KR960000498B1 - Method of preparing calcium oxide from shell - Google Patents

Abstract

The ionized calcium is prepared by (A) charging pulverized shell into an indirect sintering refractory container(10), which is made of debris of stones, (B) adding 0.2-0.4 wt% activated carbon with respect to the amount of the pulverized shell, (C) piling refractory containers on a large cart(16), (D) transferring the cart(16) into a furnace(19) and preheating it for 0.5-5.5 hours, (E) sintering indirectly the mixture at 500-1,600 deg.C under the atmospheric pressure for 4-8 minutes and (F) quenching the sintered shell and pulverizing it into 300-320 mesh.

Description

Method for preparing ionized calcium using shellfish

1 is a schematic view of a heat-resistant container using soils used in the production method of the present invention.

2 is a schematic view of a super heat resistant container using Ni-Co alloy used in the production method of the present invention.

3 is a schematic perspective view of the case where the container of FIG. 1 is used for high temperature baking.

4 is a schematic side cross-sectional view of FIG.

FIG. 5 is a schematic front view when the container of FIG. 2 is used for high temperature baking.

6 is a schematic side view of FIG.

* Explanation of symbols for main parts of the drawings

DESCRIPTION OF SYMBOLS 10 Heat-resistant container of a clay soil 11 Body of a soil-resistant container

12 Lid of Earthenware Heat Resistant Container 13 Ni-Co Alloy Super Heat Resistant Container

14: Body of Ni-Co alloy super heat resistant container 15: Lid of No-Co alloy super heat resistant container

16: mobile cart 17: rail

18: traction line 19: high temperature firing

The present invention is a method for producing ionized calcium using shells, more specifically, compared to the conventional production method, the productivity, economical efficiency and product properties are further improved, a variety of 0.1% aqueous solution of calcium ion product (21 ℃ liquid temperature) The present invention relates to a method for preparing calcium ion that provides hydrogen ion concentration.

The invention also relates to an improved invention of the inventor's prior patent application No. 92-8637.

As a conventional manufacturing method, there was a manufacturing method of calcium oxide using the shellfish as a raw material set forth in Patent No. 285 48 by the inventor in 1986, and this was put in a heat-resistant container containing shellfish in the urine or furnace. Alternatively, the furnace door was closed and sealed, preheated to a predetermined temperature, and then indirectly calcined at the main temperature for 5 to 10 minutes to control the hydrogen ion concentration of calcium oxide required.

The present inventors have been experimenting variously for the firing conditions and methods in the calcium oxide manufacturing process for over 18 years, and further developed the conventional technology, which is superior in productivity and economical efficiency as compared with the conventional manufacturing method, the physical properties of the product, The present invention was completed by discovering a method for preparing calcium ion having various hydrogen ion concentrations in a 0.1% calcium ion solution (21 ° C. liquid temperature), which is greatly improved in chemical properties.

Accordingly, an object of the present invention is to load shellfish into an improved heat-resistant container and put the improved heat-resistant container into a furnace or a urine, and then preheat it for a predetermined time, and then maintain the main temperature for about 5 to 10 minutes to quench the productivity. It is excellent in economy, the physical and chemical properties of the product is greatly improved, the product is to provide a method for producing calcium ion in a variety of hydrogen ion concentration in a 0.1% product aqueous solution (21 ℃ liquid temperature).

The present invention achieves the above object by the following technical configuration.

Method for producing calcium ion using the heat-resistant container of the present invention consists of the following steps.

1. First process: washing and crushing

The shells such as oyster shells are washed with water to remove adherent soils such as sand, and then dried naturally or artificially.

2. Second process: loading raw materials and high temperature baking

The crushed shells are placed in an indirectly fired container according to the present invention and sprayed with 0.2 to 0.4% by weight of activated carbon. The indirect fired container is a heat-resistant container 10 using earth and earth, which is composed of a hollow body 11 and a lid 12 (see FIG. 1), or nickel (Ni) -cobalt (Co) as a main raw material. The super heat-resistant alloy container 13 is composed of a body 14 and its lid 15, which are also empty inside (see FIG. 2).

After the appropriate amount of the indirect firing container is stacked on the mobile trolley 16, the mobile trolley 16 is moved into the hot baking 19 using the rail 17 and the traction line 18. At this time, in the case of the heat-resistant container 10 using the earth ore, it is manufactured relatively small and stacked a large number in accordance with the size of the high temperature baking demand 19 (see FIGS. 3 and 4), whereas an alloy container of Ni-Co steel ( In the case of 13), it can be manufactured and used in a large size according to the size of the high temperature baking demand 19 (see FIGS. 5 and 6). On the other hand, in the present invention, the high temperature firing yaw 19 is a high frequency furnace, a high frequency furnace, a magnetron, a petroleum furnace, a petroleum furnace, a diesel passage, a diesel passage, a banca A furnace, a banca A yo, a banca C yo, a gas furnace, Gas furnaces, electric furnaces and electric furnaces, and their respective furnaces and tunnels, may also be used, such as firing trees (fired wood) or other high temperature heating devices generated by natural scientific developments, such as laser beams. .

3. Third process: preheating and indirect firing

The hot baking 19 is gradually preheated to a temperature between 500 and 1600 ° C. for 30 minutes to 5 hours and 20 minutes, and then isothermally fired by maintaining its isothermal temperature at about 4 to 8 minutes.

4. Fourth Process: Cooling

After the indirect firing process, the supply of the heat source is stopped to quench the heat resistant container 19.

5. The fifth step: grinding and storage

The shells are taken out and ground to 300-320 mesh to store the product in a sealed container.

The method for producing calcium ionization according to the present invention configured as described above has a significantly shorter heating time as compared to the conventional production method. Therefore, when the Ni-Co alloy super heat resistant container 13 according to the present invention is used, the conventional method Compared to the conventional method, the heating time was shortened by about 3 hours and 30 minutes under the same conditions (see Example 1 and Comparative Example 1 below). The heating time was shortened for 2 hours or more. [See Example 2 and Comparative Example 1 below].

In addition, the method for producing calcium ionization according to the present invention provides various hydrogen ion concentrations according to the temperature and time conditions of the main office. [See Examples 1, 3 to 8 below].

In addition, the method for producing calcium ionized according to the present invention not only significantly shortened the heating time under the same conditions, but also significantly improved the physical and chemical properties of the calcium ionized produced by the method according to the present invention, compared to conventional products. It has been confirmed that the scope of application can be greatly extended. [Refer to the various analysis test result data below].

The obtained calcium ion product is excellent in removing heavy metals in the waste water, can be used as an antidote for food, and has an excellent effect as a fertilizer for crops such as corn, spinach, and wormwood.

Hereinafter, the method for producing calcium ionization according to the present invention will be described in detail with reference to preferred embodiments.

Example 1

The oyster shell (shellfish) was washed with water to remove this material, then dried naturally or artificially, lightly broken into large and large ones, and then placed in a body 14 of a Ni-Co alloy super heat-resistant container, and activated carbon 0.3 per shell. After spraying by weight%, the lid 15 was covered, and one Ni-Co alloy superheat-resistant container 13 was placed on the four trucks 16. At this time, the Ni-Co alloy super heat-resistant container 13 was 120 cm wide x 76 cm tall x 80 cm high.

The trolley 16 and shells loaded with Ni-Co alloy superheat-resistant container 14 were placed in a tunnel-type kerosene, preheated for 3 hours, and then calcined at 900 ° C. for 5 minutes. At this time, the required oil was 2 drums.

After the heat source supply was stopped and quenched, the contents were finely ground to 300 to 320 mesh using a grinder to obtain an ionized calcium product. At this time, the 0.1% aqueous calcium ion solution of the product was the hydrogen ion concentration of PH12.35 (December 23) and PH12.7 (August 23) at 21 ℃ liquid temperature.

Example 2

The earthenware heat-resistant container 10 was used, but the same was carried out under the same conditions as in Example 1 except that the above-mentioned earthenware heat-resistant container 10 was placed on the cart 16.

The heat resistant container 10 of the said earth and sand was horizontal (28.5 cm) x vertical (17.3 cm) x height (10.7 cm), and the thickness was 1.6 cm, respectively.

The trolley heat-resistant container 10 of the said trolley | bogie 16 and shellfish which were loaded above was put into a tunnel type kerosene, preheated for 5 hours and 30 minutes, and indirectly baked at 900 degreeC main temperature for 5 minutes. At this time, the required oil was three drums.

The resulting calcium ionized product was hydrogen ion concentration PH12.6 (December 23) and PH12.7 (August 23) in a 0.1% aqueous calcium ion solution at 21 ° C.

Comparative Example 1

Wash the oyster shell (shellfish) to remove this material, dry it naturally or artificially, lightly crush the thick and large one, place it in a normal heat-resistant container and spray the activated carbon 0.3% by weight with the shellfish. Covered and then put in a vaulted oil pit. The door of the safe type petroleum urine was closed and closed, and then gradually heated up, preheated for 7 hours and 20 minutes, calcined at 900 ° C. for 5 minutes, and then the heat source supply was stopped. The oil required at this time was four drums.

After the heat source supply was stopped and quenched, the contents were finely pulverized with a 300 to 320 mesh using a grinder to obtain an ionized calcium producing material. At this time, the 0.1% aqueous calcium ion solution of the product was a hydrogen ion concentration of PH12.7 at 21 ℃ liquid temperature.

This is by the conventional method of the inventor's patent No. 28548, the heating time was about 7 hours 30 minutes, and petroleum took 4 drums.

Example 3

Under the same conditions as in Example 1, baking was carried out at the main temperature of 600 ° C. for 6 minutes to obtain an ionized calcium product of the present invention having the same physical properties. The hydrogen ion concentration of 0.1% aqueous calcium ion solution (21 ° C solution temperature) of the calcium ionized product was PH7.5 (December 23) in winter and PH8 (August 23) in summer.

Example 4

Under the same conditions as in Example 1, the resulting calcium ion product was obtained by baking for 6 minutes at a temperature of 700 ° C. in the same manner. The hydrogen ion concentration of the 0.1% calcium ion solution (21 ° C. liquid temperature) of the calcium ionized product was PH8.65 (December 23) in winter and PH9 (August 23) in summer.

Example 5

Under the same conditions as in Example 1, the resulting calcium ionized product was obtained by baking for 7 minutes at the main temperature of 800 ° C. At this time, the hydrogen ion concentration of 0.1% aqueous calcium ion solution (21 ° C. liquid temperature) of the calcium ion product was PH11.5 (December 23) in winter and PH12 (August 23) in summer.

Example 6

Under the same conditions as in Example 1, the resulting calcium ionized product was fired for 7 minutes at a main temperature of 1000 ° C. to obtain the ionized calcium product having the same physical properties. The hydrogen ion concentration of 0.1% aqueous calcium ion solution (21 ° C. liquid temperature) of the calcium ionized product was PH12.6 (December 23) in winter and PH13.0 (August 23) in summer.

Example 7

Under the same conditions as in Example 1, the resulting calcium ionized product was obtained by baking at an isothermal temperature of 1100 ° C. for 7 minutes. At this time, the hydrogen ion concentration of the 0.1% aqueous calcium ion solution (21 ° C liquid temperature) of the ionized calcium product was PH12.9 (December 23) in winter and PH13.2 (August 23) in summer.

Example 8

Under the same conditions as in Example 1, firing was carried out at an isothermal temperature of 1200 ° C. for 8 minutes to obtain an ionized calcium product of the present invention having the same physical properties. At this time, the hydrogen ion concentration of the 0.1% aqueous calcium ion solution (21 ° C. liquid temperature) of the calcium ion product was PH13 (December 23) in winter and PH13.5 (August 23) in summer.

On the other hand, the manufacturing method of the present invention not only significantly shortened the heating time under the same conditions, but also significantly improved the physical properties of the product produced by the manufacturing method of the present invention, to confirm this, according to Example 1 The prepared calcium ion was taken as a sample and subjected to various physical property tests as follows.

[Quantitative analysis test]

The calcium ion product prepared according to Example 1 was quantitatively analyzed by the Korea Advanced Institute of Science and Technology, and the results are shown in Table 1 below.

TABLE 1

[Acute Toxicity Test]

LD ₅₀ toxicity test was performed on rats of the ionized calcium product prepared according to Example 1, and the acute toxicity test results are shown in Table 2 below.

TABLE 2

Toxicity test method was to physiologically extracted with saline and divided into 5 groups of 20 mice per mouse group, each to 1.0g, 2.0g, 3.0g, 4.0g, 5.0g Corresponding extract (1 ml) was injected intraperitoneally to observe mortality for 10 days. 10 control groups were injected with 1 ml of physiological saline intraperitoneally.

In addition, it was difficult to prepare a concentration of 0.5 g or more per kg of body weight due to the adsorptive properties of the test article.

[Fungal and bacterial inhibition test]

Inhibition test against fungi and bacteria of the ionized calcium product prepared according to Example 1 was carried out. Test results conducted by the National Institute of Veterinary Hygiene are shown in Tables 3 and 4 below.

TABLE 3

*week. (1) The mold inhibition test was carried out by step dilution of the specimens in Sa bouraud dextrose broth and Sa bouraud dextroseagar by concentration, and the inhibition of Aspergillus was observed. Is an investigation.

(2) It indicates that the liquid extracted from the test product with distilled water added amount (1: 3.5), + was not suppressed,-was suppressed, and the dilution drainage was the dilution drainage to the medium of the test article.

TABLE 4

[Various calcium inhibition tests]

Sample 1 was prepared by dissolving the calcium ion prepared in Example 1 in water, and electrolyzed by adding calcium lactate in water, electrolyzed by high voltage with calcium lactate in water, and calcium stannate dissolved in hydrochloric acid. C, calcium lactate and calcium citrate, and calcium hydrogen phosphate were purified as D, and the results of experiments on absorption of the living body at Wakayama University in Japan are shown in Table 5 below.

TABLE 5

* Note: Sample 1 ...

A ... ionized water generator, B ... electrolytic calcium

C ... Colloid Calcium, D ... General Calcium Purification

Therefore, calcium ionized product, which is prepared according to Example 1, has high hygroscopicity and high absorption compared with other calcium, whereas A and B are electrolyzed by putting calcium in water. In reality, however, it is separated by electricity, and only by acidic power and alkaline water.

Calcium lactate can cause kidney stones and arteriosclerosis in the case of excessive amounts, and C is dissolved in hydrochloric acid, causing the body to become acidic, causing hydrochloric poisoning. D is also dangerous in excess (kidney stones, arteriosclerosis).

[Soil Soil Calibration Test]

The product prepared according to Example 1 was dissolved in water and sprayed on acidified soil. Treatment was performed by mixing 2,200 times (0.0455g), 2,000 times (0.050g), 1,800 times (0.0556g), 1,600 times (0.0625g), and 1,400 times (0.0714g) per 100g of acidified soil. Acidity was measured before, and acidity was measured after treatment.

The results are shown in Table 6.

TABLE 6

As shown in Table 6, the amount of calcium ion, which is the product of the present invention, required for calibration of soil acidity 1 (per 100 g of soil) was 0.0455 g.

[Calcium hydroxide loading test]

As a result of requesting the calcium hydroxide loading test to the Seoul Metropolitan Institute of Health and Environment and the Incheon Metropolitan City Institute of Health and Environment for the ionized calcium product prepared according to Example 1, the test result was informed that the test result satisfies the standard. This is believed to be due to the absorption of moisture in the air during quenching after shelling.

[Component Analysis Test of Calcium Ionization]

The element containing the calcium ion product prepared according to Example 1 was analyzed and compared with the element containing the human body constituent elements and the limestone, and the results were tested by the Korea Advanced Institute of Science and Technology.

TABLE 7

Solubility Test

The solubility test for water of the ionized calcium product prepared according to Example 1 was tested by the National Institute of Industrial Testing, and as a result, 92% was dissolved. This has been described in the table above.

Sulfur Dioxide Gas and Nitric Acid Toxic Gas Removal Test

In order to confirm the adsorption performance of sulfite gas and nitrate poison gas of the ionized calcium product prepared according to Example 1, a removal test of sulfur dioxide and nitrate gas was conducted by the National Institute of Industrial Testing and Research. And Table 9.

TABLE 8

TABLE 9

[PH Correlation with Head Temperature]

In Example 1 and Example 2 to Example 8, the pH correlation between the main temperature and the calcium ionized product was compared with each other, and the results are shown in Table 10 below. In the above embodiment, the same conditions were performed in summer (August 23) and winter (December 23) in consideration of seasonal influences.

TABLE 10

As can be seen from the various measurement and analysis tests described above, it was confirmed that the calcium ionized product produced by the production method of the present invention had much better physical properties than the product produced by the conventional production method.

In addition, as can be seen by the above-described temperature test and the PH correlation test, it was also confirmed that the method for preparing calcium ion according to the present invention can give various PH values by adjusting the temperature of the main office.

As described above, the other ionized calcium in the present invention is excellent in physical and chemical properties, and can be used for applications described below due to various hydrogen ion concentrations in 0.1% aqueous calcium ionized solution.

(One). Food additives Drinking additives for industrial use; Alkaline beverage drink additives; Chewing gum additives; Soymilk additives; Alcoholic beverage additives; Polysaccharide preparation additives; For adjusting pH of water and purified water; Various preservatives, oil additives; Ramen additives; Additives to bread and noodles; Other food additives, etc.

(2). In the pharmaceutical manufacturing industry, skin ointments; Various plasters; toothpaste ; Duchess for Women 's Health; Cosmetic manufacturing; Improvement of acid constitution alkali constitution; Human odor removal; Prevention of diabetes; Burn frost remedy; For acid preventive cancer; eyewash; Allergic constitution; For removing wastes in the human body; Hepatitis preventive treatment; For prevention of hypertension; Various cancer prevention; Calcium adjuvant; Other pharmaceutical manufacturing raw materials, etc.

(3). The agricultural and livestock rearing industry includes various feeds; Livestock Animal Drink Additives; Detoxification of various pesticide poisonings; Acid soil fixation; For disinfecting bean sprouts; Flower painting; Detoxification detoxification of sulfuric acid poison, nitrate poison, Cl in the greenhouse; Side cost; Persimmon and tangerine; Cultivation for ginseng disinfection; Pears, apple grapes, peaches, peanuts, watermelons, melons, strawberries, tomatoes, cucumbers, peppers, garlic, green onions, octagons, radishes, cabbage, potatoes, carrots, buttercups, corn, lettuce, garland chrysanthemum, spinach, burdock, plum For disease prevention and upbringing; Bonsai; For growing grass or removing odors; Removal of trees after treatment with acidic acid rain after treatment of sulfuric acid and sulfuric acid; Weight agents for fertilizers and pesticides; Can be used for other crops.

(4) removal of odor in refrigerators for general industrial purposes; General odor removal; Neutral paper manufacturing; Bleaching; Wastewater heavy metal removal; For tanning; For plastic production; For deafness in the manufacture of phosphorus; Metal antioxidants; Other general industrial purposes etc.

Claims (2)

The pulverized shellfish is placed in an indirectly fired container, sprinkled about 0.2 to 0.4% by weight of activated carbon with respect to the shellfish, and then indirectly calcined at 500 ° C to 1600 ° C under normal pressure to produce calcium ionized. In the above-mentioned indirect fired container, the earthenware-resistant container 10 of the earthenware which is empty inside is used, and after stacking the appropriate amount of the earthenware-resistant container 10 of the earthenware on the bogie 16, the bogie 16 is baked at high temperature. Or moved into the furnace 19, preheated for 30 minutes to 5 hours and 30 minutes, indirectly fired at the head office for 4 to 8 minutes, followed by quenching to finely pulverize the shelled shellfish to 300 to 320 mesh. Manufacturing method. According to claim 1, wherein the indirect firing container uses an ultra-heat-resistant container 13 of Ni-Co alloy with an empty inside, and put it on the trolley 16, and the trolley 16 is subjected to high temperature firing or furnace. Moving to (19), preheating for 30 minutes to 3 hours and 30 minutes, indirect firing at the head office for 4 to 8 minutes, and then quenching to finely grind to 300 to 320 mesh.