JPH02221117A - Method for refining natural calcium base material - Google Patents

Abstract

PURPOSE:To improve a refining effect by crushing eggshells, animal bones, shells or crusts and then treating the crushed material with an alkali, an alkaline hypohalogenite or an aq. alkaline, neutral or feebly acidic soln. of a specified compd. CONSTITUTION:The neutral calcium base material such as eggshells, animal bones, shells or crusts are pulverized or crushed, as required. An alkali such as sodium hydroxide, an alkaline hypohalogenite such as sodium hypochlorite, alkaline, neutral or feebly acidic halogenates (e.g. potassium chlorate and potassium perchlorate), a weak acid (e.g. carbonated water), chloramines, halogenated isocyanuric acids, hydantoins, peroxides (e.g. hydrogen peroxide) and an aq. soln. of permanganates, etc., are used as the chemicals. The crushed material is treated with the chemicals to obtain the refined material. In this case, less than half the equivalent amt. of the chemical is used in the case of eggshells, the equivalent amt. is used in the case of bones, and more than the equivalent amt. of peroxides is used. The treatment is carried out at about 90-100 deg.C when the alkali or hypohalogenite alone is used and at room temp. or lower in other cases for about 30min to 10 days, and the refined material is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] This invention relates to a method for producing natural calcium materials such as eggshells, animal bones, shells, or shells. The purified product obtained by this invention is used in medicines or foods, for example, for the purpose of calcium supplementation.

1 Problems with Jubei's technology and inventions 1 Calcium is an important component of bionutrients.

Natural calcium materials, such as eggshells, animal bones, seashells, or shells, have a variety of absorption and other advantages over industrial synthetic materials. However, natural calcium materials
Contains lipid-based and protein-based impurities. Of these, lipid-based impurities can be removed by several extraction methods, but there is no good method for removing protein-based impurities. For example, the grains of eggshells, bone marrow components of tubes, and hard proteins of fish shells cannot be completely removed even by heat treatment. However, the former method requires repeated hot water stirring and steam blowing, which is extremely troublesome, and the latter method has the disadvantage that heating carbides are generated as a by-product and are difficult to remove.

[Method for solving the problem j This invention involves crushing or coarsely pulverizing eggshells, animal bones, seashells, or shells as necessary, and treating them in an alkaline aqueous solution, an alkaline hypohalite, or a neutral, alkaline or slightly acidic solution. , halites, /5tlF dates, perhalates, dioxides, chloramines, halogenated incyanuric acids, herodenated hydantoins, peroxides, peracids or permanganates in aqueous solutions. The present invention provides a method for purifying natural calcium materials, which comprises processing. According to this method, proteins and other foreign substances are removed without damaging the calcium portion, and a white purified calcium material is obtained.

[Embodiment 1 The configuration of this invention will be explained in detail as follows.

1) Calcium material (1) The eggshell used is a broken eggshell after removing the egg white and yolk, which has been washed in the dark with water and dried if desired.

These can be used in their freshly broken form or after being crushed. No heat treatment is required.

(2) As the animal bones, powdered or crushed bones of mammals such as cows, horses, and pigs, birds such as chickens, and fish bones such as carp are used.

It is preferable to degrease these as much as possible. In addition, steaming or heating path 1-(1) is easy to use.

(3) As the shell or shell, a shell or shell without meat is used. These are washed with water and dried if desired.

*Powder or crush into pieces.

No particular heat treatment is required.

2) Agent (1) As the alkali, use sodium hydroxide or potassium hydroxide, and when reacting with cooling, about 1 to 100 ml of ammonia water.
A 10% aqueous solution is preferred. Approximately 5% when used alone;
When used in combination with other drugs, it is preferably used at a concentration of about 2 to 3%.

<2) As elN, it is possible to use an acid equivalent to or weaker than carbonic acid and phosphoric acid, such as a 5 to 10% aqueous solution of boric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium phosphate, etc. .

(3) As the hypohalite, sodium hypochlorite, calcium hypochlorite (bleached powder), sodium hypobromite, potassium hypobromite, sodium hypoiodite, potassium hypoiodite, etc. are used. These are preferably used as a 0.2 to 1 to 10% aqueous solution.

Calcium hypochlorite is preferably used by mixing bleaching powder with water and then adding excess hydroxide +7 hum solution. Sodium hypobromite can be prepared cold from sodium hydroxide solution and bromine in excess of the calculated amount.

Since some of these are inherently alkaline, it may not be necessary to separately add an alkaline solution.

(4) Examples of halites, halogenates, perhalogenates, and halogen dioxide include sodium chlorite, sodium chlorate, potassium chlorite, barium chlorate, sodium bromate, potassium chlorate, sodium iodate, and potassium chlorate. ,
Sodium perchlorate, can. In this case, if a concentrated solution of about 10% is applied to the eggshell for a long time at room temperature, the grain membrane will dissolve, but except for chlorine dioxide, generally a 3-5% solution is applied to the eggshell and tubes at 90% The purpose can be achieved by reacting at ~100°C for about 2 hours.

chlorbenzenesulfonamide sodium), chloramine T (N-chlorotoluenesulfonamide sodium)
etc. are used.

(6) Halogenated incyanuric acids and hydantoins include chlorinated incyanuric acid and its analogues (for example, substituted with an N-alkoxy group in place of one N-C1 group or substituted in place of one C=0 group) or having an unsubstituted methylene group), or 1,3-dichloro-5,5
-nomethylhydantoin, etc. are used.

(7) Peroxides or peracids include hydrogen peroxide, adducts such as hydrogen peroxide carbamide, persulfuric acid,
potassium, ammonium (these can be used as concentrated aqueous solutions), sodium peroxide, sodium perbalate, sodium percarbonate, perbenzoic acid, peracetic acid or benzoyl peroxide (these can be added in portions as a powder) etc. are suitable.

Since peroxide is alkaline and decomposes quickly, it is preferable to drop it in small portions several times over several days at a temperature below room temperature into an alkaline solution containing eggshells, etc. while stirring.

(8) As the permanganate, a 1-3% aqueous solution of potassium permanganate is used, and in this case, it is better to add an excess of alkali.

3) Reaction Conditions Unless alkali is used alone, the zero reaction time for foaming during the normal reaction varies depending on the combination of the calcium material and the drug, and is about 30 minutes to about 10 days. In addition, when using alkali or halite alone, approximately 90
Temperatures of ˜100° C. are preferred, although in other cases it may be carried out at room temperature or below. It is preferable to use less than half the amount of chemicals for eggshells, and around the same amount for tubes.In particular, it is preferable to use more than the same amount for peroxides, etc.6 Generally, when alkali coexists, the degree of foaming is small;
The reaction time is short and the amount of drug tends to be small.

[Effect 1] According to the present invention, since protein-based impurities are completely removed, a beautiful white calcium material can be obtained. In addition, the calcium material obtained by this invention is stable and has little discoloration, and since this invention does not use organic solvents or chemicals that generate large amounts of poisonous gas under reaction conditions, it is less dangerous. Suitable for industrial implementation.

[Example 1 Next, the present invention will be explained with reference to examples.

1) Eggshell Purification Example 1 10g of washed and air-dried eggshells were added to 5% hydroxide (hydroxide) w1100z1 and heated on a hot water bath at 95-98°C for 2 hours with occasional stirring. The liquid took on a pale yellow color. After cooling, the deposited eggshells were separated by filtration, washed with water, and air-dried. The original color of the eggshell remained intact, but no grain layer was visible to the naked eye. 8
There was a small amount of white foreign material floating in the container that could not be fully decomposed and dissolved, but it was completely removed by washing with water.

Example 2 Washed and air-dried eggshells were added to 100 z1 of a solution containing 5% sodium chlorite. was added and treated in exactly the same manner as in Example g41. The liquid took on a dirty yellow-brown color and was slightly foamy. No grain layer remained in the filtered eggshells. White foreign matter floating in the liquid cannot be easily removed by washing with water.

Example 3 Sodium hypochlorite 3% 81100ij! Washed and air-dried eggshells 10. added. It immediately foamed and a chlorine odor was generated.6 Stir occasionally. After about 6 hours, the deposited eggshells were collected by filtration, washed with 0.1% sodium sulfite aqueous solution to neutralize the chlorine, and further washed with water and air-dried. Beautiful white eggshell 9.4g
The weight reduction rate obtained was 6.0%. In another experiment, when the grain layer was manually removed from 9.6 g of washed and air-dried eggshells, the weight loss rate was 4.2%, yielding 9.21 eggshells.

The eggshells used in the above experiments were selected to have a grain layer evenly attached to the inner surface of the grain.

Example 4 Add 4.8 g of washed and air-dried brown grains to 501 g of an aqueous solution containing 2% sodium hypochlorite and 2% sodium hydroxide.
was added and left to stand for 6 hours with occasional stirring, resulting in foaming that was narrower than that in the case where no alkali was added. Air dry separately at
Eggshells 4, 5. No grain layer was observed, and the original brown color of the eggshell had completely faded to white. I got it.

In addition, it was observed that the eggshell had become brittle.

The weight reduction rate was 6.3%. In another experiment, the grain layer was manually removed from 5.2 g of washed and air-dried eggshells, and eggshell 4.
9. The percentage decrease in zero weight obtained was 5.8%.

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

Example 5 Water 5011 was added to bleaching powder 1011 and ground to a uniform consistency. After shaking (shake it up), filter it through absorbent cotton, and wash the absorbent cotton with 5% alkaline solution.
10. added. After 12 hours, it was filtered to give an eggshell quality of 9.5 without grain layer.
I got 2.

Example 6 100 M1 in solution containing about 162 +7 um
4 g of the central agglomerate was gradually added dropwise to the mixture while cooling with water and stirring. After darkening, 10 g of washed and air-dried eggshells were added to this solution, and treated in the same manner as in Example 3 to obtain eggshells 8.
I got 92.

Example 7 Add 10g of washed and air-dried eggshells to 100ml of 5% sodium hydroxide solution, and add 950ml of 3.5% hydrogen peroxide while stirring.
ml was added little by little. It foamed vigorously.

Two days later, 50 ml of 3.5% hydrogen peroxide solution was added again and stirred. The same operation was repeated two more days later.

It was left as it was at room temperature for 3 days. When the eggshells were taken out and washed with water, a very beautiful white eggshell with no remaining grain layer was obtained.

Example 8 Sodium percarbonate powder 3
．． 5 g was added in small portions with stirring. Vigorous foaming occurred, and the percarbonate eventually dissolved and disappeared. Thereafter, about 3.5 grams of sodium percarbonate was added in the same manner every two days, and this operation was repeated five times, including the first time, to react a total of 17.5 g of salt.

After 10 days, the reaction solution became cloudy. When the eggshell was removed and washed with water, an eggshell without any grain layer was obtained.

Almost similar results were obtained by substituting about 5 g of ammonium persulfate or about 7 g of sodium perphosphate (tetrahydrate) in place of the above sodium percarbonate.

Example 9 5 g of washed and air-dried eggshells were added to 100 z/ml of a 5% boric acid aqueous solution.
added. While heating and stirring boiling water, an aqueous solution containing about 10% potassium bromate was added little by little over about 2 hours. After that, heating and stirring was continued for another 2 hours. The liquid became cloudy with suspended matter. After cooling, remove the eggshells. When filtered and repeatedly washed with water, the grain layer was detached and did not remain in the eggshell.

Example 10 Washed and air-dried eggshell 59 was added to 200 z1 of a 5% sodium hydroxide aqueous solution. Approximately 1,511 ml of a 2.5% aqueous solution of potassium permanganate was added in 2xl portions over a period of 2 hours while stirring in a warm bath. The liquid took on a yellow-brown color, but turned dark green at the end of the reaction. If a yellowish brown color remained, potassium permanganate solution was added. A large amount of black-brown floating matter was mixed in and deposited after the reaction, but it was possible to separate it from the eggshell and it was washed with water to obtain 4.2 g of eggshell-like matter without a grain layer.

2) Animal bones purification example 11 While stirring black-gray steamed bone powder 102 for fertilizer with a particle size of 1 to 15 #l and a 4% nitrogen and 21% phosphorus solution to a 5% sodium chlorite solution 15011. Added little by little. Hot water bath upper 95
Heated at ~98°C for 2 hours with occasional shaking. After one reaction in which the liquid became yellowish brown, slightly foamed and a chlorine odor was generated, the bone powder was filtered off, washed with 0.1% sodium sulfite solution, and then washed several times with water. The reaction solution obtained by air-drying to obtain about 6.5 g of white to slightly yellowish white bone powder was cloudy and contained a small amount of foreign matter, which was removed by washing with water. Also, a slight amount of oil precipitated, but these were able to be removed.

Example 12 The same bone meal 101 as in Example 11 above was added little by little to 100 zfl' of a 3% sodium hypochlorite solution while stirring and cooling. After the addition, cooling and stirring were continued for about 1 hour, and then the mixture was allowed to stand at room temperature. Two days later, the part where the bone powder was found was finely ground and deposited, and a considerable amount of oil was separated and suspended. The bone powder was filtered out, washed with water, and added to a fresh 3% sodium hypochlorite solution while cooling and stirring. Zero foaming and no heat generation were observed.

This operation was repeated 4 times every 2 days, a total of 5 times. As the treatment was repeated, the foaming and heat generation gradually subsided.

On the 10th day, the upper bone powder was collected by filtration and washed with water to obtain 6 g of mostly white bone powder with no bone W1 visible to the naked eye. Many parts were pulverized, and the entire structure was weakened.

Example 13 The same bone powder 5fI as in Example 11 was added to 100 zl of a 5% aqueous solution of sodium dihydrogen phosphate. 10% rum aqueous solution 401)
1 was added little by little. A strong chlorine odor was generated along with the 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.

3) Shrimp grain purification example 14 Small shrimp shells from which most of the meat has been removed are approximately 10. was added to a solution containing 2% sodium hypochlorite and 2% sodium hydroxide, stirred, and then left at room temperature. After 2 days, filter the shrimp grains, wash them with water, and add fresh hypochlorite 2% and alkali 2%.
The mixture was added to 100 ml of the solution and treated in the same manner as described above. This operation was further repeated twice every two days.

At the 80th day, the grains were filtered and washed with water to obtain a white residue in which the original red color of the grains had completely faded. After air drying, approximately 22 grains were obtained which were soft and easily crushed without retaining their original shape.

4) Purification of seashell powder Example 15 10° of crushed seashell powder with a diameter of about 2 ## for small bird feed was
The mixture was gradually stirred and added to 100 d of sodium hypochlorite solution. It foamed a little and generated heat. After 3 days, the shell powder was filtered and washed with water, resulting in a clean shell with a considerable amount of fine powder mixed in. l! ! There was no change in the original patchy colored area. The yield is about 9.5g after air drying.

Claims (1)

[Claims] (1) Eggshells, animal bones, seashells, or shells are crushed or coarsely ground as necessary, and treated with an aqueous alkaline solution or alkaline hypohalite, or in neutral, alkaline, or slightly acidic conditions. A method for purifying natural calcium materials comprising treatment with an aqueous solution of acid salts, perhalates, halogen dioxides, chloramines, halogenated isocyanuric acids, halogenated hydantoins, peroxides, peracids or permanganates. .