CN102206167A - Method for purifying lysine - Google Patents

Abstract

The purification method of lysine comprises the following steps: (1) the solution containing lysine is contacted with a cation exchange resin to carry out ion exchange, so that lysine is adsorbed on the cation exchange resin, and the lysine-containing The pH value of the solution of the acid is 3.5 to 6; (2) the cation-exchange resin that is adsorbed with lysine obtained in step (1) with eluent washing, makes the lysine-containing lysine that is not adsorbed on the cation-exchange resin The acid solution is replaced by the eluent to obtain the washing solution; (3) eluting the lysine that has been adsorbed on the cation exchange resin in step (2) with ammonia water to obtain the lysine eluent; ( 4) Regenerating the resin by contacting the cation exchange resin eluted with ammonia water in step (3) with a sulfuric acid solution, and reusing the regenerated cation exchange resin in step (1). The method of the invention can greatly increase the exchange adsorption capacity of lysine and cation exchange resin.

Description

A kind of purification method of lysine

technical field

The invention relates to a method for purifying lysine.

Background technique

Lysine is one of more than 20 kinds of amino acids. It is indispensable for humans and animals and is one of the eight essential amino acids that cannot be synthesized by humans. It is the main component of protein. The continuous improvement of people's quality of life and the change of food structure have accelerated the increase in the total consumption demand of lysine, and now it has become an important raw material for food, medicine, feed industry and cosmetics and other industries.

In 2000, the production capacity of lysine in the world was 600,000 tons, and the output reached 500,000 tons. In recent years, the total production capacity of lysine in the world has exceeded 2 million tons per year, and the international consumption of lysine has reached more than 1 million tons per year. China's annual production capacity of lysine increased from less than 50,000 tons in 2001 to 700,000 tons in 2006 and 800,000 tons in 2007. In the past two years, the growth rate of lysine production has slowed down, reaching 400,000 tons in 2008.

At present, ion exchange is generally used to separate and purify lysine. This method includes first adding sulfuric acid to the lysine fermentation broth to adjust the pH of lysine to 1.5-3.0, and then passing the lysine fermentation broth through metal membranes or ceramics. Membrane filtration to obtain lysine membrane filtrate (or flocculation and filtration of lysine fermentation broth to obtain lysine fermentation serum after removing bacteria), then use ammonium type cation exchange resin to carry out adsorption exchange, wash with water and Impurities are rinsed, and then lysine is eluted with dilute ammonia water. The eluted lysine is concentrated, pH is adjusted with hydrochloric acid, crystallized, and dried to obtain 98.5% feed-grade lysine hydrochloride product.

After adopting the method for separating and purifying lysine of the prior art to purify and separate the solution containing lysine for a period of time, the exchange adsorption capacity of the cation exchange resin will significantly decrease, thereby greatly affecting the efficiency of the separation and purification of lysine. And it is unfavorable for the continuous operation of technique, moreover, the purity of the lysine product obtained is relatively low.

Contents of the invention

The purpose of the present invention is to overcome the above-mentioned problems in the prior art and provide a lysine purification method with higher purity of lysine product and higher separation and purification efficiency.

In order to achieve the above object, the present invention provides a method for purifying lysine, wherein the method comprises the following steps:

(1) contacting the solution containing lysine with a cation exchange resin for ion exchange, so that lysine is adsorbed on the cation exchange resin, and the pH value of the solution containing lysine is 3.5 to 6;

(2) The cation exchange resin adsorbed with lysine obtained in step (1) is rinsed with eluent, so that the lysine-containing solution that is not adsorbed on the cation exchange resin is replaced by the eluent to obtain detergent;

(3) eluting the lysine adsorbed on the cation exchange resin in step (2) with ammonia water to obtain a lysine eluent;

(4) Regenerating the resin by contacting the cation exchange resin eluted with ammonia water in step (3) with sulfuric acid solution, and reusing the regenerated cation exchange resin in step (1).

The inventors of the present invention have found that because the solution containing lysine contains some impurities, such as metal ions such as calcium ions and magnesium ions, these metal ions will accumulate in the resin along with the contact with the cation exchange resin, therefore, in After a period of separation and purification, the exchange and adsorption capacity of the cation exchange resin for lysine will decrease, thereby affecting the efficiency of separation and purification. After the inventor of the present invention regenerates the eluted resin with sulfuric acid solution, the impurity ions accumulated in the resin can be easily removed, and at the same time, the ammonium-type cation exchange resin after ammonia water analysis can be transformed into a more easily adsorbed The exchanged hydrogen-type cation exchange resin is further beneficial to the continuous operation of the separation and purification process, and the purity of the lysine product purified by the method of the present invention is relatively high.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Description of drawings

Fig. 1 is the dissociation curve of lysine at different pH values;

Fig. 2 is a flowchart of purifying lysine by the method of the present invention.

Detailed ways

According to the present invention, the purification method of described lysine comprises the following steps:

(1) The solution containing lysine is contacted with a cation exchange resin for ion exchange, so that lysine is adsorbed on the cation exchange resin, and the pH value of the solution containing lysine is 3.5 to 6, preferably 3.5-4.5;

(2) The cation exchange resin adsorbed with lysine obtained in step (1) is rinsed with eluent, so that the lysine-containing solution that is not adsorbed on the cation exchange resin is replaced by the eluent to obtain detergent;

(3) eluting the lysine adsorbed on the cation exchange resin in step (2) with ammonia water to obtain a lysine eluent;

(4) Regenerating the resin by contacting the cation exchange resin eluted with ammonia water in step (3) with sulfuric acid solution, and reusing the regenerated cation exchange resin in step (1).

According to the present invention, in step (4), the condition of contacting with the cationic exchange resin of ammoniacal liquor elution with sulfuric acid solution and step (3) generally can comprise the temperature of contact and the time of contact, and the temperature of described contact can be 20- 70°C, preferably 30-50°C; the contact time may be 5-60 minutes, preferably 20-45 minutes. The amount of the sulfuric acid solution is not particularly limited, as long as the pH of the regeneration solution is guaranteed to be around 7, it can be considered that the regeneration requirement has been reached. Preferably, the weight ratio of the sulfuric acid solution to the cation exchange resin eluted with ammonia water can be 0.3- 1.5:1, preferably 0.8-1.2:1; the pH value of the sulfuric acid solution is generally 0.5-3, and the sulfuric acid solution may be an aqueous solution containing sulfuric acid.

The present invention is not particularly limited to the way that the sulfuric acid solution is contacted with the cation exchange resin eluted with ammonia water in step (3), for example, it can be soaked or rinsed. Preferably, in order to facilitate operation and facilitate regeneration of the contacted The method is to rinse the cation exchange resin eluted with ammonia water with a sulfuric acid solution, and the flow rate of the sulfuric acid solution may be 5-10 m/h.

The inventors of the present invention have found that the method for separating and purifying lysine in the prior art usually uses sulfuric acid to adjust the pH value of the lysine fermentation broth to 1.5-3.0. At this time, lysine is mainly in the form of divalent cations Existence, 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 ₂ O (2)

Therefore, a large amount of concentrated sulfuric acid needs to be consumed when adjusting the pH value, and a large amount of ammonia water also needs to be consumed when eluted with ammonia water. Moreover, when the resin adsorbed with lysine is washed with water, a large amount of waste water will be generated, which increases the burden on environmental protection and causes a waste of resources. Moreover, the concentration of the lysine eluent obtained by the method of the prior art is relatively low, and its concentration is generally lower than 14% (w/v), and further concentration needs to consume a large amount of steam, and make lysine salt When the acid salt is finished, the crystallization rate is very low, resulting in a high return rate of the crystallization mother liquor, which increases the production cost.

Therefore, the present invention preferably makes the pH of the solution containing lysine 3.5 to 6, more preferably 3.5-4.5. At this time, lysine mainly exists in the form of monovalent cations, 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 ₂ O (4)

The dissociation curves of lysine at different pH values are shown in Figure 1. The dissociation constants of lysine are pK ₁ =2.18, pK ₂ =8.95, and pK ₃ =10.53 respectively. The dissociation at different pH values are as follows:

From the comparison of formula (1) and formula (3) and formula (2) and formula (4), it can be seen that the pH value of the solution containing lysine in the preferred control step (1) is 3.5 to 6, more preferably 3.5-4.5, lysine mainly exists in the form of monovalent cations, at this time, a cation exchange resin can exchange and adsorb a lysine, and in the prior art, the pH value of the lysine fermentation liquid is 1.5-3 At this time, lysine mainly exists in the form of divalent cations. At this time, two cation exchange resins can exchange and adsorb one lysine. Therefore, according to the preferred embodiment of the present invention, its exchange with cation exchange resin can be greatly improved. Adsorption capacity; The inventors of the present invention unexpectedly found simultaneously that the adsorption force between lysine and the resin particles was not weakened, especially when the pH value of the solution containing lysine was preferably 3.5-4.5, the resin had no effect on the Lysine has a strong adsorption capacity. In addition, the same amount of lysine is separated and purified, and the consumption of sulfuric acid and ammonia water is significantly reduced, so the consumption of auxiliary materials is effectively reduced. The concentration of the obtained lysine eluate is higher and higher, therefore, in the process of concentration, the steam consumption of lysine concentration can be effectively reduced, and the purity of the collected lysine solution can reach 92% by weight above.

Preferably, the eluent in step (2) is the lysine eluent obtained in step (3); in step (1), the solution containing lysine has a pH value less than 3.5, preferably Obtained by mixing the lysine fermented serum of 2-3 with the washing liquid obtained in step (2).

In the method of the present invention, in order to save water consumption, effectively remove impurities and improve the purity of the finally obtained lysine eluate, the method also includes the addition of part of the lysine eluate used for concentration and crystallization The lysine eluent of the remaining part outside is returned to step (2), and is used as the eluent for the cation exchange resin adsorbed with lysine obtained in the eluent step (1), so that it is not adsorbed to the cation exchange resin The lysine-containing solution above is replaced by the eluent, and the washing solution is obtained, and the washing solution is used to mix with the lysine fermentation broth whose pH value is less than 4 in step (1) to obtain the lysine-containing A solution of acid for ion exchange. The washing solution obtained in step (2) is used to configure a solution containing lysine with a pH value of 3.5 to 6, preferably 3.5-4.5. On the one hand, the lysine in the unadsorbed washing solution can be effectively re- Ion exchange adsorption treatment is carried out to increase the concentration of the finally obtained lysine eluent, on the other hand it can also be used to adjust the pH value of the solution containing lysine to meet the pH value of 3.5 to 6. Require. In addition, the crystallization rate of the lysine eluent with a higher concentration is also high, so it is also beneficial to improve the crystallization rate of the amino acid eluate and reduce the return rate of the mother liquor. Since the lysine eluent obtained in step (3) is used as the washing liquid for washing and removing impurities from the resin, it replaces the use of a large amount of water in the prior art to rinse the adsorbed resin, thereby significantly reducing the amount of waste water produced , reducing the pressure on environmental protection.

The adjustable range of the weight ratio of the lysine eluate used for concentration and crystallization to the lysine eluate obtained as the eluate step (1) for the adsorption of lysine to the cation exchange resin Wider, as long as it is guaranteed that the lysine eluent that is used for the cation exchange resin adsorbed with lysine obtained in the washing step (1) as the eluent can be used for sufficient elution, and meets the requirements of the washing liquid and the pH value The pH value of the lysine-containing solution obtained by mixing the lysine fermentation broth less than 3.5 can meet the requirement of 3.5-6. Theoretically, the greater the amount of lysine eluent used as eluent for eluting the lysine fermentation supernatant that is not adsorbed on the cation exchange resin, the more lysine that is finally obtained will be eluted The content of lysine in the liquid is just higher, but the amount of the lysine eluent used for eluting the lysine fermentation supernatant that is not adsorbed on the cation exchange resin as the eluent is large, which means The amount of the lysine eluent used for concentrated crystallization is just reduced, therefore, can cause the reduction of output, so should comprehensively consider the quality and output of lysine eluent, and can according to the lysine that elutes down The concentration of the acid eluent and the pH value of the lysine-containing solution to be adjusted are used to determine the cation exchange resin adsorbed with lysine obtained in the washing step (1) to replace the lysine that is not adsorbed on the resin Weight of lysine eluate from acid fermentation supernatant. Preferably, the weight ratio of the lysine eluate used for concentration and crystallization to the lysine eluate obtained as the eluate step (1) for the adsorption of lysine to the cation exchange resin It is 1: 0.1-1, more preferably 1: 0.2-0.6; That is, the lysine eluent used for the cation exchange resin adsorbed with lysine obtained in the washing step (1) is at most preferably lysine wash Half of the total weight of dehydration can meet the above requirements.

According to the present invention, in order to better save water resources in industrialized production, the method also includes before the cation exchange resin eluted with ammonia water in step (3) is regenerated, rinsing step (3) with ammonia water The lysine that has been adsorbed on the cation exchange resin has been eluted, and air is introduced into the resin to discharge water. As long as the amount of water used for rinsing is guaranteed to fully wash away the ammoniacal liquor remaining in the resin (it is generally believed that the pH value of the washing water flowing out from the resin column is less than 9.0, it is washed), because before the analysis step is carried out with ammoniacal liquor , the lysine eluent obtained in step (3) as the eluent has been used to remove impurities once on the resin, so the consumption of water can be appropriately reduced in this water washing step. Usually, the amount of water used in this step is the amount of water used for one resin column volume. Introducing air into the resin can blow out the washing water with dissolved ammonia remaining in the resin and reuse it, which further saves water consumption, wherein the pressure of introducing air can generally be 0.03-0.09MPa.

According to the present invention, in step (1), the lysine fermentation serum is continuously contacted with a cation exchange resin for ion exchange, so that the conditions for lysine to be adsorbed on the cation exchange resin can be conventional exchange adsorption conditions For example, the contacting conditions may include a contacting temperature of 20-70°C, preferably 30-50°C. The weight ratio of the lysine-containing solution to the cation exchange resin is generally 0.75-5:1, preferably 1-3:1.

In step (2), the conditions for eluting the lysine adsorbed on the hydrogen-form cation exchange resin in step (1) with ammonia water can also be conventional eluting conditions, for example, the eluting includes The temperature that can include eluent can be 20-70 ℃, preferably 30-50 ℃; The weight ratio of described eluent and the cation exchange resin that is adsorbed with lysine can generally be 0.25-1.5: 1, preferably 0.5 -1:1.

In step (3), the conditions for eluting the lysine adsorbed on the cation exchange resin with ammonia water can also be conventional conditions, for example, the elution temperature can be 30-70° C., preferably 40° C. -60°C; the concentration of ammonia water can be 2-10% by weight; the weight ratio of ammonia water to the cation exchange resin adsorbed with lysine can generally be 0.45-4.5: 1, preferably 0.8-2.5: 1, more preferably 0.8- 1.5:1.

According to the present invention, the preparation method of the lysine fermentation liquid is well known to those skilled in the art, for example, the lysine fermentation liquid can be subjected to membrane filtration to obtain the lysine membrane filtrate, or the lysine fermentation liquid can be obtained The liquid is flocculated and filtered to obtain the lysine clear liquid after removing bacteria. The specific operation method and conditions can be carried out according to conventional methods and conditions, and will not be repeated here.

According to the present invention, as long as the concentration of lysine in the solution containing lysine meets the requirement of its pH value, usually, the mass volume concentration of lysine in the solution containing lysine is 7 -17g/100ml.

According to the present invention, the mass total exchange capacity of the cation exchange resin in step (1) is ≥ 4mmol/g, preferably 4.5-8mmol/g; the volume total exchange capacity is ≥ 2mmol/ml, preferably 2.05-5mmol/ml.

In the present invention, the mass total exchange capacity or volume total exchange capacity refers to the number of moles of ion exchange groups contained in the ion exchange resin per unit mass or unit volume measured according to the specified working conditions and test methods in the industry. For example, the method for measuring the total mass exchange capacity includes: taking the hydrogen-type cation exchange resin, washing it with desalinated water until the pH is about 6.0, filtering it with a vacuum of 5 kPa for 10 minutes, draining it, and detecting it with a rapid moisture analyzer. its moisture content. Accurately weigh 50.0 g of the drained resin with an analytical balance, and soak the resin in 500 ml of 0.5 mol/L NaOH at room temperature, stirring and soaking intermittently for 48 hours. Take its supernatant and titrate it to pH 7.0 with 0.2mol/L HCl, and calculate its mass exchange capacity according to the volume of dilute hydrochloric acid consumed. Use a graduated cylinder to measure the volume of the drained 50.0g resin, and convert it to obtain the total volume exchange capacity.

In the present invention, the quantity of ion-exchange groups refers to the quantity of ion-exchange groups capable of ion exchange, and can be calculated according to the mass total exchange capacity or volume total exchange capacity of the ion-exchange resin and the mass or volume of the resin, for example , can be calculated by the following formula:

Quantity (mole) of ion exchange groups = volume total exchange capacity (or mass total exchange capacity) of ion exchange resin × volume of ion exchange resin (or mass of ion exchange resin).

In the present invention, the cation exchange resin can be a hydrogen-type cation-exchange resin, or an ammonium-type cation-exchange resin, or a mixed resin of a hydrogen-type cation-exchange resin and an ammonium-type cation-exchange resin. The lysine in the lysine solution can undergo ion adsorption exchange. If it is a mixed resin of hydrogen-type cation exchange resin and ammonium-type cation-exchange resin, considering the cost of raw and auxiliary materials and the adsorption capacity, the molar ratio of the ion-exchange group of the hydrogen-type cation-exchange resin to the ion-exchange group of the ammonium-type cation-exchange resin The ratio may be greater than or equal to 1:1, preferably 2-5:1. In consideration of the adsorption effect alone, it is more preferable that all the resins are hydrogen-form cation exchange resins.

Usually, the method for converting at least part of the ammonium-type cation-exchange resin to the hydrogen-type cation-exchange resin can be soaking the resin eluted with ammonia water (more preferably through water leaching) with acid, and the conditions for transformation are preferably to make the transformation The molar ratio of the ion-exchange group of the hydrogen-type cation-exchange resin to the ion-exchange group of the ammonium-type cation-exchange resin that has not been transformed into the hydrogen-type cation-exchange resin is preferably greater than or equal to 1: 1, more preferably 2-5: 1 is enough. If the adsorption effect is simply considered, it is more preferable to convert all of them into hydrogen-type cation exchange resins. In general, the transformation conditions include the ratio of resin eluted with ammonia water (more preferably, rinsed with water) and acid, and the ion exchange capacity of the cation exchange resin can be calculated according to the exchange capacity of the cation exchange resin and the amount of resin used. The total number of exchange groups, and then according to the molar ratio of the cation exchange resin to be transformed into the hydrogen type and the ion exchange group of the ammonium type cation exchange resin, the consumption of acid is calculated, thereby ensuring that the consumption of acid is just in time to make the required volume The resin transforms to the hydrogen form. Generally, the mass percent concentration of the acid can be 2-10% by weight. The temperature for soaking the resin with acid can be 20-70° C., and the soaking time can be 5-60 minutes. The acid may be selected from one or more of strong inorganic acids such as sulfuric acid, hydrochloric acid, and sulfonic acid.

Since the hydrogen-type cation-exchange resin can be obtained by transforming the ammonium-type cation-exchange resin, the mass total exchange capacity or the volume total exchange capacity of the hydrogen-type cation-exchange resin can be the same as the ammonium-type cation-exchange resin, therefore, The mass total exchange capacity of the cation exchange resin in the present invention is ≥4mmol/g, preferably 4.5-8mmol/g; the volume total exchange capacity is ≥2mmol/ml, preferably 2.05-5mmol/ml.

The content of the ion-exchange resin is not particularly limited in the present invention, and can be appropriately selected according to the molar ratio and exchange capacity of the ion-exchange groups in the hydrogen-type cation-exchange resin or the ion-exchange group in the ammonium-type cation-exchange resin.

The cation exchange resin in the present invention is preferably a strongly acidic cation exchange resin, and the strongly acidic cation exchange resin may be a gel-type ion-exchange resin and/or a macroporous ion-exchange resin.

In the present invention, the matrix resin of the macroporous ion exchange resin and the gel ion exchange resin is not particularly limited. Preferably, the macroporous ion exchange resin is a styrene-based macroporous ion-exchange resin, the gel-type ion-exchange resin is a styrene-based gel-type ion-exchange resin, and the weakly acidic cation-exchange resin is acrylic acid Department of ion exchange resin. For example, the matrix resins of the macroporous styrene-based ion-exchange resin and the styrene-based gel-type ion-exchange resin can be respectively styrene-divinylbenzene copolymers, and the degree of crosslinking of the copolymers can be 4- 8 mol%.

For example, it can be any one of the following resins or their mixture: the product brand is 001×4 styrene-based gel-type strong acid cation exchange resin, the product brand is 001×4H styrene-based gel-type strong-acid cation exchange resin Resin, the product brand is 001×7 styrene-based gel-type strong-acid cation exchange resin, the product brand is 001×7H styrene-based gel-type strong-acid cation-exchange resin, the product brand is 001×7FC styrene-based gel-type Strongly acidic cation exchange resin, the product grade is 001×7MB styrene-based gel-type strong acidic cation-exchange resin, the product grade is 001×8 styrene-based gel-type strong-acid cation-exchange resin, the product grade is 001×8FC styrene It is a gel-type strongly acidic cation exchange resin, the product brand is 001×8MB styrene-based gel-type strong-acid cation-exchange resin, the product brand is 001×10 styrene-based gel-type strong-acid cation-exchange resin, the product brand is 001 ×10H styrene-based gel-type strongly acidic cation exchange resin, product grade 001×16 styrene-based gel-type strongly acidic cation-exchange resin, product grade SQ-66 styrene-based gel-type strongly acidic cation-exchange resin, The product grade is SQ-68 styrene-based gel-type strong acid cation exchange resin, the product grade is SQ-607 styrene-based gel-type strong-acid cation exchange resin, and the product grade is D001 styrene-based macroporous strong-acid cation exchange resin Resin, the product brand is D001H styrene macroporous strong acid cation exchange resin, the product brand is D001FC styrene macroporous strong acid cation exchange resin, the product brand is D001MB styrene macroporous strong acid cation exchange resin, The product brand is SQD-61 styrene macroporous strong acid cation exchange resin, the product brand is SQD-65 styrene macroporous strong acid cation exchange resin, and the product brand is SQD-67 styrene macroporous strong acid cation Exchange resin, the product brand is WA-2 special resin for amino acid, styrene-based gel-type strongly acidic cation exchange resin. The various cation exchange resins listed above are commercially available.

According to the present invention, the sphericity of the cation exchange resin is not particularly limited. From the viewpoint of further improving the mechanical strength of the ion exchange resin, the sphericity of the cation exchange resin is preferably 95% or more. In the present invention, the uniformity coefficient of the cation exchange resin may be 1.05-1.6, preferably 1.05-1.4. In the present invention, the sphericity refers to the percentage of the number of spherical particles of the resin in the total number of particles; the uniformity coefficient refers to the sieve diameter that can pass through 60% volume resin and the sieve diameter that can pass through 10% volume resin Ratio.

In the present invention, the ion-exchange groups of the cation-exchange resin can be properly selected according to specific usage conditions, and are not particularly limited.

Specifically, the ion exchange group of the hydrogen type cation exchange resin may be a -SO ₃ H group, and the ion exchange group of the ammonium type cation exchange resin may be a -SO ₃ NH ₄ group. The above-mentioned ion-exchange resins can be obtained commercially, and commercially available hydrogen-form or sodium-form cation-exchange resins can also be transformed with dilute ammonia water to obtain ammonium-form cation-exchange resins.

According to a preferred embodiment of the present invention, as shown in Figure 2, the cation exchange resin is a plurality of series of cation exchange resin column groups, and the purification method of lysine comprises making the solution containing lysine and Multiple groups of cation exchange resin column groups are contacted for ion exchange chromatographic separation, each group of cation exchange resin column groups sequentially and cyclically pass through the adsorption area 1, the impurity removal area 2, the analysis area 3 and the regeneration area 15, so that the cation exchange resin column groups Exchange adsorption, impurity removal, analysis and regeneration are carried out sequentially and cyclically:

(1) At least two groups of cation exchange resin column groups are in the adsorption zone 1 at the same time, and in the adsorption zone 1, the solution 5 containing lysine moves from the cation exchange resin column group that is in the first place in the adsorption zone 1 along the movement direction of the cation exchange resin column group Introduced from the upper end of the adsorption zone 1, it flows through each group of cation exchange resin column groups in the adsorption zone 1 in sequence, and the adsorption raffinate obtained after contacting with the resin flows out from the lower end of the cation exchange resin column group at the end of the adsorption zone 1; The lysine in the lysine-containing solution introduced into the first cation exchange resin column group is exchanged and adsorbed with the active group in the group of resin columns to reach the exchange capacity of the resin, and the exchange is stopped, and the saturated cation exchange resin The column group is moved into the impurity removal area 2; the solution 5 containing lysine is a mixture obtained by mixing the lysine fermentation serum with a pH value of less than 3.5, preferably 2-3, and the washing liquid 6;

(2) At least two groups of cation exchange resin column groups are in the impurity removal area 2 at the same time, and in the impurity removal area 2, the eluent is moved from the upper end of the resin column group that is in the first place in the impurity removal area 2 along the movement direction of the cation exchange resin column group Introduce, sequentially rinse each group of cation exchange resin column groups adsorbed with lysine in the impurity removal area 2, and flow out the washed washing liquid 6 from the lower end of the cation exchange resin column group at the end of the impurity removal area 2 ; and the cation exchange resin column group after the rinsing is moved into the analysis area 3, and the washing solution 6 after the rinsing is returned to the adsorption area 1 for preparing a solution 5 containing lysine; the eluent is Lysine eluent 7;

(3) At least two groups of cation-exchange resin column groups are in the analysis area 3 at the same time, and in the analysis area 3, use ammonia 8 to introduce from the upper end of the resin column group that is in the first place in the analysis area 3 along the movement direction of the cation-exchange resin column group and flow sequentially Through each group of cation exchange resin column groups in the analysis area 3, and flow out the lysine eluent 7 from the lower end of the cation exchange resin column group at the end of the analysis area 3; and the cation exchange resin column after the analysis The group is moved into the regeneration area 15, and part of the lysine eluent 7 is returned to the impurity removal area 2 as the eluent;

(4) at least two groups of cation-exchange resin column groups are in the regeneration zone 15 simultaneously, and in the regeneration zone 15, use sulfuric acid solution 10 to introduce from the upper end of the resin column group that is in the first place in the regeneration zone 15 along the cation-exchange resin column group moving direction and sequentially Flow through each group of cation exchange resin column groups in the regeneration area 15, and flow out the waste liquid 11 after regeneration from the lower end of the cation exchange resin column group at the end of the regeneration area 15; and the regenerated cation exchange resin column group Move into adsorption zone 1.

Wherein, the number of the resin column groups in the adsorption area, the impurity removal area, the analysis area and the regeneration area and the number of resin columns in each group of resin column groups can be selected according to actual needs. The number of resin column groups in the adsorption area, impurity removal area and analysis area is 3-8, and each group of cation exchange resin column groups includes 1-6 parallel cation exchange resin columns.

Preferably, as shown in Figure 2, the method also includes moving into the washing zone 4 sequentially before the resolved resin column group is moved into the regeneration zone 15. The upper end of the resin column group after being adsorbed on the lysine eluted on the cation exchange resin at the first place in the washing area 4 is introduced and flows through each group of cation exchange resin column groups in the washing area 4 in sequence, and from the washing area 4 The lower end of the cation exchange resin column group at the end of the zone 4 flows out the waste liquid after washing, and air is passed into the resin to discharge the water; and the washed cation exchange resin column group is moved into the regeneration zone 15.

In addition, preferably, the number of resin column groups in the washing area may also be 3-8, and each group of cation exchange resin column groups preferably includes 1-6 parallel-connected cation exchange resin columns.

The present invention will be further described in detail through specific examples below.

What adopted in following embodiment 1-5 is continuous ion exchange system, model L100-139, 20 cation exchange resin columns (every two parallel resin columns are a group of cation exchange resin column groups, ten groups of the described Cation exchange resin column groups, the ten groups of cation exchange resin column groups are connected in series), the specification of a single column is Ф35×1000mm, made of polytetrafluoroethylene, produced by CALGAN CARBON CORP in the United States. The loading amount of resin in each resin column in Examples 1-4 is 600 grams.

The resin used in the following implementation is a strongly acidic cation exchange resin, the resin model is WA-2 amino acid special resin, the mass total exchange capacity is 5.5mmol/g, the resin type is a gel type cation exchange resin, and the commercially available manufacturer is Anhui Wandong Chemical Co., Ltd., the coefficient of uniformity is 1.3, and the spherical rate is 96%.

The purity of the lysine fermentation liquid/lysine eluent described in the following examples refers to the content of lysine in the lysine fermentation liquid/lysine eluent and the difference between the lysine fermentation liquid/lysine The ratio of the dry content of the acid eluate, wherein the content of lysine is determined by the ninhydrin method, and the dry content of the lysine fermentation broth/lysine eluate is determined by an oven.

Example 1

This example is used to illustrate the purification method of lysine.

(1) 0.8m ^lysine fermentation liquid (lysine content 11.2g/100ml, purity 59.4% by weight) is subjected to membrane filtration (membrane material is ceramics (membrane surface micropore UF1 pore size 0.1um, UF2 pore size 0.2um) , the membrane filtration pressure is 1.5bar, the membrane filtration temperature is 75°C, and the filtration time is 1 hour), to obtain the lysine fermentation supernatant liquid through membrane filtration with a pH value of 3, and mix it with the washing liquid (obtained in step (3) Washing liquid) mixed, the consumption of washing liquid makes the pH value of the obtained mixed solution containing lysine be 6;

(2) at 40 DEG C, the solution containing lysine with a pH value of 6 obtained in step (1) is continuously pumped in from the upper end of the resin column group at the first place in the adsorption area (the flow rate of the solution containing lysine is 6.3m/h, the weight ratio of the solution containing lysine to the resin is 2:1), the adsorption raffinate obtained after contacting with the resin flows through each group of resin column groups in the adsorption area successively, and from the The lower end of the resin column group at the end of the zone flows out; the lysine in the solution containing lysine introduced into the first resin column group exchanges and adsorbs with the active group in the resin column to reach the exchange capacity of the resin. Stop, move the saturated resin column group into the impurity removal area, and continue to introduce the solution containing lysine from the upper end of the next group of resin column groups adjacent to the first resin column group, and repeat the above steps;

(3) In the impurity removal area, use a 45°C eluent (the lysine eluent obtained in step (3)) to introduce from the upper end of the resin column group at the top of the impurity removal area (the flow rate of the eluent is 7.6 m/h, the weight ratio of the eluent to the resin adsorbed with lysine is 0.8: 1), sequentially flow through each group of resin column groups adsorbed with lysine in the impurity removal area, and from the impurity removal area The lower end of the cation exchange resin column group at the end flows out the washed washing solution, and the washed resin column is sequentially moved into the analysis area, and the washed washing solution is returned to the adsorption area for the preparation of lysine-containing The solution;

(4) at 40 DEG C, in the analysis area, use 5% by weight of ammonia water to introduce from the upper end of the resin column group that is in the first place in the analysis area (the flow velocity of ammonia water is 9.6m/h, and the ammonia water and the resin adsorbed with lysine The weight ratio is 1: 1), flow through each group of cation exchange resin column groups in the analysis area successively, and flow out from the lower end of the cation exchange resin column group at the end of the analysis area and collect 20.1g/100ml of Lai Lysine eluate (purity 94% by weight); part of the lysine eluate is returned to the impurity removal area of step (3) as eluent.

(5) Move the resolved resin into the washing area in turn, in the washing area, introduce the upper end of the resin column group that is the first in the washing area, and each group in the washing area has been adsorbed to the cation exchange resin column with ammonia water in turn The resin column group after the lysine elution on the group is washed with water, and the washing solution after washing is flowed out from the lower end of the cation exchange resin column group at the end of the washing area; and air is passed into the resin column after the water washing, drain the water;

(6) rinsing the cation exchange resin through ammonia water elution and water washing with sulfuric acid solution (pH value is 1), the resin is regenerated, the temperature of rinsing is 40 ℃, and the time of rinsing is 20 minutes (the sulfuric acid The weight ratio of the amount of the solution to the cation exchange resin eluted with ammonia water and washed with water is 1.2:1); and the regenerated cation exchange resin is reused in step (1).

The order of movement of each group of resins is to move from the adsorption area to the impurity removal area, from the impurity removal area to the analysis area, from the analysis area to the washing area, and then return to the adsorption area from the washing area for circulation; and the lysine eluent, The washing liquid returns to the resin in the impurity removal area from the resolved resin column in the analysis area in the reverse direction of the resin, and the obtained washing liquid returns to the resin in the analysis area from the leached resin in the impurity removal area, and the resin and Materials (eluent, washing liquid) move at a speed of 7.5m/h in reverse.

Example 2

This example is used to illustrate the purification method of lysine.

Purify lysine according to the method of Example 1, except that in step (1), the amount of washing liquid is such that the pH value of the resulting mixed solution containing lysine is 3.5. In the obtained lysine eluate, the content of lysine was 21.4 g/100 ml, and the purity was 96% by weight.

Example 3

This example is used to illustrate the purification method of lysine.

According to the method for embodiment 1, lysine is purified, and difference is:

In step (1), the amount of washing liquid makes the resulting mixed solution containing lysine have a pH value of 3.5;

In step (2), the temperature of ion exchange is 50°C, the flow rate of the solution containing lysine is 5m/h, and the weight ratio of the solution containing lysine to the resin is 1.6:1;

In step (3), the temperature of the eluent is 60° C., the flow rate of the eluent is 9.5 m/h, and the weight ratio of the eluent to the resin adsorbed with lysine is 1:1;

In step (4), the analytical temperature is 60° C., and the adsorbed resin column of step (3) is eluted successively with 5.6% by weight of dilute ammonia water, and the flow rate of ammonia water is 13.6 m/h. The weight ratio of the resin of amino acid is 0.9: 1, and the lysine eluate (purity 96.5% by weight) that obtains content is 18.6g/100ml;

In step (6), the cation exchange resin eluted and washed with ammonia water is rinsed with sulfuric acid solution (pH value is 1.5), and the resin is regenerated. The temperature of the rinse is 30° C., and the rinse time is 45 minutes ( The weight ratio of the amount of sulfuric acid solution to the cation exchange resin eluted with ammonia water and washed with water is 1:1); and the regenerated cation exchange resin is reused in step (1).

The order of movement of each group of resins is to move from the adsorption area to the impurity removal area, from the impurity removal area to the analysis area, from the analysis area to the washing area, and then return to the adsorption area from the washing area for circulation; and the lysine eluent, The washing liquid returns to the resin in the impurity removal area from the resolved resin column in the analysis area in the reverse direction of the resin, and the obtained washing liquid returns to the resin in the analysis area from the leached resin in the impurity removal area, and the resin and The material (eluent, washing liquid) moves at a speed of 11.4m/h in reverse.

Example 4

This example is used to illustrate the purification method of lysine.

According to the method for embodiment 1, lysine is purified, and difference is:

The lysine content in the lysine fermentation broth is 13.2g/100ml, and the purity is 56.4%;

The amount of washing solution in step (1) makes the resulting mixed solution containing lysine have a pH value of 4.5;

In step (2), the temperature of ion exchange is 30°C, the flow velocity of the solution containing lysine is 5.7m/h, and the weight ratio of the solution containing lysine to the resin is 1.8:1;

In step (3), the temperature of the eluent is 40° C., the flow rate of the eluent is 5.7 m/h, and the weight ratio of the eluent to the resin adsorbed with lysine is 0.625:1;

In step (4), the temperature for analysis is 40°C, and the adsorbed resin column of step (3) is eluted sequentially with 4.5% by weight of dilute ammonia water, and the flow rate of ammonia water is 12.6m/h. The weight ratio of lysine to resin was 1.2:1, and a lysine eluate with a content of 19.2 g/100 ml (purity 95.3% by weight) was obtained.

In step (6), the cation exchange resin eluted with ammonia water and washed with water is rinsed with sulfuric acid solution (pH value is 2), and the resin is regenerated. The temperature of the rinse is 35° C., and the rinse time is 25 minutes ( The weight ratio of the amount of sulfuric acid solution to the cation exchange resin eluted with ammonia water and washed with water is 0.5:1); and the regenerated cation exchange resin is reused in step (1).

The order of movement of each group of resins is to move from the adsorption area to the impurity removal area, from the impurity removal area to the analysis area, from the analysis area to the washing area, and then return to the adsorption area from the washing area for circulation; and the lysine eluent, The washing liquid returns to the resin in the impurity removal area from the resolved resin column in the analysis area in the reverse direction of the resin, and the obtained washing liquid returns to the resin in the analysis area from the leached resin in the impurity removal area, and the resin and The material (eluent, washing liquid) moves at a speed of 11m/h in the reverse direction.

Example 5

This example is used to illustrate the purification method of lysine.

According to the method for embodiment 1, lysine is purified, and difference is:

The lysine content in the lysine fermentation broth is 9.2g/100ml, and the purity is 46.4% by weight;

The amount of washing solution in step (1) makes the resulting mixed solution containing lysine have a pH value of 4.2;

In step (2), the temperature of the ion exchange is 50° C., and there are 30 cationic resin columns (every three parallel resin columns are a group of cationic exchange resin columns, ten groups in total, and the ten groups of resin columns are connected in series, each Resin loading in the first resin column is 18 kilograms) the flow rate of the solution containing lysine is 5.0m/h, and the weight ratio of the solution containing lysine and resin is 1.5: 1;

In step (3), the temperature of the eluent is 50° C., the flow rate of the eluent is 6.85 m/h, and the weight ratio of the eluent to the resin adsorbed with lysine is 0.6:1;

In step (4), the temperature for analysis is 60°C, and the adsorbed resin column of step (3) is eluted sequentially with 5.4% by weight of dilute ammonia water, the flow rate of ammonia water is 15m/h, and the ammonia water and the adsorbed lysine The weight ratio of acid to resin was 0.75:1, resulting in a lysine eluate with a content of 18 g/100 ml (purity 96.2% by weight).

In step (6), the cation exchange resin eluted with ammonia water and washed with water is rinsed with sulfuric acid solution (pH value is 3), and the resin is regenerated. The temperature of the rinse is 50° C., and the rinse time is 50 minutes ( The weight ratio of the amount of sulfuric acid solution to the cation exchange resin eluted with ammonia water and washed with water is 1.5:1); and the regenerated cation exchange resin is reused in step (1).

The order of movement of each group of resins is to move from the adsorption area to the impurity removal area, from the impurity removal area to the analysis area, from the analysis area to the washing area, and then return to the adsorption area from the washing area for circulation; and the lysine eluent, The washing liquid returns to the resin in the impurity removal area from the resolved resin column in the analysis area in the reverse direction of the resin, and the obtained washing liquid returns to the resin in the analysis area from the leached resin in the impurity removal area, and the resin and Materials (eluent, washing liquid) move at a speed of 13.3m/h in reverse.

Comparative example 1

This comparative example is used to illustrate the reference method of lysine purification.

According to the method of Example 1, lysine is purified, the difference is: the pH value of the membrane-filtered lysine fermentation clear liquid obtained through sulfuric acid adjustment is 2.0, and the lysine eluent is not used in the impurity removal area. rinse with deionized water instead. And the resin is regenerated without sulfuric acid. With dilute ammonia water (mass percentage concentration is 5% by weight), the resin column through adsorption that is rinsed with deionized water is successively eluted to obtain the lysine eluent (lysine hydrochloride content in the eluent is 14.5g/100ml, purity 78% by weight).

Respectively get 100 grams of the regenerated resin of Example 1 and 100 grams of the washed non-regenerated resin of Comparative Example 1 and mix with 300 grams of lysine fermentation supernatant (wherein the concentration of lysine is 10% by weight) , placed with intermittent stirring for 48 hours, then detect the concentration of lysine in the lysine fermentation supernatant after the adsorption (the concentration of lysine in the supernatant after the resin adsorption of Example 1 is 3.4% by weight, after comparative example 1 The concentration of lysine in the supernatant liquid after adsorption by the resin is 5% by weight), and the adsorption amount can be calculated by the difference of the concentration of lysine in the supernatant liquid of lysine before and after adsorption. This shows that the adsorption capacity of the regenerated resin is 32% higher than that of the non-regenerated resin. Illustrate, adopt the method of the present invention to regenerate resin, can remove impurity metal ion in resin, the position that originally adsorbed metal ion is vacated, therefore can further adsorb lysine, and then improved separation efficiency.

According to the comparison of Examples 1-5 and Comparative Example 1, it can be seen that the content of lysine in the lysine eluent obtained by the method of the present invention is higher, and the purity of the lysine eluate is also higher , thus illustrating that the method of the present invention can greatly increase the exchange adsorption capacity of lysine and cation exchange resin. In addition, using the method of the present invention to return the resin to the adsorption area to perform the adsorption operation before regenerating the resin can effectively improve the service life of the resin, and the hydrogen-type resin has a strong adsorption capacity, which in turn improves the adsorption capacity of the resin and finally achieves separation efficiency. improvement.

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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