embodiment is used to illustrate the method for purification of Methionin.
(1) with 0.8m
3Lysine fermentation liquor (lysine content 11.2g/100ml, purity 59.4 weight %) (membrane material is pottery (film surface micropore UF1 aperture 0.1um to carry out membrane filtration, UF2 aperture 0.2um), membrane filtration pressure is 1.5bar, the membrane filtration temperature is 75 ℃, and filtration time is 1 hour), obtain the pH value and be 3 fermenting lysine clear liquid through membrane filtration, and mix with washings (washings that step (3) obtains), it is 6 that the consumption of washings makes the pH value of the mixed solution that contains Methionin that obtains;
(2) under 40 ℃, the pH value that step (1) is obtained is that 6 the solution that contains Methionin pumps into from the upper end of the resin column group that is in the adsorption zone first place continuously that (flow velocity that contains the solution of Methionin is 6.3m/h, describedly contain the solution of Methionin and the weight ratio of resin is 2: 1), with the absorption raffinate that obtains after resin contacts flow through successively be in adsorption zone respectively organize the resin column group, and flow out from the lower end of the omega-resin column group that is in adsorption zone; Be introduced into the exchange capacity that Methionin in the solution that contains Methionin of described the first resin column group and the exchange of the active group in this resin column absorption reach resin, exchange stops, the resin column group that this absorption is saturated moves into trash zone, and continue to contain of the upper end introducing of the solution of Methionin, and repeat above-mentioned steps from back one group of resin column group adjacent with described the first resin column group;
(3) at trash zone, introduce from the upper end of the resin column group that is in the trash zone first place with 45 ℃ leacheates (the Methionin elutriant that step (3) obtains) that (flow velocity of leacheate is 7.6m/h, described leacheate is 0.8: 1 with the weight ratio that is adsorbed with the resin of Methionin), each group that is in trash zone of flowing through successively is adsorbed with the resin column group of Methionin, and flow out washings after the drip washing from the lower end that is in trash zone omega-cation exchange resin column group, and the resin column after this drip washing moved into successively resolve the district, and the washings after the drip washing is returned adsorption zone be used to prepare the solution that contains Methionin;
(4) under 40 ℃, resolving the district, introduce from being in the upper end of resolving the first resin column group in district that (flow velocity of ammoniacal liquor is 9.6m/h with the ammoniacal liquor of 5 weight %, described ammoniacal liquor is 1: 1 with the weight ratio that is adsorbed with the resin of Methionin), flow through successively and respectively organize the cation exchange resin column group in this parsing district, and flow out and collect the Methionin elutriant (purity 94 weight %) that obtains 20.1g/100ml from being in the lower end of resolving district's omega-cation exchange resin column group; Part Methionin elutriant is returned the trash zone of step (3) as leacheate.
(5) will move into washing section successively through the resin of resolving, at washing section, introduce the upper end that will be in the resin column group of washing section first place, the Methionin eluted resins post group that will be adsorbed onto on the cation exchange resin column group with ammoniacal liquor each group in this washing section is washed successively, and flows out the water lotion after washing from the lower end that is in washing section omega-cation exchange resin column group; And bubbling air in the resin column after washing, water is discharged;
(6) with the described Zeo-karb of sulphuric acid soln (the pH value is 1) drip washing through ammoniacal liquor wash-out and washing, with resin regeneration, the temperature of drip washing is 40 ℃, and the time of drip washing is 20 minutes (consumption of described sulphuric acid soln is 1.2: 1 with the weight ratio of the Zeo-karb of process ammoniacal liquor wash-out and washing); And the Zeo-karb after will regenerating is reused for step (1).
The order that every group of resin moves is for to move into trash zone successively from adsorption zone, moved into by trash zone and resolves the district, moves into washing section by resolving the district, returns adsorption zone again by washing section again and circulates; Methionin elutriant, washings are then to be turned back to the resin of trash zone with the reverse mode of resin by the resin column through resolving of resolving the district, the washings that obtains is turned back in the resin of resolving the district by the resin through drip washing of trash zone, and the reverse speed with 7.5m/h of resin and material (elutriant, washings) moves.
Present embodiment is used to illustrate the purification process of Methionin.
Method according to embodiment 1 is carried out purifying to Methionin, and different is: in the step (1), it is 3.5 that the consumption of washings makes the pH value of the mixed solution that contains Methionin that obtains.In the Methionin elutriant that obtains, the content of Methionin is 21.4g/100ml, purity 96 weight %.
Embodiment 3
Present embodiment is used to illustrate the method for purification of Methionin.
Method according to embodiment 1 is purified to Methionin, and different is:
In the step (1), it is 3.5 that the consumption of washings makes the pH value of the mixed solution that contains Methionin that obtains;
In the step (2), the temperature of ion-exchange is 50 ℃, and the flow velocity that contains the solution of Methionin is 5m/h, describedly contains the solution of Methionin and the weight ratio of resin is 1.6: 1;
In the step (3), the temperature of leacheate is 60 ℃, and the flow velocity of leacheate is 9.5m/h, and described leacheate is 1: 1 with the weight ratio that is adsorbed with the resin of Methionin;
In the step (4), the temperature of resolving is 60 ℃, with the weak ammonia of 5.6 weight % the resin column through absorption of step (3) is carried out wash-out successively, ammonia flow rate is 13.6m/h, described ammoniacal liquor is 0.9: 1 with the weight ratio that is adsorbed with the resin of Methionin, and obtaining content is the Methionin elutriant (purity 96.5 weight %) of 18.6g/100ml;
In the step (6), with the described Zeo-karb of sulphuric acid soln (the pH value is 1.5) drip washing through ammoniacal liquor wash-out and washing, with resin regeneration, the temperature of drip washing is 30 ℃, and the time of drip washing is 45 minutes (consumption of described sulphuric acid soln is 1: 1 with the weight ratio of the Zeo-karb of process ammoniacal liquor wash-out and washing); And the Zeo-karb after will regenerating is reused for step (1).
The order that every group of resin moves is for to move into trash zone successively from adsorption zone, moved into by trash zone and resolves the district, moves into washing section by resolving the district, returns adsorption zone again by washing section again and circulates; Methionin elutriant, washings are then to be turned back to the resin of trash zone with the reverse mode of resin by the resin column through resolving of resolving the district, the washings that obtains is turned back in the resin of resolving the district by the resin through drip washing of trash zone, and the reverse speed with 11.4m/h of resin and material (elutriant, washings) moves.
Embodiment 4
Present embodiment is used to illustrate the method for purification of Methionin.
Method according to embodiment 1 is purified to Methionin, and different is:
Lysine content 13.2g/100ml in the lysine fermentation liquor, purity 56.4%;
It is 4.5 that the consumption of the middle washings of step (1) makes the pH value of the mixed solution that contains Methionin that obtains;
In the step (2), the temperature of ion-exchange is 30 ℃, and the flow velocity that contains the solution of Methionin is 5.7m/h, describedly contains the solution of Methionin and the weight ratio of resin is 1.8: 1;
In the step (3), the temperature of leacheate is 40 ℃, and the flow velocity of leacheate is 5.7m/h, and described leacheate is 0.625: 1 with the weight ratio that is adsorbed with the resin of Methionin;
In the step (4), the temperature of resolving is 40 ℃, with the weak ammonia of 4.5 weight % the resin column through absorption of step (3) is carried out wash-out successively, ammonia flow rate is 12.6m/h, described ammoniacal liquor is 1.2: 1 with the weight ratio that is adsorbed with the resin of Methionin, and obtaining content is the Methionin elutriant (purity 95.3 weight %) of 19.2g/100ml.
In the step (6), with the described Zeo-karb of sulphuric acid soln (the pH value is 2) drip washing through ammoniacal liquor wash-out and washing, with resin regeneration, the temperature of drip washing is 35 ℃, and the time of drip washing is 25 minutes (consumption of described sulphuric acid soln is 0.5: 1 with the weight ratio of the Zeo-karb of process ammoniacal liquor wash-out and washing); And the Zeo-karb after will regenerating is reused for step (1).
The order that every group of resin moves is for to move into trash zone successively from adsorption zone, moved into by trash zone and resolves the district, moves into washing section by resolving the district, returns adsorption zone again by washing section again and circulates; Methionin elutriant, washings are then to be turned back to the resin of trash zone with the reverse mode of resin by the resin column through resolving of resolving the district, the washings that obtains is turned back in the resin of resolving the district by the resin through drip washing of trash zone, and the reverse speed with 11m/h of resin and material (elutriant, washings) moves.
Present embodiment is used to illustrate the method for purification of Methionin.
Method according to embodiment 1 is purified to Methionin, and different is:
Lysine content 9.2g/100ml in the lysine fermentation liquor, purity 46.4 weight %;
It is 4.2 that the consumption of the middle washings of step (1) makes the pH value of the mixed solution that contains Methionin that obtains;
In the step (2), the temperature of ion-exchange is 50 ℃, (resin column of per three parallel connections is one group of cation exchange resin column group to totally 30 of cationic resin column, totally ten groups, described ten groups of resin column group series connection, the resin loadings is 18 kilograms in every resin column) flow velocity that contains the solution of Methionin is 5.0m/h, describedly contains the solution of Methionin and the weight ratio of resin is 1.5: 1;
In the step (3), the temperature of leacheate is 50 ℃, and the flow velocity of leacheate is 6.85m/h, and described leacheate is 0.6: 1 with the weight ratio that is adsorbed with the resin of Methionin;
In the step (4), the temperature of resolving is 60 ℃, with the weak ammonia of 5.4 weight % the resin column through absorption of step (3) is carried out wash-out successively, ammonia flow rate is 15m/h, described ammoniacal liquor is 0.75: 1 with the weight ratio that is adsorbed with the resin of Methionin, and obtaining content is the Methionin elutriant (purity 96.2 weight %) of 18g/100ml.
In the step (6), with the described Zeo-karb of sulphuric acid soln (the pH value is 3) drip washing through ammoniacal liquor wash-out and washing, with resin regeneration, the temperature of drip washing is 50 ℃, and the time of drip washing is 50 minutes (consumption of described sulphuric acid soln is 1.5: 1 with the weight ratio of the Zeo-karb of process ammoniacal liquor wash-out and washing); And the Zeo-karb after will regenerating is reused for step (1).
The order that every group of resin moves is for to move into trash zone successively from adsorption zone, moved into by trash zone and resolves the district, moves into washing section by resolving the district, returns adsorption zone again by washing section again and circulates; Methionin elutriant, washings are then to be turned back to the resin of trash zone with the reverse mode of resin by the resin column through resolving of resolving the district, the washings that obtains is turned back in the resin of resolving the district by the resin through drip washing of trash zone, and the reverse speed with 13.3m/h of resin and material (elutriant, washings) moves.
Comparative Examples 1
This Comparative Examples is used to illustrate the reference method of Methionin purification.
Method according to embodiment 1 is purified to Methionin, and different is: the pH value of regulating the fermenting lysine clear liquid of the process membrane filtration that obtains with sulfuric acid is 2.0, carries out drip washing at trash zone without the Methionin elutriant, carries out drip washing but use deionized water instead.And resin is regenerated without sulfuric acid.To carry out wash-out successively with the resin column through absorption of deionized water drip washing with weak ammonia (mass percent concentration is 5 weight %), obtain Methionin elutriant (lysine hydrochloric acid salts contg 14.5g/100ml in the elutriant, purity is 78 weight %).
The process regenerated resin and 300 through after the washing of regenerated resin and 100 gram Comparative Examples 1 of getting 100 gram embodiment 1 respectively restrains the fermenting lysine clear liquids (wherein, the concentration of Methionin is 10 weight %) mix, intermittently stir and placed 48 hours, (through lysine concentration in the clear liquid after the resin absorption of embodiment 1 is 3.4 weight % to the concentration of Methionin in the fermenting lysine clear liquid after detection is adsorbed then, through lysine concentration in the clear liquid after the resin absorption of Comparative Examples 1 is 5 weight %), by the difference of lysine concentration in the Methionin clear liquid before and after the absorption, can calculate its adsorptive capacity.Explanation thus, the adsorptive capacity ratio of process regenerated resin has not improved 32% through the adsorptive capacity of regenerated resin.Illustrate, adopt method of the present invention with after the resin regeneration, can remove the foreign metal ion in the resin, the position that was adsorbed with metal ion is originally vacated, and therefore can further adsorb Methionin, and then improve separation efficiency.
According to embodiment 1-5 and Comparative Examples 1 more as can be seen, adopt the content of Methionin in the Methionin elutriant that method of the present invention obtains higher, and the purity of Methionin elutriant is also higher, illustrates that thus method of the present invention can improve the exchange adsorptive capacity of Methionin and Zeo-karb greatly.In addition, adopting method of the present invention that resin is returned adsorption zone again carries out before the adsorption operations resin regenerated and can effectively improve the work-ing life of resin, and the high adsorption capacity of h type resin, and then improved the adsorptive power of resin, finally reach the raising of separation efficiency.
Claims (18)
1. the method for purification of a Methionin is characterized in that, this method comprises the steps:
(1) solution that will contain Methionin contacts with Zeo-karb, carries out ion-exchange, and Methionin is adsorbed onto on the described Zeo-karb, and the described pH value that contains the solution of Methionin is 3.5 to 6;
(2) Zeo-karb that is adsorbed with Methionin that obtains with leacheate drip washing step (1) makes the solution that contains Methionin that is not adsorbed on the described Zeo-karb be replaced by leacheate, obtains washings;
(3) with ammoniacal liquor with step (2) be adsorbed onto Methionin wash-out on the described Zeo-karb, obtain the Methionin elutriant;
(4) contact resin regeneration with the Zeo-karb through the ammoniacal liquor wash-out of step (3) with sulphuric acid soln, and the Zeo-karb after will regenerating is reused for step (1).
2. method according to claim 1, wherein, in the step (4), the condition of described contact comprises that the temperature of contact is 20-70 ℃, the time of contact is 5-60 minute.
3. method according to claim 1 and 2, wherein, in the step (4), the mode of described contact is the Zeo-karb with the described process of sulphuric acid soln drip washing ammoniacal liquor wash-out.
4. method according to claim 3, wherein, the consumption of described sulphuric acid soln is 0.3-1.5 with the weight ratio of the Zeo-karb of process ammoniacal liquor wash-out: 1, the pH value of described sulphuric acid soln is 0.5-3.
5. method according to claim 1, wherein, the described leacheate of step (2) is the Methionin elutriant that step (3) obtains; In the step (1), the described solution that contains Methionin is the mixture of washings that the pH value is obtained less than 3.5 fermenting lysine clear liquid and step (2).
6. method according to claim 1, wherein, in the step (1), will contain the temperature that the solution of Methionin contacts with Zeo-karb is 20-70 ℃, containing the solution of Methionin and the weight ratio of Zeo-karb is 0.75-5: 1.
7. according to claim 1 or 6 described methods, wherein, in the step (1), the described pH value that contains the solution of Methionin is 3.5-4.5.
8. method according to claim 1, wherein, in the step (2), the temperature of described leacheate is 20-70 ℃, described leacheate is 0.25-1.5 with the weight ratio that is adsorbed with the Zeo-karb of Methionin: 1.
9. method according to claim 1, wherein, in the step (3), the condition that will be adsorbed onto the Methionin wash-out on the described Zeo-karb with ammoniacal liquor comprises that the temperature of wash-out is 30-70 ℃, the concentration of ammoniacal liquor is 2-10 weight %, and ammoniacal liquor is 0.45-4.5 with the weight ratio that is adsorbed with the Zeo-karb of Methionin: 1.
10. method according to claim 1, wherein, this method comprises that also the Methionin elutriant that step (3) is obtained concentrates and crystallization.
11., wherein, be used for concentrating and crystalline Methionin elutriant is 1 with weight ratio as the Methionin elutriant of leacheate: 0.1-1 according to claim 1 or 10 described methods.
12. method according to claim 1, wherein, before this method also is included in the Zeo-karb through the ammoniacal liquor wash-out of step (3) is regenerated, to be adsorbed onto Methionin eluted resins on the Zeo-karb with water wash step (3) with ammoniacal liquor, bubbling air in resin is discharged water then.
13. method according to claim 1, wherein, the quality complete exchange capacity of Zeo-karb is 〉=4mmol/g that the volume complete exchange capacity is 〉=2mmol/ml.
14. method according to claim 13, wherein, described Zeo-karb is a storng-acid cation exchange resin, described storng-acid cation exchange resin is gel-type ion-exchange resin or macroreticular ion exchange resin, described gel-type ion-exchange resin is the polystyrene gel-type ion-exchange resin, and described macroreticular ion exchange resin is the polystyrene macroreticular ion exchange resin; The ion-exchange group of described Zeo-karb comprises-SO
3The H group and-SO
3NH
4Group.
15. method according to claim 5, wherein, described Zeo-karb is the placed in-line cation exchange resin column groups of many groups, the purification process of described Methionin comprises that making the solution that contains Methionin carry out ion-exchange chromatography with many groups cation exchange resin column set of contact separates, every group of cation exchange resin column group passed through adsorption zone, trash zone, parsing district and breeding blanket successively and circularly, so that the cation exchange resin column group exchanges absorption, impurities removal, parsing and regeneration successively and circularly:
(1) at least two group cation exchange resin column group is in adsorption zone simultaneously, at adsorption zone, the solution that contains Methionin is introduced from the upper end along the cation exchange resin column group that is in the adsorption zone first place of cation exchange resin column group travel direction, flow through successively to be in and respectively organize the cation exchange resin column group in this adsorption zone, and flow out and the absorption raffinate that obtains after resin contacts from the lower end that is in adsorption zone omega-cation exchange resin column group; Be introduced into the exchange capacity that Methionin in the solution that contains Methionin of described the first cation exchange resin column group and the exchange of the active group in this group resin column absorption reach resin, exchange stops, and the cation exchange resin column group that this absorption is saturated moves into trash zone; The described solution that contains Methionin is for mixing the mixture that obtains with the pH value less than 3.5 fermenting lysine clear liquid with washings;
(2) at least two group cation exchange resin column groups are in trash zone simultaneously, at trash zone, leacheate is introduced from the upper end along the resin column group that is in the trash zone first place of cation exchange resin column group travel direction, in this row's impurity range of drip washing each group is adsorbed with the cation exchange resin column group of Methionin successively, and flows out the washings after the drip washing from the lower end that is in trash zone omega-cation exchange resin column group; And the cation exchange resin column group after this drip washing move into resolved the district, and the washings after the described drip washing is returned adsorption zone be used to prepare the solution that contains Methionin; Described leacheate is the Methionin elutriant;
(3) at least two group cation exchange resin column groups are in simultaneously resolves the district, resolving the district, with ammoniacal liquor from the upper end of resolving the first resin column group in district along being in of cation exchange resin column group travel direction introduce and this parsings district that flows through successively in respectively organize the cation exchange resin column group, and distinguish the lower end outflow Methionin elutriant of omega-cation exchange resin column group from being in parsing; And the cation exchange resin column group after will resolving moves into the breeding blanket, and part Methionin elutriant is returned trash zone as leacheate;
(4) at least two group cation exchange resin column groups are in the breeding blanket simultaneously, in the breeding blanket, with sulphuric acid soln from introduce along the upper end of the resin column group that is in the first place, breeding blanket of cation exchange resin column group travel direction and this breeding blanket of flowing through successively in respectively organize the cation exchange resin column group, and flow out regeneration back waste liquid from the lower end that is in breeding blanket omega-cation exchange resin column group; And the cation exchange resin column group after will regenerating moves into adsorption zone.
16. method according to claim 15, wherein, the described number that is in the resin column group of adsorption zone, trash zone, parsing district and breeding blanket is 3-8, and every group of cation exchange resin column group comprises 1-6 cation exchange resin column in parallel.
17. method according to claim 15, wherein, this method also was included in before moving into the breeding blanket through the resin column group of resolving and moves into washing section successively, at washing section, water from introduce along the upper end that will be adsorbed onto the Methionin eluted resins post group on the Zeo-karb that is in the washing section first place of cation exchange resin column group travel direction and this washing section of flowing through successively in respectively organize the cation exchange resin column group, and from being in outflow washing back, the lower end waste liquid of washing section omega-cation exchange resin column group, and in resin bubbling air, water is discharged; And the cation exchange resin column group after will washing moves into the breeding blanket.
18. method according to claim 17, wherein, the described number that is in the resin column group of washing section is 3-8, and every group of cation exchange resin column group comprises 1-6 cation exchange resin column in parallel.
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| CN104725258A (en) * | 2013-12-24 | 2015-06-24 | 中粮生物化学（安徽）股份有限公司 | Purification method of lysine fermentation liquid |
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| US10974168B2 (en) | 2015-04-08 | 2021-04-13 | Inv Nylon Chemicals Americas, Llc | Materials and methods for the selective recovery of monovalent products from aqueous solutions using continuous ion exchange |
| CN106748871A (en) * | 2016-11-29 | 2017-05-31 | 岳阳科罗德联合化学工业有限公司 | A kind of green circulatory industrial production process of amino acid surfactant |
| CN106748871B (en) * | 2016-11-29 | 2019-03-05 | 岳阳科罗德联合化学工业有限公司 | A kind of green circulatory industrial production process of amino acid surfactant |
| CN108620140A (en) * | 2018-07-03 | 2018-10-09 | 山东寿光巨能金玉米开发有限公司 | A kind of high efficiency continuously resistance tocrocking lysine ion-exchange process |
| US12090420B2 (en) | 2018-09-18 | 2024-09-17 | Inv Nylon Chemicals Americas, Llc | Systems and methods for recovering amines and their derivatives from aqueous mixtures |
| CN111635344A (en) * | 2020-06-08 | 2020-09-08 | 九江中星医药化工有限公司 | Post-treatment method of homocystine reaction solution |
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| Publication number | Publication date |
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| CN102206167B (en) | 2014-02-26 |
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