KR19990068370A - A new processing method of the liquid fertilizer using ion exchange resin column - Google Patents

Abstract

The present invention relates to a process for obtaining glutamic acid fermentation by-products from liquid fertilizer (hereinafter referred to as liquid ratio) and adsorption mother liquor, which is a raw material of liquid feed, by improving the current glutamic acid seasoning manufacturing process using an ion exchange resin tower.

There are several ways to separate glutamic acid (GA) from glutamic acid fermentation broth. In Korea, the direct method and decomposition method are adopted to reduce the generation of mother liquor (or waste fluid) for about 20 years.

Twenty years ago, briquettes were abundant, so that the mother liquor of glutamic acid was adsorbed and dried on briquettes to make organic fertilizers.

Then, as the amount of briquettes is reduced, glutamate seasoning (MSG) method is used to first extract GA by direct crystallization using isoelectric point in order to reduce the amount of waste liquid, and remaining mother liquor (glutamic acid mother-liquor): The process was changed to a method of concentrating GA-ML) and acid hydrolysis as a strong acid, that is, decomposition. In this method, organic matter (other than GA, ie, cells, sugars, etc.), which are fertilizers and adhesives, in the mother liquor are decomposed into humus. According to this method, high-quality raw materials for useful organic fertilizers can be used. The organic matter is discarded.

The amount of waste is reduced to less than one-tenth, but the resulting waste, namely glutamic acid hydrochloride mother-liquor (G-Hcl-ML) and filter-cake (humus, in this process) is called humus. ) Is difficult to recycle and is disposed of by dumping at sea. However, since 2001, dumping of ocean dumping has been banned, and new breakthrough manufacturing methods have to be found.

The present invention can be easily by-produced fermentation adsorption mother liquor by adding one more cation exchange resin tower process, leaving the skeleton of the current purification process, and this mother liquor contains a lot of sugars and cells as a raw material for fertilizer and feed It can be recycled and solve wastewater pollution problems at the same time.

Glutamic acid is a zwitterion with an isoelectric point of pH 3.2 and is well adsorbed on strong acid resins. Using this principle, GA is adsorbed by passing through a strong acid ion exchange resin tower of NH ₄ ⁺ Form without concentrating the 3rd GA-ML (ML is an abbreviation of mother liquor, ML) in FIG. 1.

At this time, GA is adsorbed and the mother liquor is separated and concentrated, and the pH is adjusted immediately. The solution becomes liquid, and it can be used as a raw material of feed (mainly adhesive of pellet feed).

GA-adsorbed resin tower is washed and then eluted as ammonia solution to obtain eluent of GA and sent to the transition crystallization process.

The new manufacturing method may be called a direct method, an ion exchange resin method, or a decomposition method, and an ion exchange resin method is added to the conventional direct method and decomposition method. This resin process can replace the decomposition process, but the decomposition process must remain as it is.

The reason is that the adsorption mother liquor of this resin method is mainly used as a raw material for liquid fertilizer, and this liquid fertilizer is used as a fertilizer for compost and an adhesive for siliceous fertilizer. In other words, since it is a seasonal commodity, the remaining mother liquor should be treated with acid decomposition when the demand for liquid fertilization decreases.

As an effect obtained by adding the process of the present invention to the current process:

First, it can eliminate the pretreatment process that removes Ca ²⁺ ions from molasses. (CaSO ₄ by-products in the pretreatment process are byproducts difficult to treat due to their low purity and little use.)

Second, the process of acid decomposing 3D GA-ML is a very complicated and long process, which increases the manufacturing cost. By-product hydrochloride or lactate waste and Humas (filtration cake) contributed greatly to reducing the amount of waste liquid. It is a pollutant that is difficult to treat due to its little use. The process of the ion exchange resin method of the present invention can replace all or part of this acid decomposition step.

The ion exchange resin method has the advantage of easy automation due to the simple process, and organic adhesives (saccharides, cells, etc. other than GA) remain intact in the by-product adsorption mother liquor, so that the adhesive for organic fertilizer and siliceous fertilizer , Compost housing supplements, feed raw materials, pellet feed adhesives have the advantage of being recycled.

Third, recently, UR and GR agriculture has become the government's goal of 21st century agriculture, and the soil revitalization movement is being strongly promoted by improving the soil with coal ash of power plants and slag of steel mills. Since it is a fine powder, it is difficult to fertilize, and as a mother liquid fertilizer of the seasoning industry, it is common to separate them and to fertilize them mechanically. However, the current liquid ratio is GA-ML mixed with CaSO ₄ in the pretreatment process and lactate waste solution in the decomposition process (GH ₂ SO ₄ -ML: weak adhesion due to strong acid decomposition), and it is inferior in adhesiveness and contains yuan. It is difficult to use in paddy fields, and is used in small amounts as adhesives for soil improvers and as composting agents. Therefore, by applying the ion exchange resin process of the present invention can obtain a good liquid ratio, can contribute to the problems of wastewater in the glutamic acid industry as well as the vitalization of agriculture.

Description

A new processing method of the liquid fertilizer using ion exchange resin column}

Among amino acids, glutamic acid has a history of 100 years, which is used as a seasoning due to its high taste and accounts for about 60% of the total amino acid production.

Glutamic acid production methods include extraction methods, synthesis methods, fermentation methods, and enzyme production methods, and are produced by fermentation methods in Korea. The purification process following the fermentation process has been developed as a compromise method of direct method, decomposition method, direct method, and decomposition method.

The reason why the purification method is diversified is not because of the comparative advantage of manufacturing cost, but because the manufacturing process has been changed according to the level of wastewater treatment technology of the time and the intensity of the authorities' crackdown.

The present invention relates to this purification method, and instead of decomposing the fermentation mother liquor by decomposition in the present process, GA is adsorbed to the ion exchange resin column and the adsorption mother liquor is separated separately without impairing the properties. The present invention relates to a method for obtaining and recycling the siliceous fertilizer for pressure-sensitive adhesive, animal husbandry, and the like.

The method of refining seasonings has been developed in such a way that it does not cause or reduce wastewater pollution. The direct method and decomposition method currently adopted in Korea is a method of carbonizing (humidifying) using strong acid and ignition without recycling the mother liquor. The amount of (waste) has been drastically reduced (ie, the total amount of BOD), but the hummus generated here are durable humus, which is difficult to disintegrate by microorganisms, and is a glutamic acid hydrochloride mother-liquor or GA lactate. The mother liquor (glutamic acid sulphuric acid-ML) is strongly acidic, which is about 2N, and the inactive ingredients such as organics and bacteria are carbonized and filtered out.

Therefore, at present, the treatment of the ocean dumping method, but since the dumping of the ocean since 2001, the refining method that can be solved fundamentally in the car must be found, the present invention is one of the answers.

MSG generates about 85% of the waste liquid because the concentration of fermentation broth is about 15%. Since the BOD of the fermentation broth is 100,000 ppm or more, it becomes a huge pollution factor for the total quantity.

Therefore, according to the conditions of the pollution treatment of the times, the industry has improved the process by reducing wastewater pollution.

Decomposition was a classic method of the 50's when hydrolyzed gluten protein from skim soybeans and wheat flour was used to make MSG.In the 60's, a method of fermentation using molasses as a medium was developed. It was changed to decomposition (aka hydrochloride method). (Refer to Fig. 2) This purification method has a long process and difficult automation, and the hydrochloric acid waste liquid is a strong acid, so there is a problem of pollution treatment (at that time, it is possible to make unsanitary soy sauce with the hydrochloric acid waste liquid and send it to the soy factory for pollution problems. It is not used now, but some of the processes are used in the current direct method or decomposition process.

Amino acids are constituents of the protein and are positive electrolytes with amino groups (amino base,-NH ₂ ) and carboxyl groups (Carboxyl base, -COOH).

Due to this property, amino acids can be used in various seasonings (MSG, glutamate soda), food additives, feed additives (L-Lysin), chemicals and pharmaceuticals.

In 1996, the world's estimated production was 1,650,000 tonnes, of which 60% were MSG, the seasoning, 36% of the feed additives methionine and L-Lysin hydrochloride, and the remaining 4% were for pharmaceuticals and sweeteners (aspartame).

The fermentation medium mainly uses molasses, and the strain uses micrococcus strains such as Corynebacterium sp., Brevibacterium lactofermentum.Because the cells are too fine to be filtered, various problems occur in the purification process. As the mixture was mixed up to the process, it was necessary to use an excessive process of acid-decomposing (humidifying) to remove the cells and the residue.

Direct method and decomposition method:

GA is a positive ion with isoelectric point and pH is 3.2. At this time, the solubility is the lowest. Therefore, GA is obtained by fermentation by conventional method using this property.

The fermented broth is concentrated two to four times, and acid is added to it to cool to pH 3.2, which results in GA crystallization.

The GA crystals are separated and the remaining mother liquor is concentrated again to pH 3.2 and the crystallization is repeated. This process is repeated 2-3 times.In the final mother liquor (the 3rd mother liquor of process 1), residues, cells and salts ( Or yuan) is contained in a large amount to interfere with crystallization, this process is called a direct acdifying method.

GA in the fermentation broth is in the form of ammonium salts.

GANH ₄ ⁺ + Hcl → GA (pH 3.2) + NH ₄ Cl

The above reaction is established.

First, 70-80% of GA was recovered by the direct method, but a large amount of GA remained in the GA and ML, and it was necessary to recover more.These impurities and GA were also contained because a large amount of impurities such as cells, residues, and salts were contained. Different techniques are used to separate them.

GA does not destroy (2-3N) even in strong acidity, and has the property to form GA-hydrochloride or GA-lactic acid in weak bond with hydrochloric acid or lactic acid.

GA + Hcl (reacts with more than 2N Hcl) → GA · Hcl

GA + H ₂ SO ₄ (reacts with 2N or more H ₂ SO ₄ ) → GA · H ₂ SO ₄

Using this property, the concentration of tertiary GA · ML is concentrated, and the acid concentration of the whole liquid is adjusted to 2N with strong acid, and then decomposed for 8 hours at 100 ° C.

Carbonization (dehydration by acidic dehydroxylation acid) leads to hum and GA remains in acidic state in solution.

The scheme is;

GA + C-Hcl + Organics (reaction for 8 hours at 100 ° C) → AGHcl + NH ₄ cl + Hcl + Humus

GA + CH ₂ SO _{4 +} Organics → GAH ₂ SO ₄ + (NH ₄ ) ₂ SO ₄ + H ₂ SO ₄ + Humus

The decomposed solution is filtered to remove the hum, which is the filtration foil, and the solution of the acid salt of GA, the filtrate, is concentrated. At this time, a salt (or yuan) having low solubility in strong acid precipitates first, and the salt is discharged to the bottom of the concentration tube. When the concentrated solution of the concentrated GA salt is cooled and crystallized for 5 to 8 days, GA and acid salts are crystallized. The GA and acid salts are separated by a centrifuge, and the separated solution is called GA and acid waste. This process is called an acid decomposition method or a decomposition method, and the entire process is called a direct method or a decomposition method when connected to the former direct method.

This decomposition method has the advantage of drastically reducing the amount of GA and ML and fundamentally removing organic matter (cells, residues, etc.) from the process, and Korea has adopted this method for more than 20 years.

However, in this process, by-products of humus and acid waste are very difficult to treat the pollution, which is usually carried out at sea dumping, but since 2001, the dumping of sea dumping is prohibited.

Humus originally refers to corrosives and corrosive soils with many nutrient elements due to the natural decay of plants in soil fertilizers.In the seasoning process, the so-called Humas has been called Humas for decades, but in the exact sense it is the characteristics of humus. It has only a little bit, so it is GA and acid decomposing wastepaper.

The animals, plants, microorganisms, the soil Hugh Marsden and at most plant-corrosive food, positive ionization to have a suction function and the soil _{(, Humus-NH 2, Humus} -NH 3 + Humus-COO - -, Humus-O) It should be composed of edible humin body, humic acid, sugar-amine, nucleic acid, phospholipid, sulphurlipid, polysaccharide, etc. to have the effect of soil chemical, physical and biological soil improvement.

Humas in GA hydrochloride lungs are a type of durable humas that are difficult to decompose in nature, leaving only -CCC- to decompose into strong acids, which improves the physical properties of the soil. However, when it is used in soil, it should be mixed with a small amount of natural humus. In other words, the amount that can be exhausted with fertilizer. (Reference: Jeong Yeon-gyu, Fertilizer and Fertilization Technology, p. 178)

On the other hand, one of the waste liquid of the GA hydrochloride, sulfate of other waste from this process is salt inside and ammonium sulfate, which is much contained in the got registered as a fertilizer, just neutralized when used be used in the soil, but CL ^-, SO ₄ Strong acidic radicals, such as ^2- , remain, and when used in the form of liquid fertilizers, they cannot be used alone by soil caking without soil granulating. Disadvantages: It is low in viscosity due to strong acid decomposition and can be used as a binder for segregation of soil modifiers such as coal ash and blast furnace slag. In other words, the amount of by-products and the amount recycled are not balanced, and a large amount of waste remains, but most of all, their use is seasonal, and thus a large amount may be accumulated in the off-season.

Therefore, this direct method and decomposition method should be supplemented by inserting another process due to these environmental problems, and a recycling system harmonized with the mother liquor obtained in the new process should be urgently developed.

As a technique related to this technical field, there is a technique using an organic flocculant (Korean Patent Publication No. 94-14767, a method for separating cells from amino acid and nucleic acid fermentation broth), which is made by adding 50 to 300 ppm of the organic flocculant to the fermentation broth at 50 to 80 ° C. It is a method of separating the cells by heating for 30 minutes to 2 hours, and the cell separation is also partial (the patent mentions that the mechanical throughput is reduced to 18 to 31%) and when heated at 50 to 80 ° C. for 2 hours, There is a lack of countermeasures against the problem of pigmentation due to the maillard reaction of the main components [amino acids + NH ₄ ⁺ + sugars], and no countermeasures against the treatment of the remaining non-aggregated BOD.

Patent Publication 96-8658 (Manufacturing method of fertilizer in the form of water-soluble powdered solid salt using amino acid mother liquor) concentrates GAML after removing bacteria and supplements it with phosphate, and aged for 4-6 hours at 45 ℃ It is a method of making fertilizers in the form of fertilizers, which do not corrode organic matters. So when fertilized in soil, there is a risk of damaging the roots of plants due to the heat of maturity. There is a fear that it may cause a bad effect on the crops by freezing.

In the present invention, GA-ML, which contains a large amount of impurities such as cells, residues, and salts, is adsorbed to a strong acid resin tower of NH ₄ ⁺ form by adsorption of GA, and these highly ineffective impurities are discharged together with the adsorption mother liquor. The GA adsorbed on the ion exchange resin then relates to a process of purely separating GA and impurities by eluting as an eluent. (See Figure 3)

This process eliminates the pretreatment of molasses, the first ingredient.

Molasses is the mother liquor that is determined, separated and left in the sugar process of raw sugar and baekji sugar.

In the sugar making process, there is a carbontation process, in which unreacted excess Ca ²⁺ is dissolved in molasses. This ca ²⁺ has no problem in the fermentation process, but it interferes with the crystallization process of GA or MSG during the purification process, and pretreatment removes molasses with H ₂ SO ₄ before fermentation to co-precipitate pigments, proteins and polysaccharides. There is also an effect. The reaction is:

Ca (OH) ₂ + H ₂ SO _{4 →} CaSO ₄ ↓ + 2H ₂ O

CaSO ₄ has low solubility and easily forms insoluble salts to settle and removes CaSO ₄ using nozzle separator.

However, this CaSO ₄ is mixed with organic materials, making it difficult to recycle as a gypsum resource, because gypsum by-products in the chemical industry remain in Korea. It has to be recycled as fertilizer, but it is insoluble, so it cannot be mixed with fertilizer so the remaining amount becomes waste.

Ca ²⁺ is very well adsorbed and removed in the strong acidic ion exchange resin tower, and thus, when the GA-ML ion exchange resin process is adopted, the pretreatment process of the raw molasses is unnecessary.

The reaction scheme with the resin is as follows.

^{_{Adsorption: R-SO 3 - · NH}} 4 + + Ca 2+ → R-SO 3 - · Ca 2+ + NH 4 +

^{_{Elution: R-SO 3 - · Ca}} 2+ + NH 4 OH → R-SO 3 - and NH ₄ + Ca (OH) ₂

Ca ²⁺ is adsorbed with GA on the resin and then separated from GA by column chromatography at the time of elution. That is, the adsorption affinity series of the cation exchange resin has Ca ²⁺ in front of GA, GA comes out first when elution (ie, column chromatography), and Ca comes after (Fig. 4). Ca is separated. Ca ²⁺ is contained in the tail cut and is sent to the wastewater treatment plant.

Second, when the ion exchange resin tower is used as described above, the adsorption mother liquor can be obtained without any damage to organic matter.

This resin tower adsorption mother liquor contains a large amount of organic matter of about 65 to 70%, which has high organic ineffectiveness, and its viscosity is high because about half of the organic matter is sugar (sugar, glucose, fructose, polysaccharide, etc.). It can be used as an adhesive to isolate soil improver (coal ash, slag slag) and is a useful resource that can be used as adhesive for pellet feed due to its high protein content.

In GA-ML (the mother liquor left after crystallizing and separating GA in 2 or 3 GA crystallization process, or final GA-ML in the case of continuous crystallization process), about 3 to 5% of GA, cells, organic matter, sugars, etc. It is mixed.

Since GA is dissolved in 3 to 5%, it should be recovered further. In the ion exchange resin method of the present invention, GA is recovered as follows. (See Figure 3)

Adsorption Process:

When GA-ML is concentrated in NH ₄ ⁺ form strong acid resin (Amberlite IR 120B, Diaion SK-1B), the GA is adsorbed to the resin and the remaining adsorption mother liquor is discharged to the outside of the tower and sent to a separate adsorption mother liquor process. .

^{_{R-SO 3 · NH 4 +}} + GA → R-SO 3 · GA + NH 4 +

Elution Process:

GA adsorbed on the resin is eluted as a 2N NH ₄ OH solution, and the rich-cut (intermediate eluent containing a large amount of the desired component) of the eluent is sent to the GA crystallization process.

_{R-SO 3 · GA + NH} 4 OH → R-SO 3 · NH 4 + + GA

Adsorption mother liquor treatment process:

In the adsorption process, GA and organic matter are separated, but GA remains adsorbed on the resin and organic matter (cells, sugars, etc.) comes out of the tower mixed with the adsorption mother liquor.

The adsorption mother liquor is a solution of organic matter such as high quality sugars and bacteria which is not damaged by any chemical reaction, and can be used for feed and as a composting agent. (See Figure 5)

The mother liquor is concentrated to 1.25∼1.4 in order to reduce transportation costs. Neutralize as NaOH for feed and NH ₄ OH for fertilizer.

Missing short description in the drawing

The present invention relates to a process of separating the GA as a strong acid resin, separating only GA as a strong acid resin, and acquiring the adsorption mother liquor separately without damaging the organic component.

Therefore, the present invention is composed of the resin tower treatment process of the third GA-ML and will be described the process.

(See Figures 1 and 3)

Example 1

Resin Tower and Resin:

Resin towers are to be designed to allow both upflow and downflow.

The reason is that when the fermentation broth becomes the 3rd GA-ML, the cell concentration increases and the cells become clogged with clumps on the ion exchange resin tower resin bed, so they have to be adsorbed upstream.

The resin is a strong acid cationic resin such as Amberlite IR 120B, Diaion SK-1B and the like, and the regeneration is performed as 2N-NH ₄ OH.

Adsorption Process:

In the 3rd GA-ML, GA is 3 ~ 5%, and many organic cells such as a large amount of cells are adsorbed in the upstream, and 3 ~ 5 times of GA-ML of resin VOLUME is passed through the column. The flow rate is expressed as SV (space velocety), and when the volume of the dendritic is 1, the total flow rate of 1 per hour is referred to as SV = 1. The amount of GA-ML should be calculated by test in advance.

Adsorption Equation:

^{_{R-SO 3 - · NH 4}} + GA → R-SO 2 · GA + NH 4 +

After adsorption, all GA-ML remaining in the resin bed (BED) is extracted in the downflow, and the washing water is injected into the resin about 1.5, and air is added to wash the resin adsorbed GA sufficiently, and the washing water is again flowed down into the 1RV (resin bed). The abbreviation for volume, where 1RV of wash water when the resin bed volume is 1 means the same amount as resin bed volume 1).

Elution Process:

The washed GA adsorption resin is eluted as a 2N-NH ₄ OH solution as eluent. The SV of flow rate is 2 and the amount of eluent used is about 2RV. (SV = space velocity: For example, if the resin bed volume is 1, the volume of his ship in one hour is SV = 2.)

This elution causes column chromatography, so that the desired GA enters the rich cut and the unwanted NH ₄ ⁺ , Ca ²⁺ , Fe ^2+, etc. are pre-cut or tail-cut. These pre-cuts and tail-cuts are sent to an activated sludge wastewater treatment plant. (See FIG. 1)

According to this process, the process can be simplified, GA can be separated and concentrated separately and concentrated, and unnecessary inorganic salts can be removed, and pigments, cells, and sugars can be collected as adsorption waste liquid and recycled for feed and fertilizer. It becomes possible.

Treatment process of adsorption waste liquid:

The adsorption waste liquid obtained in this patent is amino nitrogen, that is, the amount of amino acid is high as shown in (Table 1), and the total organic matter is 70% (building ratio), and is processed by the process as shown in FIG.

Concentrate to a specific gravity of 1.3 to 1.4 to reduce transportation costs.

In the case of fertilizers, tail-cuts can be mixed and concentrated. The tail-cut contains a lot of organic materials such as other amino acids along with inorganic substances such as Ca ²⁺ and Fe ³⁺ . If the treatment is difficult due to high BOD (especially winter), the tail-cut is mixed with fertilizer for treatment. can do.

Ammonia is recommended for pH adjustment.

For feed, neutralize with NaOH. When the hay is buried in the hay to enhance the nutrition or use as a fermentation aid, the amount of use varies depending on the type of animal, age, sex, etc., and the right amount is used according to the specification of the ranch.

Table 1 Components and Properties of Fermented Mother Juice Concentrate

1. The existing process focuses on the pollution treatment of fermented mother liquor, and is a method of decomposing organic matter which can be a basic material of fertilizer and feed by strong acidity and removing it. It relates to the process of adding a process.

In the present invention, by allowing fermentation mother liquor to be recycled as long as there is demand in the fertilizer industry and feed industry, it is possible to secure fertilizer resources and feed resources cheaply.

2. In particular, the agricultural sector and fertilizer industry are demanding fertilizers capable of fertilizing the work force, ie, Zhejiang fertilizers, which can be machined in order to enhance international competitiveness after UR.

Since the liquid ratio obtained by this process does not destroy organic matter, the adhesive of high quality for granulation of a fertilizer can be obtained, and it can contribute to the vitalization of agriculture.

3. Therefore, the seasoning process can be rationalized to help reduce the manufacturing cost of seasoning and reduce the cost of waste water and waste cake treatment.

Claims (1)

Strong acidic cation exchange resin tower process (strong acidic cation exchange resin tower process for processing glutamic acid mother liquor), which can obtain the glutamic acid mother liquor after the second and third glutamic acid crystallization added to the existing seasoning process purely without destroying organic matter. Glutamic acid fermentation broth in which the organic substances obtained by using the process are not damaged.