KR102582387B1 - Manufacturing Method for Soluble Ionized Organic Calcium Using Shell and Reaction Tank Thereof - Google Patents

Abstract

The present invention relates to a method and reaction tank for producing water-soluble ionized organic calcium using waste shells. More specifically, the step of obtaining crushed shells by crushing and separating oyster shells, egg shells, crab shells, or abalone shells, and mixing and stirring the shell crushed material and purified water in a shell dissolution reaction tank (Figure 2) to add the shell crushed material to purified water. A step of dispersing, adding an organic acid to the water-dispersed crushed shell material and reacting it, adding a defoaming agent to destroy the air bubbles, causing a swelling reaction of the water-dispersed crushed shell material and the organic acid, and further adding purified water and inspecting the physical properties. It consists of preparing water-soluble ionized organic calcium, filtering the water-soluble ionized organic calcium to remove foreign substances, screening to obtain water-soluble ionized organic calcium, and then packaging the water-soluble ionized organic calcium.

Description

{Manufacturing Method for Soluble Ionized Organic Calcium Using Shell and Reaction Tank Thereof}

The present invention relates to a method and reaction tank for producing water-soluble ionized organic calcium using waste shells. More specifically, the step of obtaining crushed shells by crushing and separating oyster shells, egg shells, crab shells, or abalone shells, and mixing and stirring the shell crushed material and purified water in a shell dissolution reaction tank (Figure 2) to add the shell crushed material to purified water. A step of dispersing, adding an organic acid to the water-dispersed crushed shell material and reacting it, adding a defoaming agent first to destroy the air bubbles, and swelling reaction of the water-dispersed crushed shell material and the organic acid, further adding purified water and testing the physical properties ( pH, specific gravity, viscosity) to prepare water-soluble ionized organic calcium, filtering the water-soluble ionized organic calcium to remove foreign substances, obtaining purified water-soluble ionized organic calcium, and then packaging the water-soluble ionized organic calcium.

The water-soluble ionized organic calcium using waste shells of the present invention has high solubility, so when used as a fertilizer for fruit trees or crops, organic calcium is moved and delivered to fruits, thereby extending the storage period of fruits or crops, improving color, and improving texture. .

In molluscs, the shell is a mineral secretion that surrounds and protects the mollusk. In bivalves, there are two on each side, in gastropods, there is one spiral-shaped tube, and in oysterpods, it is shaped like a horn with an opening at the upper end. It is composed of 95% inorganic salts (mostly calcium carbonate, with 1-2% calcium phosphate and less than 0.5% magnesium carbonate) and protein conchiolin. The outer part is covered with a thin cuticle layer, followed by the stratum corneum, and the inner part, adjacent to the membrane surface of the mantle, is the subcortical layer. At the end of the mantle, the hypertrophic part secretes the stratum corneum, the inner part secretes the stratum corneum, and the subcortical layer is made from the entire surface of the mantle.

Oyster shell is also called morye (牡蠣) or stone flower (石花). It is a hardened product made by secreting the limestone of the oyster's mantle, and contains 91.5-92.5% calcium carbonate (CaCO ₃ ), 4.5-5.2% inorganic matter, 2.4-2.7% organic matter, and 0.6-0.7% moisture. Among the inorganic substances, in addition to 1-2% calcium phosphate and 0.4-0.6% MgCO _3, 0.3-0.6% each of Na ₂ O, MgO, Al ₂ O ₃ , SiO ₂ , SrO, P ₂ O ₅ , and SO ₃ are contained. . Approximately 300,000 tons of oyster shells (as of 2020) are generated, of which approximately 50% are used as fertilizer or feed, 17.5% for seedlings, and 11.9% for oyster shells, and 20% (approximately 90,000 tons) of oyster shells are neglected. There is a need to urgently come up with a solution. Oyster shelling causes serious problems, such as causing not only bad odor but also environmental pollution, but it is not easily solved due to the high unit cost of processing by existing oyster shell recycling companies and wastewater treatment problems.

Oysters are so nutritious that they are also called ‘milk of the sea.’ Per 100g of raw oysters, the calories are 81 cal, protein 9.45g, carbohydrate 4.95g, fat 2.3g, phosphorus 115mg, iron 75mg, as well as copper, manganese, iodine, calcium, zinc, etc. Among carbohydrates, it contains glycogen, and among vitamins, it contains a lot of vitamins A, B1, B2, and B12, so it is known to be good for anemia and the liver. It is easy to digest and has an acid blood effect that purifies cloudy blood, so it is used as a medicinal food for patients with heart disease and high blood pressure.

The egg shell accounts for 10% of the egg weight and contains 93% calcium carbonate, 1% magnesium carbonate, 1% calcium phosphate, 5% organic conchiolin, 3% protein, and 2% organic polysaccharides and water. do. It is composed of three layers and has an average thickness of about 0.3mm. Eggshell calcium is also used as a liquid fertilizer by diluting the extracted eggshell calcium by soaking it in vinegar and diluting it with water.

Chitin, contained in crab shells, is a polysaccharide that is widely distributed in the outer skin of crustaceans such as crabs, shrimp, etc., insects, and in the cell walls of microorganisms and forms a complex with protein. This chitin becomes a raw material for making glucosamine, a component of cartilage that supports joints. Chitosan is chitin that has been processed to be easily absorbed by the human body. It prevents fat accumulation in the body and lowers cholesterol levels, so it is often contained in diet supplements and health functional foods.

In addition, many shells are generated from abalone, cockles, scallops, clams, and lilies among lungworms, but they are neglected due to lack of proper disposal methods.

Conventional technologies related to ionized calcium water using lungworts include Korean Patent Registration No. 10-0604353 (Method and device for producing calcium ionized water using lungworms), which includes a grinding process of washing, drying, and pulverizing lungfish; A sintering process in which the washed and pulverized waste shells are put into a furnace at 900 to 1,200°C and heat treated for 4 to 6 hours; A powdering process of powdering the spent shell powder fired in a furnace into fine powder of 400 to 700 mesh; A process of manufacturing the powder into a ball shape with a diameter of 2 to 5 mm by a conventional method, and filling the closed ball into a calcium oxide filled filter; A purified water passing process of passing purified water through a calcium oxide filled filter to produce calcium ion water in which calcium ions are dissolved; A process of neutralizing the calcium ion water by adding it to a stirrer and adding 99% or more acetic acid as a neutralizing agent and stirring it; A filtration process of passing the neutralized calcium ion water through a filtration filter and an activated carbon filter to remove reaction products and impurities; It relates to a method of producing calcium ion water using waste shells, which consists of a process of sterilizing filtered calcium ion water.

Korean Patent Publication No. 2001-98992, “Method for producing calcium hydrogen citrate and calcium citrate using limestone or clams,” powders limestone, quicklime, slaked lime, and shellfish such as oyster shells, cockles, clams, and calcined clams into 50-325 mesh. It relates to a method of producing calcium hydrogen citrate or calcium citrate by reacting it with citric acid. And it relates to a method of producing calcium hydrogen citrate or calcium citrate by reacting calcined waste shells or quicklime obtained by calcining limestone at 800-1,300°C with citric acid. Korean Patent Registration No. 10-2024537 (Calcium water using waste shells) Manufacturing method) includes the steps of 1) washing the shell and then drying it; 2) After step 1), placing the dried shellfish in a kiln and performing primary heating at 300-350°C for 9-15 hours; 3) After step 2), raising the temperature of the kiln to 700-750°C within 10-20 minutes and then secondarily heating the first heated closed shell for 6-8 hours; 4) After step 3), raising the temperature of the kiln to 1100-1200°C and then heating the second-heated closed shell a third time for 7-15 hours; 5) After step 4), the temperature of the kiln is lowered to 250-450℃, the third heated closed shell is heated the fourth time for 8 to 15 hours, and then left until the heat is completely cooled, and then the fired closed shell is heated. Obtaining; and 6) 5 to 15 L of water was added to 300 to 700 g of the calcined waste shell in step 5), heated at 80 to 120°C for 3 to 7 hours, aged at 70 to 90°C for 10 to 15 hours, and then precipitated. It is a method of producing calcium water including the step of removing and obtaining calcium water.

Korean Patent Registration No. 10-0481286 (Method for producing liquid calcium chloride using spent shells) includes a reaction step of dissolving the spent shells in hydrochloric acid in a reaction tank; A neutralization step of adding CaO or CaCO ₃ to the calcium chloride mixed solution (A) obtained in the reaction step; Purification step 1 of adding potassium permanganate (KMnO ₄ ) to the calcium chloride mixed solution (B) that has passed the neutralization step; Purification step 2 of adding hydrogen peroxide (H ₂ O ₂ ) and activated carbon to the calcium chloride mixed solution (C) that passed the purification step 1; and filtering the calcium chloride mixed solution (D) that has passed the second purification step.

Korean Patent Registration No. 10-0604353 (Method and device for producing calcium ion water using shellfish) includes a grinding process of washing, drying, and pulverizing shellfish; A sintering process in which the washed and pulverized waste shells are put into a furnace at 900 to 1,200°C and heat treated for 4 to 6 hours; A powdering process of powdering the spent shell powder fired in a furnace into fine powder of 400 to 700 mesh; A process of manufacturing the powder into a ball shape with a diameter of 2 to 5 mm by a conventional method, and filling the closed ball into a calcium oxide (CaO) filled filter; A purified water passing process of passing purified water through a calcium oxide (CaO) filled filter to produce calcium ion water in which calcium ions are dissolved; A process of neutralizing the calcium ion water by adding it to a stirrer and adding more than 99% acetic acid (glacial acetic acid) as a neutralizing agent and stirring it; A filtration process of passing the neutralized calcium ion water through a filtration filter and an activated carbon filter to remove reaction products and impurities; It relates to a method of producing calcium ion water using waste shells, which consists of a sterilization process of sterilizing filtered calcium ion water with a sterilizer.

Korean Patent Publication No. 2001-98992, “Method for producing calcium hydrogen citrate and calcium citrate using limestone or clams,” powders limestone, quicklime, slaked lime, and shellfish such as oyster shells, cockles, clams, and calcined clams into 50-325 mesh. It relates to a method of producing calcium hydrogen citrate or calcium citrate by reacting it with citric acid. Republic of Korea Patent No. 397682, “Method for producing ionized calcium water using pearl shells,” involves crushing pearl shells and baking them at a temperature of 200-300°C for 5-6 hours and at a temperature of 600-700°C for 6-7 hours. process, a grinding process in which the calcined pearl shells are pulverized into a fine powder of about 160 to 200 grains, a precipitation process in which solids are precipitated by mixing and stirring the pulverized material at a ratio of 4L of distilled water per 1 kg, and pearl liquid is completed. It consists of a liquid process, an ionized calcium water process in which 6g of citric acid, 2g of malic acid, and 2g of succinic acid are added per liter of prepared pearl liquid, stirred and chemically reacted, and solids are precipitated for 5 to 6 hours to obtain a fluid, and an ionized calcium process. It is about manufacturing method.

Korean Patent Registration No. 10-1676200 (Method for producing ionized calcium using waste shells) involves putting waste shells in a firing vessel body, forming a ventilation hole at the bottom, and covering the entrance of the firing vessel body with a lid containing activated carbon and putting it into the firing furnace. Next, it relates to a method of producing high purity ionized calcium by raising the temperature inside the furnace to 850 to 950°C and then cooling and powdering. According to the present invention, a relatively low firing temperature of 850 to 950°C is used. High purity ionized calcium can be produced without additional purification processes. Korean Patent Registration Patent No. 10-1499292 (Method for producing calcium citrate using oyster shells) includes 1) a preliminary step of removing foreign substances attached to oyster shells, washing them with water, and drying them to powder them; 2) A reaction step of obtaining a reaction product by adding 10 liters of a 0.1 to 1.0 M citric acid aqueous solution to 1 kg of oyster shell powder obtained in the above preliminary step and reacting at 4 to 100° C. for 1 to 24 hours; 3) a precipitation step of centrifuging the reaction product obtained in the reaction step to obtain a pellet-shaped precipitate; 4) a drying step of drying the pellet-shaped sediment obtained in the precipitation step with hot air; 5) It includes the completion step of pulverizing the above-mentioned calcium citrate with an air mill and commercializing it.

As described above, various methods for producing liquid calcium citrate or solid calcium citrate have been introduced in the prior art. However, since they cannot be ionized and have poor water solubility, they have the disadvantage of being difficult to put into practical use due to low water absorption even when applied to crops, and the process is too complicated to make them difficult to work with. The problem is that this is bad and not economically feasible.

1) Korean Patent Registration No. 10-1499292 2) Korean Patent Registration No. 10-0604353 3) Korean Patent Publication No. 10-2001-98992 4) Korean Patent Registration No. 10-397682

Sources of organic calcium that exist on Earth include animal bones, crustaceans, shellfish, and eggshells. The main component of all these organic calcium sources is calcium carbonate (CaCO ₃ ), and small amounts of calcium phosphate, MgCO ₃ , Na ₂ O, MgO, Al ₂ O ₃ , SiO ₂ , SrO, P ₂ O ₅ , SO _{3 ,} etc. It is made up of proteins, organic substances, etc.

The oyster shells that are being recycled among the closed shells go through a combustion process and a firing process as listed in the prior art above, so it is difficult to put them into practical use due to excessive energy costs and excessive installation costs because the firing furnace is manufactured on a large scale. In addition, the ionized calcium process in the impurity removal process requires multiple steps, requires long-term natural cooling after primary combustion and secondary firing, and requires a long period of 7 to 10 days to obtain the supernatant after natural precipitation after immersing and stirring the obtained pulverized material in water. This is not economically feasible due to the time required. In addition, the solubility of calcium in water is also low at 0.95 g/L (25 °C), so it is difficult to obtain water-soluble calcium.

The present invention relates to a method and reaction tank for producing water-soluble ionized organic calcium using waste shells. More specifically, there is no proper disposal method for oyster shells, egg shells, crab shells, and abalone shells that are disposed of as waste after harvest (use), so the environmental pollution problem is becoming more serious in each local government. In order to solve this problem, after extensive research, the present inventor discovered that calcium carbonate is the main ingredient of shellfish and completed the method of water-soluble ionized organic calcium by adding organic acid as follows.

A step of first crushing the closed shells and then separating them with a vibrating sieve with a diameter of 1.0 to 1.5 cm to obtain the crushed shells, and mixing the crushed shells and purified water at 1: 5 to 7 (wt) to prevent precipitation in the closed shell dissolution reaction tank (Figure 2). A step of dispersing the spent shell shreds in purified water by stirring at 60 to 150 rpm while mixing at a ratio of 100 to 200 (wt/wt) % of organic acids (citric acid, acetic acid, malic acid) compared to the water-dispersed spent shell shreds. Adding 1.25 to 2.5 (kg/min) and reacting, adding 0.05 to 0.1 (w/w) % of antifoaming agent (silicone-based) and allowing swelling reaction by water-dispersed crushed shell material and organic acid for 4 to 8 hours, and adding A step of preparing water-soluble ionized organic calcium by adding 4 to 6 (w/wt) % of purified water based on the total weight and testing physical properties (pH, specific gravity, viscosity), and filtering the water-soluble ionized organic calcium to remove foreign substances (seaweed). ) is removed, water-soluble ionized organic calcium is obtained, and then packaged.

When the water-soluble ionized organic calcium of the present invention is used on fruit trees or crops, the ionized water-soluble organic calcium is moved and delivered to the fruits, thereby prolonging the storage period of fruits and crops, improving color, and improving texture.

1 is a manufacturing process diagram of the present invention.
Figure 2 is a diagram of a calcium citrate reaction tank.
Figure 3 is a diagram of a baffle in a calcium citrate reaction tank.

The method and reaction tank for producing water-soluble ionized organic calcium using shell shells of the present invention include the steps of crushing and sifting one or two or more shell shells among oyster shells, egg shells, crab shells, or abalone shells to obtain crushed shells, and a shell dissolution reaction tank ( 2 and 3), the step of dispersing the spent shell shreds in purified water by mixing and stirring the spent shell crushed material and purified water, and adding an organic acid (citric acid, acetic acid, or malic acid) to the water-dispersed spent shell crushed material and adding an antifoaming agent during reaction. A step of swelling the water-dispersed crushed shell material with an organic acid while destroying the bubbles by adding (silicon-based), additionally adding purified water and testing physical properties (pH, specific gravity, viscosity) to prepare water-soluble ionized organic calcium, It consists of filtering the water-soluble ionized organic calcium to remove foreign substances, then screening to obtain the water-soluble ionized organic calcium, and then packaging it.

1) Waste shell shredded material

Egg shells and crab shells are easy to crush, so they can be easily crushed with a regular crusher, but oyster shells have the strength of the shell, so a hammer mill or ball mill can be used. For shells with hard shells, such as abalone, a pre shreder, 2-shaft shreder, 4-shaft shreder, or super shreder can be used. The oyster shells are first crushed and separated using a vibrating sieve with a size of 1.0-1.5 cm, and the remaining shells are sent back to the crusher for secondary crushing, and then crushed using a vibrating sieve with a size of 1.0-1.5 cm to obtain crushed shells.

2) Dispersion and swelling of waste shell fragments

As described above, any one or two or more of the shells of oysters, eggs, crabs, or abalone are first and secondly crushed, and then separated using a vibrating sieve with an eye size of 1.0 to 1.5 cm, and the crushed shells obtained are placed in a shell dissolution reaction tank (Figure 2, FIG. Add to 3) and fill 65-75% with purified water. Mix purified water at a ratio of 5 to 7 parts by weight (wt%) with respect to 1 part by weight (wt%) of the above shredded shell material and stir at 60 to 150 rpm to prevent precipitation to disperse the crushed shell material in the purified water.

For 100 (wt) % of the water-dispersed waste shell shredded material, 100 to 200 (wt) % of citric acid, acetic acid or malic acid as an organic acid is supplied at 1.25 to 2.5 (kg/min) for reaction. When organic acid infiltrates the fine pores of the oyster shell, a reaction with calcium citrate occurs. Since the reaction occurs explosively in an instant, 0.05 to 0.1 (w/w) % of a silicone-based defoaming agent is used to prevent overflow out of the reaction tank. is first added to destroy the air bubbles for 4 to 8 hours, causing a swelling reaction between the water-dispersed crushed shell material and the organic acid.

3) Production and filtration of water-soluble ionized organic calcium

After the swelling reaction of the water-dispersed waste shell shreds and the organic acid is completed, 4 to 6 (w/wt) % of the total weight of purified water is added and the reaction is performed again to produce water-soluble ionized organic calcium. The reaction is considered complete when no more bubbles of CO ₂ gas are generated. At this time, the concentration of the water-soluble ionized organic calcium solution is about 2.5 to 3.0 w/wt %, and it exists in an unsaturated water-soluble state. Therefore, when the viscosity of the water-soluble ionized organic calcium solution approaches gel form, purified water must be added to make it into an aqueous solution. If the concentration of the water-soluble ionized organic calcium solution is less than 2.0%, when applied to crops, the ionization concentration of the calcium source is low and movement and delivery to the flesh is insufficient, shortening the storage period of the fruit and adversely affecting texture and color. It is also possible. However, when the concentration of the water-soluble ionized organic calcium solution exceeds 3.5%, it becomes a gel, making it difficult to discharge from the container, and operating in a sprayer is inconvenient, making it unsuitable for fertilizing crops. Preferably, the concentration of water-soluble ionized organic calcium is 2.5 to 3%.

As in the above process, 49 kg (ℓ) of purified water as process water was added to the reaction solution (700 kg (ℓ) of purified water, 100 kg of oyster shells, 150 kg of citric acid, 1 kg of antifoam) for a total of 1,000 kg (100 wt %), and a gold mesh filter was added. By passing it through, impurities such as seaweed and plastic string that may remain are removed to obtain a water-soluble ionized organic calcium solution. The physical properties of the above water-soluble ionized organic calcium solution, such as concentration of 1.85 to 3.00 w/wt %, pH of 1.8 to 2.5, specific gravity of 1.088 to 1.220, and viscosity of 2,858 to 3,500 cp, are tested.

4) Sorting and packaging of water-soluble ionized organic calcium

The water-soluble ionized organic calcium solution is filtered to remove foreign substances (seaweed), then screened using a 5-20 mesh mesh shaker to obtain water-soluble ionized organic calcium, which is then packaged.

5) Reaction of citric acid and calcium carbonate

The reaction formula between citric acid and calcium carbonate or calcium hydroxide is as follows.

2C ₆ H ₈ O ₇ + 3CaCO ₃ → Ca ₃ (C ₆ H ₅ O ₇ ) ₂ + 3CO ₂ + 3H ₂ O

2C ₆ H ₈ O ₇ + 3Ca(OH) ₂ → Ca ₃ (C ₆ H ₅ O ₇ ) ₂ + 6H ₂ O

Ca ₃ (C ₆ H ₅ O ₇ ) ₂ 3(Ca) ²⁺ + 2(C ₆ H ₅ O ₇ ) ^3-

As described above, in the aqueous solution of calcium citrate (Ca ₃ (C ₆ H ₅ O ₇ ) _{2 )} , calcium is +2-valent (3Ca ²⁺ ) and citric acid is -3-valent (2C ₆ H ₅ O ₇ ^3- ). It is in an ionized state.

As shown in the reaction equation, when citric acid and calcium carbonate react, three carbon dioxide gases (CO ₂ ) and water molecules (H ₂ O) are generated from one molecule of calcium citrate, and the carbon dioxide gas flies into the atmosphere, but the inorganic calcium source and Differently, the viscosity of the organic calcium source increases rapidly as the reaction progresses, and the bubbles of the generated CO ₂ gas are not destroyed, causing it to instantly overflow out of the reaction tank.

6) Closed shell dissolution reaction tank (Figures 2 and 3)

Stir at more than 150 rpm to prevent the crushed oyster shells from reacting with citric acid (organic acid) and overflowing out of the reaction tank. In the closed-shell dissolution reaction device, stirring baffles are mounted on the stirring rod (1) in four stages (A, B, C, D) at equal intervals, and the stirring baffles A and C are shaped to pump the dissolved material upward when rotating. It is driven, and the stirring blades B and D are driven in such a way that the melt is pushed downward when rotating. In other words, the solution pumped up by stirring wing A is angled at a 45 degree angle so that it is pushed downward by stirring wing B, so that it can be stirred by giving extreme collision. In addition, the solution pumped up by stirring wing C is configured at a 45-degree angle to be pushed downward by stirring wing D, which accelerates the reaction by providing extreme collisions and prevents overflow out of the reaction tank by destroying air bubbles.

The baffle attached to the wall of the reaction tank is installed at an angle of 45 degrees in the shape of a Y (lowercase letter) and at equal intervals between the stirring blades, so that the solution stirred by the stirring blades hits the baffle on the wall of the reaction tank, causing a violent reaction. Let it come true. If this forced reaction is performed, the bubbles formed by CO ₂ gas are destroyed and discharged, and a 100% complete reaction occurs, allowing water-soluble ionized organic calcium to be obtained. As evidence, according to the analysis report (issue number: 15-FER-4-00478, July 24, 2015) obtained by Nanum Co., Ltd. (12-5, Hanbul-ro 69beon-gil, Eumseong-eup, Eumseong-gun, Chungcheongbuk-do, 369-803) upon request from the Agricultural Technology Commercialization Foundation, As a result of the analysis of ionized organic calcium, the total calcium content was 2.64% and the water solubility was 99.95%, indicating that oyster shell calcium is water-soluble ionized calcium.

<Example 1-4>

The shells were first crushed and 100 kg (equivalent to 10 wt%) of the shell waste separated through a vibrating sieve with a diameter of 1.0 to 1.5 cm was mixed with 700 kg (ℓ) (equivalent to 70 wt%) of purified water as process water. When 150 kg (corresponding to 15 wt%) of citric acid is added to the above mixed solution of crushed shell material at a rate of 1.25 to 2.5 kg (corresponding to 0.125 to 0.25 wt%) per minute and infiltrated into the fine pores of the shell, a reaction of calcium citrate occurs. 500 to 1,000 g (equivalent to 0.05 to 0.1 wt%) of silicone-based antifoaming agent is added to destroy air bubbles for 4 to 8 hours, and the water-dispersed spent shell material solution and organic acid cause a primary swelling reaction. An additional 49 kg (ℓ) of purified water as process water is added to the primary swelling reaction solution of water-dispersed waste shell shreds and organic acids to bring the total total to 1,000 kg (100 wt %) for the secondary reaction. The swelling reaction solution of the above crushed shell material and organic acid is passed through a gold mesh filter to remove foreign substances or contaminants to obtain a water-soluble ionized organic calcium solution. The physical properties of the above water-soluble ionized organic calcium solution were tested, including concentration of 1.85 to 3.0 w/wt%, pH of 1.8 to 2.5, specific gravity of 1.088 to 1.220, and viscosity of 2,858 to 3,500 cp.

Organic acid usage by shell type (wt%) division Example 1 Example 2 Example 3 Example 4 Comparative example shell cave 10 - - 5 10 egg - 10 - - - crab - - 10 5 - organic acid citric acid 15 - - 8 - acetic acid - 15 - - - malic acid - - 70 7 - inorganic acid Hydrochloric acid - - - - 15 process water Primary 70 70 70 70 70 Secondary 5 5 5 5 5 defoamer 0.1 0.1 0.1 0.1 0.1 total 100 100 100 100 100

In the above comparative example, when hydrochloric acid was used as an inorganic acid to dissolve the oyster shell, the calcium carbonate in the oyster shell was dissolved, but the viscosity did not increase, so the phenomenon of CO ₂ gas bubbles not overflowing out of the reaction tank did not occur. Since this uses hydrochloric acid, it can be seen that it does not become organic calcium. If the amount of hydrochloric acid added is large, the concentration of calcium increases slightly, but the concentration of hydrochloric acid is high, so it cannot be used on crops.

<Test example>

The calcium content and water solubility (water, solubility) of the water-soluble ionized organic calcium solution obtained by reacting as above were measured and shown as follows.

Calcium content (wt%) of water-soluble ionized organic calcium solution division Example 1 Example 2 Example 3 Example 4 Comparative example Total amount of calcium 2.76 2.71 2.65 2.61 1.85 Even if I accept it 99.95 99.13 99.26 99.38 87.54 pH 2.2 2.3 2.5 2.5 1.8 importance 1.220 1.210 1.200 1.198 1.088 Viscosity (cp) 3,500 3,447 3,235 3,208 2,858

From the above results, while the pH of Examples 1 to 4 was 2.2 to 2.5, the comparative example showed a tendency to increase towards acidity at pH 1.8, and the specific gravity was 1.220 to 1.198, but decreased to 1.088. Additionally, the viscosity was 3.500 to 3.208 (cp), while it was 2,858 (cp). From this phenomenon, the present invention confirms that while citric acid reacts with dead calcium to produce water-soluble ionized organic calcium, the inorganic acid of the comparative example exhibits a phenomenon in which the content of water-soluble ionized organic calcium is lower than that of the example in terms of pH, specific gravity, viscosity, etc. I was able to.

<Configuration and operation of closed shell dissolution reaction tank>

The spent shell dissolution reaction tank (FIGS. 2 and 3), in which the spent shell material reacts with organic acid to produce a water-soluble ionized organic calcium reaction, is composed as follows. In the closed shell dissolution reaction tank ⑩, 100kg of waste shell shredded material is input into the reaction tank ⑩ through the hopper ③ and screw conveyor ② at the inlet. 700kg of process purified water is added in advance to submerge the waste shell material. When 150 kg of citric acid is supplied to the above mixed solution of crushed shells at a rate of 1.25 to 2.5 kg per minute and infiltrated into the fine pores of the shells, a water-soluble ionized organic calcium reaction occurs.

Stirring impellers (impeller) ⓐⓑⓒⓓ are attached to the stirring rod ① in four stages in the vertical direction, and stirring impellers ⓐ and ⓒ are provided at a 45-degree angle so that the solution is driven upward when rotated, and the stirring impellers ⓑ and ⓓ are provided and installed at a 45-degree angle so that the solution is driven downward when rotated. In other words, the solution pumped up by stirring wing ⓐ is pushed downward by stirring wing ⓑ, causing extreme collision so that it can be stirred. In addition, the solution pumped up by stirring wing ⓒ is pushed downward from stirring wing ⓓ, causing extreme collisions to accelerate the solution reaction and destroy air bubbles to prevent overflow out of the reaction tank.

Baffles ④⑤⑥ are installed on the left and right sides of the reaction tank wall to prevent the adhesion of the solution to the walls by colliding with the solution and to destroy CO ₂ gas bubbles to block overflow out of the reaction tank. Lowercase letter) Attach to the wall of the reaction tank ⑩ at an angle of 45 degrees, and place and attach it between the stirring blades ⓐⓑⓒⓓ. The dissolved solution is stirred by stirring blades ⓐⓑⓒⓓ and hits the baffle baffles ④⑤⑥ on the wall of the reaction tank, causing the reaction to occur violently.

<Addition of citric acid and antifoaming agent to waste shell material solution>

When 150 kg (corresponding to 15 wt%) of citric acid is supplied to the crushed shell material solution at a rate of 1.25 to 2.5 kg (corresponding to 0.125 to 0.25 wt%) per minute and infiltrated into the fine pores of the shell, the calcium citrate undergoes a swelling reaction and bubbles are generated, forming a calcium citrate reaction solution. Leakage to the outside must be prevented. In order to calm the violent swelling reaction and destroy the bubbles, 500 to 1,000 g (corresponding to 0.05 to 0.1 wt%) of a silicone-based defoamer is added for 4 to 8 hours to destroy the bubbles and cause a swelling reaction between the spent shell material solution and the organic acid. If the swelling reaction is completed within 4 hours, the reaction solution may overflow and unreacted, and if the swelling reaction occurs over 8 hours, the reaction time becomes longer and the economic feasibility is poor.

Water-soluble ionized organic calcium concentration in the reaction solution compared to the amount of oyster shell and citric acid added division Example 1 Example 2 Example 3 Example 4 Comparative example Shredded shell material: citric acid
1:1.0 2.22 2.31 2.16 2.19 1.77 1:1.2 2.11 1.97 1.89 1.93 1.78 1:1.5 2.76 2.71 2.65 2.61 1.85 1:2.0 2.59 2.63 2.54 2.60 1.89 Defoamer (wt%) 0.1 0.1 0.1 0.1 0.1 0.1

In the above reaction, when 0.1 (wt%) of antifoaming agent was added and the crushed shell material and citric acid were added and reacted at a ratio of 1: 1.0 to 2.0, the concentration of water-soluble ionized organic calcium was 2.59 to 2.76 (at a ratio of 1: 1.5 to 2.0 times). wt%) was found to be good. Meanwhile, in the reaction using hydrochloric acid in the comparative example, the concentration of ionized organic calcium was found to be 1.77 to 1.89 (wt%), and when citric acid was used, the concentration efficiency of water-soluble ionized organic calcium was found to be 31.5 to 31.7% higher.

<Experimental example>; Cultivation experiments of water-soluble ionized organic calcium

The experimental group was made of water-soluble ionized organic calcium of the present invention, and the control group was made of ionic calcium fertilizer (commercially available), each diluted 1,000 times in agricultural water and used as a sample.

The above experimental and control groups were fertilized on strawberry seedlings being cultivated hydroponically from January 19, 2020 to March 5, 2021. Among the strawberries harvested every week, medium fruits, large fruits, and special fruits were divided by size and weight (g) was measured. , Hardness (kgf), and Sugar (%Brix) were measured, and the average values are shown in Table 4 below.

Strawberry cultivation results division Weight (g) Hardness (kgf) Sugar content (% brix) sowing date strawberry control group experimental group control group experimental group control group experimental group 1.21 heavy punishment 13.8 15.3 1.30 1.61 8.50 9.02 follicle 14.2 19.4 1.36 1.67 8.42 9.52 special 25.5 29.7 1.36 1.66 8.14 8.98 1.28 heavy punishment 12.2 15.2 1.36 1.68 7.98 8.91 follicle 18.6 19.6 1.18 1.45 7.89 8.95 special 25.5 28.6 1.20 1.54 8.22 9.01 2.03 heavy punishment 12.9 15.9 1.24 1.66 8.33 8.98 follicle 19.1 22.2 1.22 1.59 8.43 9.46 special 24.1 28.3 1.38 1.65 7.40 8.90 2.10 heavy punishment 14.3 15.4 1.42 1.62 8.26 8.95 follicle 18.0 20.0 1.37 1.60 8.34 8.89 special 25.9 28.4 1.28 1.54 8.07 8.92 2.18 heavy punishment 13.6 16.2 1.30 1.61 8.64 9.00 follicle 19.0 20.9 1.25 1.65 8.49 8.99 special 24.4 29.6 1.23 1.63 8.19 8.89 2.25 heavy punishment 15.0 16.2 1.36 1.56 8.67 9.27 follicle 18.4 19.8 1.30 1.60 8.74 9.26 special 24.2 27.4 1.48 1.58 8.48 8.95 3.05 heavy punishment 14.2 15.0 1.47 1.62 8.38 9.19 follicle 19.0 21.0 1.58 1.64 8.80 9.13 special 24.1 26.7 1.48 1.65 8.40 8.93

From the above results, in terms of strawberry weight increase rate, the average weight (g) of the fruit in the control group was 13.7g and the experimental group was 15.6g, which was an increase of 12.2% in weight increase rate. The average weight (g) of the large fruit was 18.04g in the control group and 20.41g in the experimental group, and the weight increase rate improved to 11.9%. The average weight (g) of the special fruits was 24.8g for the control group and 28.3g for the experimental group, and the weight increase rate improved to 12.6%. In addition, in terms of the increase rate of strawberry sugar content, the average sugar content of the fruit was 8.39 (% brix) in the control group and 9.04 (% brix) in the experimental group, which improved to 7.25%. The average sugar content of the large fruit was 8.44 (% brix) in the control group and 9.16 (% brix) in the experimental group, which improved the sugar content increase rate to 7%. The average sweetness of the special treats was 8.12 (% brix) for the control group and 8.94 (% brix) for the experimental group, which improved the sugar content increase rate to 9.17%. Meanwhile, from the above results, the weight (g) of medium, large, and special fruits showed a weight increase rate of 12.2%. The hardness (kgf) of medium, large, and special fruits showed a hardness increase rate of 6%. The sweetness (% brix) of medium-sized fruits, large fruits, and special fruits showed a 7.8% increase in sugar content. In terms of the above strawberry quality indicators such as weight, hardness and sweetness, it can be seen that the water-soluble ionized organic calcium of the present invention is effective in fertilizing fruit trees. In addition, according to the reports of farmers who used the water-soluble ionized organic calcium of the present invention, the present invention was evaluated as having good marketability because there were almost no deformed strawberries when fertilized and harvested on strawberries, the red gloss of the strawberries was very excellent, and the white part was clear. .

When the water-soluble ionized organic calcium of the present invention is used on fruit trees or crops, the water-soluble ionized organic calcium is moved and delivered to the fruits, thereby extending the storage period of fruits and crops, improving color, and improving the texture.

①; Agitator, ②; Screw conveyor, ③; Hopper, ④⑤⑥; Stirring wing, ⓐⓑⓒⓓ; Baffle baffle, ⑩; reaction tank

Claims (5)

A step of obtaining crushed oyster shells by crushing and removing oyster shells, and mixing crushed oyster shells and purified water in a shell dissolution reaction tank (Figure 2) at a ratio of 1:5-7 (wt%) to obtain crushed oyster shells of 60-150%. A step of dispersing by stirring at rpm, a step of swelling reaction by adding citric acid and an antifoaming agent to the water-dispersed oyster shell shreds, and additionally adding 4 to 6 (w/wt) % of purified water based on the total weight and testing the physical properties. It is characterized in that it consists of the step of producing water-soluble ionized calcium citrate, filtering the water-soluble ionized calcium citrate to remove foreign substances, then screening with a 5-20 mesh eye shaker to obtain water-soluble ionized calcium citrate, and then packaging it. In the method for producing water-soluble ionized calcium citrate using oyster shells,
The oyster shell shreds, citric acid, and an antifoaming agent are added to cause a primary swelling reaction of the water-dispersed oyster shell shatter solution and citric acid while destroying the air bubbles for 4 to 8 hours, and then purified water is added to the primary swelling reaction solution of the water-dispersed oyster shell shreds and citric acid. A method of producing water-soluble ionized calcium citrate using oyster closure, characterized in that a secondary swelling reaction is performed by adding an additional 49 kg (ℓ) to a total of 1,000 kg (100 wt %). delete delete Crushed oyster shells, purified water, citric acid, and antifoaming agent are fed into the reaction tank ⑩ through the hopper ① and screw conveyor ②, and the stirring rod ① and four-stage stirring blades ⓐⓑⓒⓓ are installed at equal intervals in the vertical direction at the center of the reaction tank ⑩. In the water-soluble ionized calcium citrate reaction tank of the cave closure, characterized in that baffle plates ④⑤⑥ are installed on the left and right sides of the wall of the reaction tank ⑩ at equal intervals,
The stirring wings ⓐ and ⓒ are attached at a 45° angle so that the solution can be pumped upward when rotating, and the stirring wings ⓑ and ⓓ are attached at a 45° angle so that the solution can be pushed down when rotating, and the wall of the reaction tank The baffle plates ④⑤⑥, which are installed on the left and right sides, are installed at a 45° angle in the form of a y-shape (lowercase letter), and are installed between the stirring blades ⓐⓑⓒⓓ. A water-soluble ionized calcium citrate reaction tank with a closed angle. delete