KR100604353B1 - The manufacturing method of calcium ionic water using a shell and equipment thereof - Google Patents

Abstract

The present invention provides a method and apparatus for producing calcium carbonate, which is a constituent of a shell, with calcium ionized water having high body absorption.

That is, the present invention relates to a method and apparatus for preparing calcium oxide water, which is prepared by calcination of shells such as oyster shell, cockle, clam, clam, shellfish and the like, which is composed of calcium carbonate, and suitable for drinking. More specifically, the present invention relates to a method for producing calcium ionized water of strong alkali with calcium ionized water of pH 5 to 10.5 using acetic acid having a purity of 99% or more in the production of calcium ionized water, and an apparatus thereof.

As a result, it is excellent in food safety, and can provide colorless, tasteless, and odorless calcium ionized water, and can increase the absorption of calcium in the body, thereby solving the problem of lack of calcium ingestion faced by modern people. Functional beverages containing calcium ions, beverages such as functional bottled water, food processing fields such as calcium ion tofu, ice cream, kimchi, grain processing fields such as functional rice and functional wheat flour, fertilizers such as meat improver, vegetable nutrition, Various applications have been made in the field of feed and health supplements.

Calcium ion, shell, calcium oxide, acetic acid, colorless, tasteless, odorless

Description

The manufacturing method of Calcium ionic water using a shell and equipment according to shellfish

1 is a manufacturing process diagram showing the configuration of the present invention

Figure 2 is a graph comparing the content ratio and absorption rate of calcium according to the presence form of calcium

Figure 3 is a block diagram of a device for producing calcium ion water according to the present invention.

<Description of the symbols for the main parts of the drawings>

10: storage tank 11: pump

12: Transportation pipe 13: CaO filter

14: stirrer 15: stirring wing

16: Filtration filter 17: Activated carbon filter

18: sterilizer

The present invention relates to a method for producing calcium ionized water suitable for drinking by using calcium oxide prepared by calcining shells such as oyster shell, oyster, clam, clam, clam, etc., which are composed of calcium carbonate, and a device thereof. More specifically, the present invention relates to a method for producing calcium ion water suitable for drinking by using acetic acid having a purity of 99% or more in the production of calcium ion water, and an apparatus thereof.

Calcium is the most minerals that make up the human body and should be the highest intake. Despite being abundant in food materials, calcium is a component that is difficult to absorb and always deficient. The cause of calcium deficiency in modern people is that the absorption of calcium is caused by acidification of soil, the ingestion of fat, the intake of fat, the preference of instant food, and the excessive intake of phosphate compounds due to the excessive drinking of soft drinks. Calcium compounds, that is, calcium phosphate, calcium carbonate, calcium lactate, and shells, powders such as shellfish, etc., to compensate for the lack of calcium.

Calcium present in natural products exists in the form of compounds, and they are absorbed and metabolized into atomic particles rather than in the molecular state, so calcium intake as a natural product has a fundamental problem. In order to help the absorption of calcium in the body it is preferable that the ionic state of the water-soluble form.

Shells such as cocktail, clam, clam, and shellfish as natural products have a large amount of bound calcium present in the form of calcium carbonate, and efforts have been made to separate and use them.

However, as mentioned above, the calcium in the shell is poorly absorbed in the body and is used to make it suitable for intake and drinking through the combination with aqueous solutions or other compounds.

Here are a few things to introduce:

Republic of Korea Patent Publication No. 1995-567 "Method for preparing ionic calcium (CaO) sap" is a method for producing ionic calcium (CaO) sap by firing calcium raw materials such as shells containing a calcium component to extract calcium oxide The process of baking the raw material and baking the calcium raw material for 20 to 30 minutes in an electric furnace of 2500 ~ 3000 ℃, and to produce the ionic calcium sap prepared by hydrating the calcined calcium raw material to be within pH 12.00 ~ 12.5 It is about a method.

As can be seen from the result, the concentration of hydrogen ions in the ionic calcium sap is too high to deviate from the legal regulation pH 5.8 to 8.5 for drinking water, thus having no practical utility.

Republic of Korea Patent Publication No. 2001-98992 "Method for producing calcium citrate and calcium citrate using limestone or shellfish" is a 50 ~ 325mesh shells and plastic shells such as oyster shell, oyster, clam, etc. After oxidization, and to react with citric acid to produce calcium hydrogen citrate or calcium citrate.

Citric acid, also known as citric acid, is contained in fruits such as lemons and unripe citrus fruits, and is used as an ingredient that adds sour taste to fruit juices, soft drinks, or sours medicines and diuretic beverages. Due to the inherent taste of citric acid, it is not suitable to use calcium hydrogen citrate and aqueous calcium citrate solution as ordinary drinking water. In addition, there is a disadvantage that the absorption rate in the body is only about 60%.

Republic of Korea Patent No. 397682 "Method for producing ionized calcium water using a pearl clam" is a calcination to heat the pearl shell to heat 5 ~ 6 hours at a temperature of 200 ~ 300 ℃, 6 ~ 7 hours at a temperature of 600 ~ 700 ℃ Process, pulverizing the calcined pearl clam into fine powder of 160-200 necks, a precipitation process of mixing and stirring the solids at a ratio of 4 L of distilled water per 1 kg of pulverized powder, and completing the pearl liquid After the reaction with the mother liquor, 6 g of citric acid, 2 g of malic acid, and 2 g of succinic acid are added to the mother liquor, the mixture is stirred and chemically reacted, and then precipitated solids for 5 to 6 hours. It relates to a method for producing the ionized calcium and ionized calcium water.

This decreases the hydrogen ion concentration of calcium water by adding organic acids such as citric acid, malic acid, succinic acid, etc., but they also have a sour taste, and so on, a separate process for removing the taste in general drinking water or food manufacturing using the same. This must be preceded. In addition, there is a disadvantage in that pure calcium water cannot be obtained because there is only a precipitation process.

Korean Unexamined Patent Publication No. 2002-23845 "Manufacturing Process of High Purity Calcium Chloride Using Shellfish" is based on 2 ~ 38wt% of calcium dissolution tank using calcium carbonate, calcium oxide and calcium hydroxide made from shells such as oyster shell, oyster shell and clam shell. React with aqueous hydrochloric acid solution to pH7 or above and remove unreacted silicic acid and organic impurities using a precipitation tank to prepare calcium chloride aqueous solution, and further add ammonia to precipitate water-soluble impurities with hydroxide It relates to a process for producing calcium chloride.

It uses hydrochloric acid, which is a strong acid, to reduce the hydrogen ion concentration. Hydrochloric acid may be suitable for reducing the hydrogen ion concentration. However, when the aqueous calcium solution is used as a food additive and food water, the food safety is significantly lower. There is a problem.

Republic of Korea Patent No. 14682, "Preparation Method of Calcium Oxide," is a method of preparing calcium oxide by heating a dried shell in a furnace to reduce the atmospheric pressure in the furnace under a vacuum of about 2 mmHg and firing at 1200 to 1500 ° C for 2 to 30 minutes. It relates to a process for the production of activated calcium oxide, characterized in that. This relates to the production of calcium oxide. When it is used as a water additive in food additives or food manufacturing, there must be a separate treatment for the aqueous solution of calcium oxide, and even if it is aqueous solution through the stirring method, it is produced due to strong alkalinity. There is a disadvantage that can not be used as a raw material.

As described above, the calcium present in the shell is present in the form of a salt of calcium carbonate, and in order to use it, it must be prepared by using calcium oxide through a process such as calcination. Therefore, they must be neutralized through the mountains.

As described above, in order to reduce the strong alkalinity of calcium water, strong acids such as hydrochloric acid and sulfuric acid or organic acids such as succinic acid, malic acid and citric acid are used. However, strong acids such as hydrochloric acid and sulfuric acid are so toxic that they cannot be used as food additives or raw materials for food manufacturing. Succinic acid, malic acid and citric acid have their own unique taste and aroma when added to foods due to their unique sourness or color. There is a problem that can inhibit.

Therefore, the present invention intends to use shellfish such as oyster shell, oyster, clam, clam, clam, etc. to manufacture calcium water, which is widely used industrially, and adjusts the hydrogen ion concentration (pH) to be suitable for drinking. It is intended to provide a method for producing calcium ion water and a device having safety, colorless, tasteless, and odorless state.

In addition, the body absorption conditions of calcium should be in the state of water-soluble ions and to prevent recombination with other inorganic ions to become a non-aqueous inorganic salt. The present invention is a water molecule around calcium ions by accepting and ionizing calcium By enclosing is stabilized without recombination with other inorganic ions to increase the body's absorption rate of calcium.

The present invention relates to a method for producing calcium ion water suitable for drinking by using calcium oxide prepared by firing shells such as oyster shell, oyster, clam, clam, clam, etc., which are composed of calcium carbonate, and a device thereof. In more detail, the present invention relates to a method for producing calcium ionized water suitable for drinking and using the acetic acid having a purity of 99% or more in the production of calcium ionized water, and a device thereof.

That is, the grinding step of washing, drying and pulverizing shells such as oyster shell, cockle, clam, clam, shellfish;

Firing the washed and crushed shells into a furnace at 900-1200 ° C. for heat treatment for 4-6 hours;

A powdering step of powdering the shell powder fired in the furnace into 400 to 700 mesh fine powder;

A step of producing the powder into a ball shape having a diameter of 2 to 5 mm by a conventional method,

Filling the shell ball into a calcium oxide (CaO) filler filter;

Passing the purified water through a calcium oxide (CaO) filling filter to pass the purified water to produce calcium ion water in which calcium ions are dissolved;

Adding calcium ionized water to a stirrer and neutralizing the mixture by adding and stirring 99% or more of acetic acid (glacial acetic acid) as a neutralizing agent;

A filtration step of removing the reaction product and impurities by passing the neutralized calcium ion water through a filtration filter and an activated carbon filter;

It relates to a method for producing calcium ion water using a shell consisting of a sterilization process for sterilizing the filtered calcium ion water with a sterilizer.

Looking at the manufacturing apparatus for producing calcium ion water made by the above manufacturing method as follows.

A plurality of CaO-filled filters (13) configured in a storage tank (10) to accommodate purified water on one side and connected in series to the bottom of one side of the storage tank (10) and connected to a feed pipe (12) in which a pump (11) is installed on one side (13) )Wow;

A stirrer (14) having a stirring blade (15) installed at the center to stir the calcium ionized water and the neutralizing agent introduced from the CaO filler (13);

A filtration filter 16 and an activated carbon filter 17 are installed at the other side end of the transfer pipe 12 connected to one lower end of the stirrer 14, and a normal sterilizer 18 is installed at one side of the activated carbon filter 17 to supply calcium ionized water. It is a configuration of a calcium ion water production apparatus that can be formed.

The CaO filling filter 13 is filled with a shell ball therein, and a calcium ion measuring device 20 is installed at one side of a plurality of CaO filling filters 13 at a distal end of the feed tube 12, and at one side of the agitator 14, a pH is provided. It is the structure in which the measuring device 30 was installed.

Hereinafter, the calcium ionized water production method manufactured by the manufacturing apparatus of the present invention will be described in detail.

1. Crushing process that washes, dries and grinds shellfish such as oyster shell, cockle, clam, clam, shellfish

Abandoned shells, which are rich in calcium carbonate and are used as a raw material of calcium, are washed and dried using a separate washer, and then first crushed into a grinder having an appropriate size for convenience of transportation. This is for ease of transportation and handling and does not limit the size.

The shell used in the present invention is a raw material for producing calcium ionized water, and the collection of the shell is used in the fish market, the beach, etc., and the shells are collected in discarded oyster shells, cocktails, clams, snails, shells, etc. do.

The washing machine is generally used, and the outer cylinder is not rotated, but a shaft having a stirring blade is installed inside, so that the shell can be washed while stirring the water and the shell while the shaft rotates. It is possible to use any of the washing tubs for washing the shells by installing stirring blades to wash the shells by rotating the water and the shells while the washing tub is rotating.

In the present invention, the size of the shell that is primarily crushed by the crusher is not a crushed form, but is pulverized to reduce the volume and ease of handling when transporting the shell, and also to be evenly calcined in the firing process.

The process from the wash tub to the primary grinder can be installed at the site of shelling or at one side of the kiln in the manufacturing process.

2. Firing process of crushed shell

The shell pulverized in the first step is put into a conventional firing furnace and heated at a temperature of 900 to 1200 ° C. for 4 to 6 hours to prepare calcium carbonate in the form of calcium oxide.

In this case, the shell is changed from calcium carbonate (CaCo ₃ ), which is the main component of the shell, to calcium oxide (CaO) by a heat source in the kiln.

Firing below the temperature and time does not cause sufficient firing of the shell, and firing above the temperature and time results in poor economic efficiency due to excessive supply of the heat source, so firing under the above conditions is suitable.

In addition, the temperature of the kiln is limited to 900 ~ 1200 ℃ and the time of 4 to 6 hours is also because the difference in the time and temperature to be fired according to the type of shell.

In other words, because the shell is thin, the oyster, clam, clam, clam, etc. are fired at a low temperature of 900 ℃ ~ 1000 ℃ because the shell is thin, but when the shell is thick like oyster, it needs to be fired at 1000 ~ 1200 ℃ to change to the desired calcium oxide (CaO). The firing temperature of the furnace is to be 900 ~ 1200 ℃ and time is limited to 4 to 6 hours.

3. Powdered shell shell powder into fine powder

Calcium oxide (CaO) powder prepared through the firing process is powdered into a fine powder having a particle size of 400 ~ 700mesh using a grinder. The powdering to the particle size is for the purpose of making the shell powder produced by the present process suitable for producing a ball shape having a diameter of 2 to 5 mm.

The washing machine, the pulverizer, the firing furnace, etc., which are performed in each of the above steps, use a device that is commonly used.

4. Shell ball formation process

Through the above process, a powder having a particle size of 400 to 700 mesh (mesh) is manufactured into a ball shape having a diameter of 2 to 5 mm (formation of a shell ball).

The method of forming the shell ball is generally carried out in the same manner as when the powder is manufactured in a ball shape. If the diameter is smaller than the above range, when the purified water passes through the filter, the shell ball is agglomerated with the purified water, so that the drainage of water is not easy. If the diameter is larger than the above range, the contact time between the purified water and the calcium oxide is large due to the large voids between the balls. This decreases and the problem that calcium oxide is not sufficiently dissolved. Therefore, a diameter of 2 to 5 mm is suitable.

5. Calcium ion water generation process

The shell ball by the above process is filled in the filter case to form a calcium oxide (CaO) filler filter (13). Calcium oxide (CaO) filling filter 13 is provided with a plurality of connected in series to the transfer pipe (12). The filling filter should be a normal 800 ~ 1000cc capacity. However, the present invention is not necessarily limited thereto. However, when the capacity is smaller than the above capacity, the working time will be longer, which is not suitable.

Therefore, the purified water stored in the storage tank 10 passes through a plurality of calcium oxide (CaO) filling filters 13 through a transfer pipe 12 connected to one lower end of the storage tank 10. At this time, the purified water passing through the plurality of calcium oxide (CaO) filling filter 13 is passed from the top to the bottom of the calcium oxide (CaO) filling filter located at the head, and from the upper end of the other calcium oxide (CaO) filling filter to the bottom In the process of passing through a plurality of calcium oxide (CaO) filling filter 13 is produced with calcium ion water.

In this process, it is possible to adjust the calcium ion concentration of the calcium ion water generated according to the number of filling filters installed. That is, the number of filling filters can be varied according to the intention of those skilled in the art to manufacture calcium ion water. However, since purified water flows into the filter, only one filling filter is inadequate, resulting in insufficient dissolution of calcium oxide.

 In addition, the installation of five or more filling filters results in excessively increasing the concentration of calcium ions in the ionized water, so two to four filling filters are most suitable.

For example, when 1 L of purified water is passed through three filling filters, 300 mg of calcium oxide is melted to contain 300 mg of calcium ions. PH is 12.3. This is a result of several experiments, which are measured by the calcium ion meter 20 installed in the end feed tube 12 of the filter filled with calcium balls and the pH meter 30 installed on one side of the stirrer 14. Can be.

That is, by installing a conventional calcium ion meter and pH meter at the bottom of the arranged calcium oxide filler, the operator can adjust the concentration and pH of the calcium ion according to the number of installed filter filter.

The purified water passing through the CaO filling filter 13 is smoothly transferred by the pressure of the pump 11 installed on one side of the conveying pipe 12 connected between the storage tank 10 and the calcium oxide (CaO) filling filter 13. do.

The transfer pipe 12 used in the present invention uses any one of a metal pipe or a hose, and there is no need to specifically limit either.

6. Stirring Process

Calcium ion water flowing out through the CaO filter 13 has a hydrogen alkalinity (pH) of about 13 strong alkalinity, it can not be directly used as food raw materials, drinking water, drinking water. This is added to the stirrer (14) containing calcium ion water with a purity of 99% or more of acetic acid (glacial acetic acid) as a neutralizing agent and mixed by stirring with a stirring blade (15).

The acetic acid mixed in the stirrer 14 is mixed with 0.8-2.5 μl of acetic acid per 1 mg of calcium oxide dissolved in 1 L of purified water.

It has strong acidity in silver acetic acid (Acetic Acid, CH ₃ COOH) aqueous solution of more than 99% purity. When the mixing amount of acetic acid is adjusted, the hydrogen ion concentration (pH) of calcium ion water can be adjusted to 5 to 10.5, which is suitable for drinking calcium ion water.

Hydrogen ion concentration (pH) of calcium ion water according to acetic acid incorporation amount is shown in Table 1 below.

Acetic acid pH 0.8 10.5 0.9 10.0 1.0 9.7 1.1 9.0 1.2 8.5 1.3 7.5 1.4 7.0 1.7 6.5 1.9 6.1 2.15 5.63 2.3 5.3 2.5 5.0

7. Filtration Process

Calcium ion water produced through the above process passes through the filtration filter 16 and the activated carbon filter 17 to remove the suspended matter generated during the reaction process.

The filtration filter 16 of the present invention is mixed with acetic acid in the stirrer 14 to filter the sludge contained in the calcium ionized water adjusted to the degree that the pH can be drunk, the activated carbon filter 17 to the calcium ionized water Remove odors, etc., to make it odorless and tasteless.

8. Sterilization Process

The calcium ion water passed through the filtration filter 16 and the activated carbon filter 17 is sterilized by passing through a conventional sterilizer 18 installed at one side.

Calcium ionized water after all the above processes is colorless, tasteless, and odorless calcium ionized water of pH 5-10.5.

The calcium ionized water of pH 5 ~ 10.5 is calcium ionic bonds with water molecules, unstable calcium ions are chelated to recombine with other inorganic ions or to avoid interference of obstacles. As a result, the calcium ions are stabilized and the calcium ions are absorbed by the selective action of the channel protein as the water molecules peel off when passing through the narrow cell pores or channels in the cell membrane.

2 is a table comparing the content ratio and absorption rate of calcium according to the presence form of calcium. As can be seen from Figure 2 it can be seen that the ionized calcium is significantly higher than the other bound calcium in the absorption rate.

Calcium ionized water is produced in functional beverages containing calcium ions, beverages such as functional bottled water, food processing fields such as calcium tofu, ice cream and kimchi, grain processing fields such as functional rice and functional wheat flour, meat improver, and vegetables. It can be used in a variety of fertilizers such as nutrients, feed, health supplements.

Experimental Example 1

This experiment is an analysis result according to the drinking water conformance criteria of calcium ion water prepared in the same manner as in Experimental Example 1. The results are shown in Table 2 below.

As can be seen from Table 2 above, the calcium ionized water prepared through the present invention is to be suitable for drinking calcium ionized water.

The present invention stabilizes calcium ions by preparing calcium carbonate, which is a combined type of calcium contained in shells such as oyster shell, cockle, clam, clam, and shellfish, with calcium ionized water, thereby increasing calcium body absorption. Functional beverages containing ions, beverages such as functional bottled water, food processing fields such as calcium ion tofu, ice cream and kimchi, grain processing fields such as functional rice and functional wheat flour, fertilizers such as meat improver and vegetable nutrition In the end, it has become widely available in health supplements.

As a result, it is possible to solve the problem of insufficient calcium intake of modern man, and it is possible to use the discarded shell usefully.

In addition, by using acetic acid (glacial acetic acid) with a purity of 99% or more in the production of calcium ion water, it adjusts the hydrogen ion concentration (pH) of calcium ion water to 5.0 ~ 10.5, making it suitable for drinking colorless, tasteless and odorless, and maintaining food safety. Calcium ionized water can be prepared.

Claims (4)

In the calcium ion water production method using a shell, A crushing step of washing, drying and pulverizing shellfish such as oyster shell, cockle, clam, clam, and shellfish; Firing the pulverized shell into a calcining furnace at 900-1200 ° C. and calcining for 4-6 hours to form calcium oxide; A powdering step of powdering the shell shell after the firing step into 400-700 mesh; Preparing a shell ball by preparing the powdered shell powder into a ball shape having a diameter of 2 to 5 mm; A filling step of filling the shell ball with a calcium oxide filler; Flowing purified water to a filling filter to produce calcium ion water; A neutralization step of putting the calcium ion water into a stirrer and mixing acetic acid; A filtration step of sequentially passing the neutralized calcium ion water through a filtration filter and an activated carbon filter; Calcium ion water production method using shellfish consisting of sterilization process to sterilize filtered calcium ion water in a conventional way The method of claim 1, wherein the acetic acid is acetic acid having a purity of 99% or more. The method for preparing calcium ion water according to claim 1 or 2, wherein the amount of acetic acid incorporated is 0.8 to 2.5 µl per 1 mg of calcium oxide dissolved in purified water.  A plurality of CaO-filled filters 13 connected to the lower side of the storage tank 10 and connected in series to the transfer pipe 12 having the pump 11 installed at one side thereof; A stirrer 14 connected to a feed tube 12 connected to the CaO filling filter 13 and provided with a stirring blade 15 at a central portion thereof; A filtration filter 16 and an activated carbon filter 17 are installed at the other end of the transfer pipe 12 connected to one lower end of the stirrer 14, and a normal sterilizer 18 is installed at one side of the activated carbon filter 17 to produce calcium ionized water. Calcium ion water production apparatus using shells, characterized in that it can be.

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