CN104086454A - Glutamic acid chelated calcium product prepared from shell and preparation method thereof - Google Patents

Abstract

The invention provides a glutamic acid chelated calcium product prepared from shells and a method thereof, relates to the green chemical preparation of marine biological functional materials and calcium nutrition enhancers, and belongs to the high-value utilization and utilization of shell resources and amino acid resources. Recycling field. Using shells as raw materials, acid solution is used to convert water-insoluble calcium in shells into water-soluble ionized calcium, solid-liquid separation removes impurities, and then control the pH value, temperature, concentration and molar ratio of glutamate and calcium ions of the filtrate, and chelate After calcium ions form a precipitate, it is processed into calcium glutamate chelate. The purity of chelated calcium glutamic acid in this product is ≥91%, of which the content of calcium ions is ≥16%, and the content of glutamate is ≥72%. The invention can significantly improve the purity, yield and quality of glutamic acid chelated calcium, has novel concept, rich raw materials, low cost, simple process, easy implementation, great popularization, and can be used for high value of shell and amino acid resources Use and recycle to find new ways.

Description

Chelated calcium glutamic acid product prepared from shells and method thereof

technical field

The invention relates to a glutamate chelated calcium product prepared from shells and a method thereof, relates to the green chemical preparation of marine biological functional materials and calcium nutrition enhancers, and belongs to the high-value utilization and recycling of shell resources and amino acid resources field of use.

Background technique

The mollusk mantle has a special glandular cell, and its secretion is a series of biologically active organic compounds. In the natural environment, it can form calcifications to protect the soft part of itself, which is the shell.

The structure of the shell can generally be divided into three layers, the outermost layer is the cuticle with pigment, which is composed of the exudate secreted by the edge of the mantle; the middle layer is the prismatic layer, which is composed of the prismatic calcite secreted by the edge of the mantle, and the outer layer And the middle layer can expand the area of the shell, but does not increase the thickness; the inner layer is the nacre layer, which is made of leaf-shaped aragonite secreted by the entire surface of the mantle, which has a beautiful luster and can thicken with the growth of the body.

Shells are an important natural source of calcium, the main components of which are water-insoluble inorganic calcium such as calcium carbonate, calcium sulfate and calcium phosphate, and a small amount of chitin. There are great differences in the types and shapes of shells, some are spiral shells (such as snails, snails, abalones), some are petal-shaped shells (such as mussels, clams), and some are plate-shaped shells (such as soft-shelled turtles). species, turtles), and some shells are wrapped in the body (such as squid, squid, sea cucumber).

Calcium is one of the essential elements of the human body. It is the fifth constituent element of the human body after C, H, N, and O. It is an important component of human bones, teeth, organs, blood, and muscle tissue. Physiological dysfunction will occur when the human body is deficient in calcium. . Prevention and treatment of calcium deficiency and dietary calcium supplementation have become one of the global research hotspots.

Excessive salt intake is a worldwide phenomenon. Modern medicine has proven that calcium deficiency is more harmful than high sodium. The incidence of high blood pressure, diabetes, obesity and other diseases caused by high sodium and calcium deficiency is increasing year by year and showing a trend of younger age. Therefore, dietary calcium supplementation is one of the main ways to solve the problem of calcium deficiency.

As a nutritional fortifier, calcium nutritional supplements can be used to fortify a variety of foods. Its development has gone through four generations of products including inorganic calcium, organic calcium, complexed calcium and chelated calcium. A good calcium nutrition enhancer should have the following characteristics: high bioavailability, safe and non-toxic and side effects, good calcium absorption rate, and calcium content not less than 10%.

Amino acid chelated calcium is an organic compound with a ring structure formed by a chelation reaction between one or more amino acid groups and calcium ions. It has good chemical and biological stability, is easily absorbed by the human body, has few side effects, and has high bioavailability. High, can effectively solve the disadvantages of traditional calcium nutritional supplements, such as poor solubility, low absorption rate, large side effects, and easy generation of stones.

Calcium glutamate is a kind of amino acid chelated calcium, which is the fourth generation calcium nutritional supplement. The pure product is white crystal or crystalline powder, odorless and tasteless, with special umami taste, soluble in acid, slightly soluble in water and Alkali, insoluble in ethanol and other organic solvents, can be used as salt substitute, calcium nutrition enhancer and food flavoring agent.

The absorption effect of calcium glutamate is better than that of inorganic calcium, organic calcium and complexed calcium. It has the advantages of high bioavailability, stable performance, no toxic and side effects, and good palatability. It has supplementary amino acids and calcium that the previous three generations of calcium products did not have. The dual effects of elements can reduce the antagonism between various elements in the organism. It is an ideal calcium nutritional supplement for humans, animals and plants, and is widely used in the nutritional enhancement of food, medicine, plant fertilizer and animal feed.

Pure glutamic acid is a colorless crystal, slightly soluble in water, soluble in hydrochloric acid and sodium hydroxide, is the most productive amino acid variety, and is mostly obtained by isoelectric precipitation or ion exchange extraction from microbial fermentation broth.

Monosodium glutamate, the sodium salt of glutamic acid, has good water solubility. It is mainly obtained by neutralizing glutamic acid concentrate with sodium hydroxide or sodium carbonate. The pure product is white columnar crystal or crystalline powder. China is the world's largest producer and consumer of MSG, and its output ranks first in the world. In 2012, China's production and consumption of MSG was 2 million tons.

Contents of the invention

The purpose of the present invention is to provide a calcium glutamic acid chelate product prepared from shells and its method, which can find a new way for high-value utilization and recycling of shell resources and amino acid resources.

To achieve the above object, the present invention adopts the following technical solutions:

A glutamic acid chelated calcium product, using shells as raw materials, using an acid solution to convert the water-insoluble calcium in the shells into water-soluble ionized calcium, separating the solid and liquid to remove impurities, and then controlling the pH value and temperature of the filtrate. After the amino acid radical chelates calcium ions to form a precipitate, it is processed into glutamic acid chelated calcium products. The purity of this product chelated calcium glutamate is ≥91%, of which the content of calcium ions is ≥16%, and the content of glutamate is ≥72%.

A preparation method of the described calcium glutamic acid chelated product, using shells as raw materials, using acid solution, under certain temperature and acidity conditions, the water-insoluble calcium in the shells is first converted into water-soluble ionic calcium, solid-liquid Separation and removal of impurities, and then adding glutamate-containing substances to the filtrate, by controlling the pH value, temperature, concentration and molar ratio of glutamate and calcium ions, chelating calcium ions to form a precipitate, and the chelated precipitate is processed Get Calcium Glutamate Chelated Products.

The acid used in the acid solution is one or more of hydrochloric acid, acetic acid, nitric acid, hydrobromic acid, hydroiodic acid, propionic acid, lactic acid; the temperature of conversion to generate water-soluble ionic calcium is not lower than room temperature; the acid The concentration of hydrogen ions in the solution should not be lower than 1.5 mol/L.

Said shells are one or more of marine shells, aquatic shells and terrestrial shells except abalone shells, and may be one or more of original shells, fragments and powders.

The glutamate-containing substance is one or more of monosodium glutamate, glutamic acid and its water-soluble salt products or extracts, glutamate-containing extract, production wastewater, and crystallization mother liquor.

During the chelation precipitation, the concentration of glutamate is not less than 150 g/L, the concentration of calcium ions is not less than 50 g/L, and the molar ratio of glutamate to calcium ions is 0.9:1.0 to 1.5:1.0.

The chelating temperature is not lower than room temperature; the chelating pH is not lower than 6.8.

The processing includes filtering, washing and drying. The drying is one or more of oven drying, sun drying, microwave drying, airflow drying and spray drying.

Significant advantage of the present invention is:

(1) The present invention uses resource-rich shells as raw materials, and does not make lime milk through calcination, but directly uses acid solution to convert water-insoluble calcium into water-soluble ionic calcium under certain temperature and acidity conditions, solidifying The liquid is separated to remove impurities, and the filtrate is processed by chelating calcium ions with glutamate-containing substances to form a precipitate, which can find a new method for the high-value utilization and recycling of shell resources and amino acid resources.

(2) The present invention efficiently dissolves calcium ions under room temperature, low acidity and short time conditions, and through simple procedures such as solid-liquid separation and chelation precipitation, it can efficiently remove impurities such as protein, pigment, chitin, etc., and the obtained glutamic acid The chelated calcium product has high purity, reasonable calcium acid ratio, has the characteristics of slightly soluble in weak acid and weak base, insoluble in water and insoluble in alcohol, low preparation cost, simple process, green and environmental protection, easy to implement, and has great popularization.

(3) The present invention makes full use of the solubility difference of shells and their impurities, and directly uses acid solution to convert water-insoluble calcium into water-soluble ionic calcium. Compared with existing processing methods, the acid used has a high solubility to water-insoluble inorganic calcium such as calcium carbonate, but the dissolution rate of impurities such as proteins, polysaccharides, pigments, and chitin is very low. Under certain conditions, water-insoluble calcium can be efficiently converted into water-soluble ionic calcium, which is helpful for the subsequent chelation precipitation and purification of calcium ions. The process is simple and the production efficiency is high. Moreover, the acid used is a bulk conventional product and is cheap It is easy to obtain and helps to reduce the preparation cost.

(4) The present invention makes full use of the characteristics of weak acid, weak base, slightly soluble and insoluble in water of glutamic acid chelated calcium, and the solubility difference of impurities and glutamic acid chelated calcium under different pH values and temperature conditions, and controls pH value, temperature, concentration and molar ratio of glutamate and calcium ions, chelated calcium ions form a precipitate, which can significantly improve the purity, yield and quality of glutamic acid chelated calcium products, and can realize glutamic acid chelated calcium Efficient separation from impurities.

Detailed ways

A glutamic acid chelated calcium product, which uses shells as raw materials, uses an acid solution, and under certain temperature and acidity conditions, first converts water-insoluble calcium into water-soluble ionized calcium, and removes protein, pigment, and shell by solid-liquid separation. Impurities such as quality and acid insoluble matter, then add glutamate-containing substances to the filtrate, control pH, temperature, concentration and molar ratio of glutamate and calcium ions, chelate calcium ions to form precipitates, and chelate precipitates It is processed into calcium glutamic acid chelate products after being processed by filtration, washing and drying. The purity of this product chelated calcium glutamate is ≥91%, of which the content of calcium ions is ≥16%, and the content of glutamate is ≥72%.

The acid is one or more of hydrochloric acid, acetic acid, nitric acid, hydrobromic acid, hydroiodic acid, propionic acid, and lactic acid.

The calcium salt conversion temperature is not lower than room temperature; the calcium salt conversion hydrogen ion concentration is not lower than 1.5 mol/L.

Said shells are one or more of marine shells, aquatic shells and terrestrial shells except abalone shells, and may be one or more of original shells, fragments and powders.

The glutamate-containing substance is one or more of monosodium glutamate, glutamic acid and its water-soluble salt products or extracts, glutamate-containing extract, production wastewater, and crystallization mother liquor.

During the chelation precipitation, the concentration of glutamate is not less than 150 g/L, the concentration of calcium ions is not less than 50 g/L, and the molar ratio of glutamate to calcium ions is 0.9:1.0 to 1.5:1.0.

The temperature of the chelation precipitation is not lower than room temperature; the pH value of the chelation precipitation is not lower than 6.8.

The drying is one or more of oven drying, sun drying, microwave drying, airflow drying and spray drying.

The purity and calcium content of glutamic acid chelated calcium products are determined by EDTA method, and the content of glutamate is determined by genipin colorimetric method. When evaluating product solubility, the pH value of the solvent is controlled at 5.0-9.5.

Example 1

Take 105 kg of squid and sea cucumber bone slice mixture in a horizontal extractor, add 1.5 mol/L hydrochloric acid solution with a weight ratio of 3.2 times to spray and dissolve calcium ions, and convert water-insoluble calcium into water-soluble ions at room temperature Calcium, solid-liquid separation to remove impurities such as protein, pigment, chitin and acid insoluble matter, the filtrate is sent to the crystallization tank, and the glutamic acid extract is added to the crystallization tank to 58.6 liters, and the concentration of glutamate in the solution is controlled to 258-260 g /L, calcium ion concentration 68-70 g/L, pH value 6.8-7.0, chelate calcium ions at room temperature to form a precipitate, filter through a three-legged centrifuge, and dry the chelated precipitate to obtain glutamic acid Chelated calcium crystalline powder.

After testing, the obtained crystalline powder product of chelated calcium glutamate has the characteristics of weak acid and weak base slightly soluble, insoluble in water and insoluble in alcohol; the purity of calcium glutamate chelate is 91.4%, and the content of calcium ion is 19.2%. The content of amino acid radicals is 72.2%; the total recovery rate of calcium ions in this process is 96.9%, and the total recovery rate of glutamic acid radicals is 95.2%. The obtained crystalline calcium glutamate chelate powder can be further put into a granulator to keep the water content of the material at 26-30%, stir the material at a speed of 150-300 r/min, and granulate for 25-35 minutes. Dried into granules, which is more convenient for packaging and transportation of finished products.

Example 2

Take 7.6 kg of the original shell and fragments of snail shells in a tank-type extractor, add 1.5 mol/L nitric acid solution with a weight ratio of 2.8 times to percolate and dissolve calcium ions, and convert water-insoluble calcium into water-soluble ions at 45°C Calcium, solid-liquid separation to remove impurities such as protein, pigment, chitin and acid insoluble matter, the filtrate is poured into the crystallization tank, 10.1 kg of monosodium glutamate solid is added to the crystallization tank, water is added to 56.8 liters, and the monosodium glutamate is completely dissolved by stirring to control the grains in the solution. Amino acid radical concentration 152-155 g/L, calcium ion concentration 50.5-52.8 g/L, pH value 7.8-8.0, chelate calcium ions at 37°C to form a precipitate, filter through a plate and frame filter press, and chelate the precipitate A crystalline powder product of calcium glutamate chelate is obtained after drying.

After testing, the obtained crystalline glutamic acid chelated calcium powder product has the characteristics of weak acid and weak base slightly soluble, insoluble in water and alcohol insoluble; the purity of glutamic acid chelated calcium is 95.6%, of which calcium ion content is 23.5%, glutamine The content of acid radicals is 72.1%; the total recovery rate of calcium ions in this process is 93.6%, and the total recovery rate of glutamic acid radicals is 95.2%. The obtained crystalline calcium glutamate chelate powder can be further purified under non-acidic conditions by washing with water and 95% ethanol, and drying to obtain a white crystal product of glutamate chelate calcium with a purity of 98.3%.

Example 3

Take 10.3 kg of the original shells and broken shells of conch shells and sea mussel shells in the extraction tank, add 2 times the weight ratio of acetic acid aqueous solution, reflux and dissolve calcium ions under boiling water bath conditions, and maintain the hydrogen ions in the system by feeding acetic acid in a continuous stream. The concentration is not lower than 2.0 mol/L, the water-insoluble calcium is first converted into water-soluble ionic calcium, the solid-liquid separation removes impurities such as protein, pigment, chitin and acid insoluble matter, the filtrate is sent to the crystallization tank, and then poured into the crystallization tank Monosodium glutamate extract to 51.3 liters, control the concentration of glutamate in the solution to 310-315 g/L, the concentration of calcium ions to 75-78 g/L, and the pH value to 9.3-9.5, and chelate calcium ions to form a precipitate under boiling water bath conditions. The foot type centrifuge filters, and the chelated precipitate is air-dried to obtain the calcium glutamic acid chelate product.

After testing, the obtained chelated calcium glutamic acid product has the characteristics of weak acid and weak alkali slightly soluble, insoluble in water and insoluble in alcohol; the purity of calcium glutamic acid chelated product is 96.9%, of which the calcium ion content is 18.6%, the glutamic acid root content 78.3%; the total recovery rate of calcium ions in this process is 90.3%, and the total recovery rate of glutamate is 92.9%.

Example 4

The mixture of oil clams, flower clams, green moths and oyster shells purchased in the market is not sorted, and 80 kg is taken in a tunnel leaching device, and a mixed acid solution with a weight ratio of 2.5 times is added to countercurrently dissolve calcium ions. It is made by mixing 1 mol/L acetic acid solution and 1 mol/L hydrochloric acid solution at a ratio of 1:1, and converts water-insoluble calcium into water-soluble ionic calcium at 65°C, and removes protein, pigment, and chitin by solid-liquid separation. and impurities such as acid insoluble matter, the filtrate is poured into the crystallization tank, and the monosodium glutamate production wastewater and the crystallization mother liquor are added to the crystallization tank to 58.5 liters, and the concentration of glutamate in the solution is controlled at 250-255 g/L, and the concentration of calcium ions is 52-55 g/L L, pH value 12.5～13.0, chelated calcium ions at 55°C to form precipitates, filtered through a plate and frame filter press, and microwave dried the chelated precipitates to obtain glutamic acid chelated calcium crystalline powder.

After testing, the obtained chelated calcium glutamic acid product has the characteristics of weak acid and weak alkali slightly soluble, insoluble in water and insoluble in alcohol; the purity of calcium glutamic acid chelated product is 94.5%, of which the calcium ion content is 16.1%, the glutamic acid root content 78.4%; the total recovery rate of calcium ions in this process is 96.6%, and the total recovery rate of glutamate is 93.1%. The calcium glutamate chelate powder can be further purified by washing with water, 50% methanol-50% acetone at pH 8.3 to 8.5, and drying to obtain white crystals of calcium glutamate chelate with a purity of 99.1%.

The above embodiments are intended to further illustrate the present invention, but not to limit the present invention in any way. All equivalent changes and modifications made according to the patent application scope of the present invention, or directly or indirectly used in other related technical fields, are all equally included in the patent protection scope of the present invention.

Claims (9)

1. a product of calcium-glutamate chelate, it is characterized in that: taking shell as raw material, adopt acid solution that water-insoluble calcium in shell is first changed into water soluble ion calcium, solid-liquid separation is removed impurity, control again pH value and the temperature of filtrate, after the material chelating calcium ion containing glutamate forms precipitation, be processed into product of calcium-glutamate chelate.

2. the calcium-glutamate chelate of preparing taking shell as raw material according to claim 1, is characterized in that: product of calcium-glutamate chelate purity >=91%, wherein calcium ion content >=16%, glutamate content >=72%.

3. the preparation method of a product of calcium-glutamate chelate as claimed in claim 1, it is characterized in that: taking shell as raw material, adopt acid solution, at certain temperature and acidity condition, water-insoluble calcium in shell is first changed into water soluble ion calcium, solid-liquid separation is removed impurity, in filtrate, add the material containing glutamate again, by controlling concentration and the mol ratio of pH value, temperature, glutamate and calcium ion, chelating calcium ion forms precipitation, and chelating throw out obtains product of calcium-glutamate chelate after processing treatment.

4. the preparation method of product of calcium-glutamate chelate according to claim 3, is characterized in that: the acid that described acid solution adopts is one or more in hydrochloric acid, acetic acid, nitric acid, Hydrogen bromide, hydroiodic acid HI, propionic acid, lactic acid; The temperature that transforms generation water soluble ion calcium is not less than room temperature; In described acid solution, hydrogen ion concentration is not less than 1.5 mol/L.

5. the preparation method of product of calcium-glutamate chelate according to claim 3, is characterized in that: described shell is one or more in the ocean shell except abalone shells, aquatic shell, Lu Sheng shell; Described shell is one or more in protoconch, fragment, powder.

6. the preparation method of product of calcium-glutamate chelate according to claim 3, it is characterized in that: the described material containing glutamate is product or the extract of monosodium glutamate, L-glutamic acid and water-soluble salt thereof, containing one or more in the extracting solution of glutamate, factory effluent, crystalline mother solution.

7. the preparation method of product of calcium-glutamate chelate according to claim 3, it is characterized in that: when described chelating calcium ion, glutamate concentration is not less than 150 g/L, calcium ion concn is not less than 50 g/L, the mol ratio of glutamate and calcium ion is 0.9:1.0～1.5:1.0, temperature is not less than room temperature, and pH value is not less than 6.8.

8. the preparation method of product of calcium-glutamate chelate according to claim 3, is characterized in that: described processing treatment comprises filtration, washing, dry.

9. the preparation method of product of calcium-glutamate chelate according to claim 8, is characterized in that: described be dried as drying, dry, one or more in dry of microwave drying, air stream drying, spraying.