JPH0818829B2 - Method for producing calcium material mainly composed of natural calcium compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for purifying a calcium material such as egg shell and animal bones, which contains calcium carbonate as a component. The purified product obtained by the present invention is used in medicine or food for the purpose of supplementing calcium, for example.

PRIOR ART AND PROBLEMS OF THE INVENTION Calcium is an important component of bionutrients. Calcium materials such as egg shells and animal bones have various advantages over industrial synthetic products in terms of absorption and the like. However, such calcium material contains lipid-based and protein-based impurities. Among them, lipid impurities can be removed by several kinds of extraction methods, but there is no good removal method for protein impurities. For example, shell membranes of eggshells, bone marrow components of bones, etc. cannot be completely removed by heat treatment. For eggshells, a method of spraying a water stream and a method of heating have been put to practical use, but the former is extremely complicated by repeating hot water stirring and steam blowing, and the latter is difficult to remove by heating carbide as a byproduct. There was a drawback.

[Solution to Problem] According to the present invention, an egg shell and an animal bone are crushed or coarsely crushed as necessary to obtain an alkaline hypohalite salt or a neutral,
In alkaline or slightly acidic conditions, halous acid salts,
The present invention provides a method for purifying a calcium material, which comprises treating with a halogenate, a perhalogenate or a halogen dioxide. According to this method, proteins and other foreign substances are removed without damaging the calcium part,
A white purified calcium material is obtained.

[Embodiment] The configuration of the present invention is described in detail below.

1) Calcium material (1) As an egg shell, a split egg shell after removing egg white and egg yolk, which is easily washed with water and dried if desired, is used. These are used in the form immediately after breaking eggs or after crushing. No heat treatment is necessary.

(2) As animal bones, bones of mammals such as horses, horses and pigs, birds such as chickens and fishes such as carp are pulverized or crushed into fragments. It is preferable to degrease these as much as possible. Also, steamed or heat-treated products are easy to use.

2) Chemicals (1) As the acid, use an acid having the same or weaker acidity as carbonic acid and phosphoric acid, for example, 5 to 10% aqueous solution of boric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, etc. You can

(2) As the hypohalite, sodium hypochlorite, calcium (bleaching powder) and the like, sodium hypobromite, potassium, sodium hypoiodite, potassium and the like are used. These are preferably used as 0.2 to 1 to 10% aqueous solution. Calcium hypochlorite is preferably used by mixing the bleaching powder with water and then adding excess sodium hydroxide solution. Sodium hypobromite can be prepared cold from sodium hydroxide solution and bromine in excess of the calculated amount.

 Some of these are alkaline in nature.

(3) Examples of the halous acid salt, halogenic acid salt, perhalogenic acid salt, and halogen dioxide include sodium chlorite, sodium chlorate, potassium potassium, barium, sodium bromate, potassium potassium, sodium iodate, and potassium iodate. , Sodium perchlorate, potassium permeate, barium permeate, sodium metaperiodate, potassium periodate or chlorine dioxide can be used. In this case, the shell membrane dissolves in the eggshell when a concentrated liquid of about 10% is allowed to act at room temperature for a long time. However, except for chlorine dioxide, 90% of the eggshell and bones generally contain 3% to 5% liquid. The purpose can be achieved by reacting at about 100 ° C for about 2 hours.

3) Reaction conditions Foams during normal reaction. The reaction time varies depending on the combination of calcium material and drug, about 30 minutes to about 10 hours,
10 days only in special cases. When using a halous acid salt, a temperature of about 90 to 100 ° C is suitable,
In other cases, it can be carried out at room temperature or lower. The amount of the drug is preferably half or less for eggshells and about the same amount for bones.

[Effect] According to the present invention, since protein impurities are completely removed, a white and beautiful calcium material can be obtained. Further, the calcium material obtained by the present invention is stable and has little discoloration. Moreover, since the present invention does not use an organic solvent or a chemical agent that generates a large amount of poisonous gas under reaction conditions, it is less dangerous and suitable for industrial implementation.

[Examples] Next, the present invention will be described by examples.

1) Purification of egg shells Example 1 To 100 ml of an aqueous solution containing 5% sodium chlorite was added about 10 g of washed and air-dried egg shells, and the mixture was heated in a hot water bath at 95 to 98 ° C. for 2 hours with occasional stirring. The liquid was pale yellow and slightly foamed. After cooling, the egg shell to be deposited was filtered off, washed with water and air dried. Although the original color of the eggshell remained the same, no shell membrane was visually observed. The turbid matter in the liquid could be completely removed by washing with water.

Example 2 To 100 ml of a 3% sodium hypochlorite solution was added 10 g of egg shells washed with water and air-dried. The product immediately foamed and a chlorine odor was generated.
Stir occasionally and, after about 6 hours, filter the egg shells that have been deposited,
% Sodium sulfite aqueous solution to neutralize chlorine, further washed with water and air-dried to obtain 9.4 g of a beautiful white egg shell. The weight loss rate was 6.0%. In another experiment, 9.2 g of eggshells were obtained when 9.6 g of eggshells washed with water and air-dried were used to remove the egg membrane.
The weight loss rate was 4.2%.

The eggshells used in the above experiments were selected and used with the shell membrane uniformly attached to the inner surface of the shell.

Example 3 To 100 ml of a 2% sodium hypochlorite solution was added 4.8 g of brown egg shells washed with water and air-dried, and the mixture was left for 6 hours with occasional stirring.
After filtering and air-drying, 4.5 g of eggshell was obtained in which the shell membrane was not recognized at all and the original brown color of the eggshell was completely white. It was also confirmed that the eggshell was weakened. The weight loss rate was 6.3%. In another experiment, 5.2 g of eggshells washed with water and air-dried were removed in a conventional manner to obtain 4.9 g of eggshells. The weight loss rate was 5.8%.

In these cases, it was considered suitable that the amount of hypochlorite corresponded to the amount of proteinaceous substance to be removed.

Example 4 50 ml of water was added to 10 g of the bleached powder, and the mixture was ground and homogenized. Shake well and filter with absorbent cotton, absorbent cotton is 5%
Washed with alkaline solution. 100 ml of the whole filtrate with the same alkaline solution
Then, about 10 g of egg shells washed with water and air-dried were added thereto. After 12 hours, filtration was performed to obtain about 9.5 g of eggshell without a shell membrane.

Example 5 About 100 ml of a solution containing about 16 g of sodium hydroxide was cooled with ice,
About 4 g of bromine was gradually added dropwise with stirring. After 1 hour, about 10 g of egg shells washed with water and air-dried were added to the solution and treated in the same manner as in Example 3 to obtain about 8.9 g of shells having no shell membrane.

Example 6 To 100 ml of a 5% aqueous solution of boric acid was added 5 g of water-washed and air-dried egg shells. Approximately 10% potassium bromate while heating and stirring in boiling water
20 ml of the containing aqueous solution was added little by little in about 2 hours, and then heating and stirring was continued for another 2 hours. The liquid was a suspension and became cloudy. After cooling, the eggshell is filtered and washed repeatedly with water, the shell membrane is detached,
It did not remain in the eggshell.

2) Purification of animal bones Example 7 Approximately 10 g of 4% nitrogen, 21% phosphorus, particle size of 1 to 15 mm, black-gray steamed bone powder for fertilizer, about 10 g, was added little by little to 150 ml of 5% sodium chlorite solution while stirring. Was added. Heated on a hot water bath at 95-98 ° C for 2 hours with occasional shaking. The liquid became yellowish brown and slightly foamed to generate a chlorine odor. After the reaction, the bone meal was filtered off,
After washing with a% sodium sulfite solution, washing with water was continued several times. Air-dried to obtain about 6.5 g of white to pale yellowish white bone powder. The reaction solution was turbid, and a small amount of foreign matter was floating, but it was removed by washing with water. Also, a small amount of oil was deposited, but this could also be removed.

Example 8 10 g of the same bone meal as in Example 7 was added little by little to 100 ml of 3% sodium hypochlorite solution while stirring and cooling.
Cooling and stirring were continued for about 1 hour after the addition, and then the mixture was left at room temperature. After 2 days, the part with bone grains has been finely pulverized and deposited,
A considerable amount of oil was separated and suspended. Bone meal was filtered off, washed with water, and again added to a fresh 3% sodium hypochlorite solution with cooling and stirring. Foaming and heat generation were observed. This operation was repeated 4 times every 2 days for a total of 5 times. After repeated treatment, foaming and heat generation gradually subsided.

On the 10th day, bone powder was collected by filtration and washed with water, and the bone marrow portion was not visually observed, and about 6 g of almost white bone powder was obtained. There were many finely pulverized parts, and the whole was fragile.

Example 9 About 5 g of the same bone meal as in Example 7 was added to 100 ml of a 5% aqueous solution of sodium dihydrogen phosphate. While heating and stirring on a warm bath, 40 ml of 10% aqueous solution of sodium chlorite was added little by little. A strong chlorine odor was generated with foaming. After about 30 minutes, the bone powder became almost colorless, and after cooling, it was filtered, washed with water and air-dried to obtain about 3 g of white bone powder.

Claims (1)

[Claims] 1. An egg shell or animal bone is crushed or coarsely crushed as necessary to give an alkaline hypohalite, or a neutral, alkaline or slightly acidic halohalite, a halogenate or a perhalogenic acid. A method for producing a calcium material containing a natural calcium compound as a main component, which comprises treating with salt or halogen dioxide.