CN1775742A - Decolorization method in the production of L-arginine extracted by hair hydrolysis process - Google Patents

Abstract

The invention relates to a decolorizing method for the production of extracting L-arginine by hair hydrolyzing process, relating to the technique of producing amino acid by protein hydrolyzation. The invention adopts D293 macroporous basic quaternary ammonium I-type ion exchange resin as decolorizing agent column, and operates in turn according to the steps of on-column decolorizing, pigment eluting and resin regenerating. The invention solves the decolorizing difficulty, and the produced L-arginine has the purity and photopermeability stably up to 99.9% and 98.5%, respectively and the producing flow is simple and the synthetic production cost is remarkably lower than that of the activated carbon decolorizing method.

Description

Decolorization method in the production of L-arginine extracted by hair hydrolysis process

Technical field:

The invention relates to the technology of producing amino acid by protein hydrolysis, especially the decolorization method in the production of L-arginine extracted by hair hydrolysis technology.

Background technique:

L-Arginine (L-Arginine), whose chemical name is L-2-amino-5-guanidinopentanoic acid, and whose molecular formula is C ₆ H ₁₄ N ₄ O ₂ , is a white crystalline powder. The international general standard of this product, such as the Japanese Ajinomoto AJI standard, wherein the purity is 98.5-100.3%, and the light transmittance is ≥98.5%. At present, L-arginine is mainly produced by bio-fermentation process and genetic engineering technology. The technology is difficult and the overall cost is high, and most of them are concentrated in foreign enterprises. It is an innovation in our country to hydrolyze the hair with concentrated hydrochloric acid to finally extract the substance. Using concentrated hydrochloric acid to hydrolyze hair and finally extract L-arginine, the biggest feature is low production cost and turning waste into treasure. But at present, the grade of L-arginine produced by this process is not high, mainly because its purity and light transmittance are low, which can only reach 98.4% and 92% respectively. This makes the product very limited in its scope of application, and cannot be used in the fields of medicine and food, and can only be used as a low-grade product.

It is difficult to produce high-quality L-arginine with the hair hydrolysis process. The main reason is that the technical problem of decolorization has not been well solved. At present, the decolorization in the production of L-arginine in this process generally adopts the activated carbon decolorization method. Activated carbon decolorization method is to use activated carbon powder or activated carbon particle decolorization column to carry out pigment molecular adsorption on the passing liquid to be decolorized, so as to realize decolorization. In fact, the activated carbon decolorization method is only suitable for the decolorization of feed liquids under acidic conditions, such as sugars, amino acid salts and other acidic feed liquids, and the decolorization effect is better. For strong basic amino acids, such as arginine, the pigment cannot be removed by activated carbon, so the color of the product is darker, so that the light transmittance and purity are low. People are groping for the decolorization method that the grade of the L-arginine product produced under this process is improved always, but so far there is not a kind of ideal decolorization method that is really applied in the industry, and the active carbon decolorization method is still being used. Therefore, The low-grade problem of the L-arginine produced by the hair hydrolysis process has also not been solved.

Invention content:

The purpose of the present invention is to provide a decolorization method for the production of L-arginine by the hair hydrolysis process, so as to solve the problems of low purity and light transmittance of the produced L-arginine. In addition, the overall cost of production will be lower. reduce.

The method of the present invention adopts D293 macroporous strongly basic quaternary ammonium type I anion exchange resin as the decoloring column of the decolorizing agent, and the operation steps are: the resin decoloring method of column decolorization, pigment elution, and resin regeneration, the resin decolorization method of the resin The structural formula is:

The resin decolorization method is to pass the feed liquid of the material to be decolorized through the resin decolorization column, and through ion exchange, absorb the pigment in the feed liquid to achieve decolorization.

Adopt the resin that the present invention selects for use, in the upper column decolorization step, through the L-arginine decolorization liquid of the decolorization column, the colored substance (pigment) wherein is completely absorbed by the resin, and the effluent is pure arginine product liquid. The decolorization mechanism and process are as follows:

Ion exchange decolorization includes electrostatic interaction and hydrophobic binding force. The colored substances (pigments) in arginine solution are mainly organic compounds produced under alkaline conditions. These organic compounds have amphiphilic properties in alkaline media. , both hydrophilic and hydrophobic, generally anionic. The pigment in the solution is mainly combined with the strongly basic anion resin through two reaction mechanisms: among them, the anions on the resin exchange with the pigment anion in the form of ionic bonds; The phenyl groups bind with hydrophobic forces. If R=NCL is used to represent macroporous strong base anion exchange, and the pigment is represented by F, then the decolorization reaction is Of course, the adsorbed pigment does not show a chemical reaction (no qualitative change), but because the pigment’s affinity to the R=NCL macroporous resin is greater than that of other media in the arginine solution, it is firmly adsorbed into the pores of the resin to play a role. Depigmentation.

The resin used in the present invention is selected from many types of resins. In the process of establishing the present invention, multiple other types of resins, such as styrene, acrylic, and other resins and D293 macroporous strong alkali, have been used. A large number of comparative experiments have been carried out on non-toxic quaternary ammonium type I anion exchange resins. Other types of resins and styrene-based other resins cannot achieve the desired effect on the decolorization of L-arginine to be decolorized. The main performance is that the product quality is up to It is less than the Japanese Ajinomoto AJI92 version standard, the product has low light transmittance, low purity, etc.; the resin has a large amount of adsorption on the product, resulting in excessive product loss and low yield. D293 resin, which is originally used to prepare pure water, copper pyrophosphate and other wastewater treatment and organic reaction catalysts, has produced unexpected effects and effects on the decolorization of L-arginine.

Adopt the method of the present invention, the L-arginine product produced, its purity, light transmittance are stable respectively 99.9%, 98.5%, reach Japan Ajinomoto AJI92 version standard, have become more high-grade products, have solved the problem of using hair The technical problem that the hydrolysis process is difficult to produce high-quality L-arginine products greatly improves the use value of the L-arginine products produced by this process.

The resin used in the present invention basically does not adsorb arginine, but only adsorbs pigments and other impurities, so there is no need for cumbersome operations for re-recovering L-arginine. In addition, this type of resin has a large decolorization capacity on the column, and the adsorbed pigment is easily eluted, and the regeneration is simple.

The invention is applied in the production test, and the produced L-arginine product has stable quality and yield, simplified production process, and the material consumption is regenerant alkali and acid.

The following table is the comparison of the present invention with other aforementioned test resins and the application effect of activated carbon decolorization method.

Hair hydrolysis extraction L-arginine this invention Other resin decolorization Activated carbon decolorization AJI92 standard Transmittance% ≥98.5 94.8～96.4 92.5～93.5 ≥98.0 Purity % ≥99.9 98.0～98.5 98.0～98.4 98.0～100.3 Product Yield Increase % 3.0 (only a small amount of adsorption to the product) For product adsorption, the product needs to be recovered again, and the operation is cumbersome. Adsorbed to the product, not easy to recycle environmental pollution None (resin-treated acid and alkali wastewater can be recycled None (acid and alkali wastewater treated with resin can be recycled Yes (waste activated carbon is discharged directly)

It is used for harvesting, and finally discharged as fertilizer for agricultural production) used, and finally discharged as fertilizer for agricultural production) Production cost/ton 45,000 55,000 to 58,000 60,000 to 62,000 Output: 1000 tons/year 45 million/year 55 million/year 60 million/year Difference in annual cost 10 million/year 15 million/year

Detailed ways:

Below by embodiment the present invention will be further described.

The present invention selects D293 macroporous strongly basic quaternary ammonium type I anion exchange resin as the decolorizing column for decolorizing in the production of L-arginine extracted by the hair hydrolysis process, and its

Structural formula:

Full exchange capacity mmoL/g (dry): ≥3.3

Wet true density (20°C) g/mL: 1.03～1.12

Wet density g/mL: 0.65～0.75

Moisture content%: 50～60

Granularity %: ≥95

pH range: 0～14

Resin decolorization column aspect ratio: 1:4

The steps of the decolorization process are: column decolorization, pigment elution, resin regeneration, and operate according to the following indicators:

Column decolorization: the L-arginine to be decolorized liquid is fed into the decolorized column at a flow rate of 0.4-0.5BV/h (from top to bottom). During the feeding process, the pH value is detected and the effluent is recovered. When the pH value is 9 At -10 o'clock, start to collect the product solution until the outflow of pigment is detected, that is, the resin is saturated, and the column is stopped;

Pigment elution: flush the saturated decolorization column with pure water at a flow rate of 0.5BV/h until the pH value of the effluent is 7-9.5, and flush the decolorization column with 4% acid water at a flow rate of 0.5BV/h to the pH of the effluent value of 0.5, then flush the decolorization column with pure water at a flow rate of 0.4BV/h until the PH value of the effluent is 6, and collect the flushing liquid for recovery and use mechanically;

Resin regeneration: Use the prepared 4% alkaline water to flush the decolorization column at a flow rate of 0.4BV/h until the pH of the effluent is about 12, stop the alkali injection, and use pure water to backwash the decolorization column at a flow rate of 0.55BV/h for 0.5 ~ 1 hour, until the upper outlet liquid is clear, all the backwash water is collected and sent to the storage tank, and finally the decolorization column is flushed with pure water at a flow rate of 0.4BV/h until the pH value is about 6, and the effluent is collected and sent to the alkali Recycle buckets.

The 4% acid water is prepared from 30% HCl and pure water;

The 4% alkaline water is prepared from 30% NaOH or 18% NH ₃ ·H ₂ O and pure water;

The BV/h is the volume of the resin loaded in the resin column flowing through it per hour, and BV is the abbreviation of the volume of the resin loaded in the resin column.

Claims (2)

1. A decoloring method in the production of extracting L-arginine by a hair hydrolysis process adopts a decoloring column which adopts D293 macroporous strongly basic quaternary ammonium I type anion exchange resin as a decoloring agent, and sequentially operates according to the steps of column decoloring, pigment elution and resin regeneration, wherein the structural formula of the resin is as follows:

2. the method for decoloring in the production of extracting L-arginine according to claim 1, wherein when the ratio of the height to the diameter of the resin decoloring column is 1: 4, the steps of decoloring on the column, eluting the pigment and regenerating the resin are operated according to the following indexes:

and (3) column loading and decoloring: positively feeding the L-arginine to-be-decolorized solution into a decolorizing column at the flow rate of 0.4-0.5 BV/h, recovering the effluent liquid to the pH value of 9-10, and collecting the L-arginine feed liquid until the resin is saturated;

pigment elution: positively flushing the decolorizing column with pure water at the flow rate of 0.5BV/h until the pH value of the effluent is 7-9.5, positively flushing the decolorizing column with 4% acid water at the flow rate of 0.5BV/h until the pH value of the effluent is 0.5, positively flushing the decolorizing column with pure water at the flow rate of 0.4BV/h until the pH value of the effluent is 6, and respectively collecting flushing liquids;

resin regeneration: positively flushing a decolorizing column with 4% alkaline water at the flow rate of 0.4BV/h until the pH value of an effluent is 12, reversely flushing the decolorizing column with pure water at the flow rate of 0.55BV/h for 0.5-1 hour until the effluent is clear, positively flushing the decolorizing column with pure water at the flow rate of 0.4BV/h until the pH value of the effluent is 6, and respectively collecting the effluents;

the 4% acid water is prepared from 30% HCL and pure water;

the 4% alkaline water is composed of 30% NaOH or 18% NH₃·H₂O and pure water.