JPH1014535A - Calcium agent for foods and beverages - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a calcium agent for foods and beverages, easily producible with an inexpensive facility without necessitating the burning at a high temperature and useful for the treatment of osteoporosis, etc., by bringing a calcium- containing natural material into contact with an organic acid in an unburnt state. SOLUTION: A calcium-containing natural material such as shell, coral, sea urchin shell or egg shell is brought into contact with an organic acid such as acetic acid, gluconic acid, lactic acid, malic acid, fumaric acid, citric acid, succinic acid or tartaric acid in unburnt state or after a heat-treatment at <700 deg.C, subjected to purification process including acid-treatment, gel-filtration, polymer membrane filtration, ion exchange resin treatment and chelate resin treatment and finally treated with a reverse osmosis membrane to obtain the objective calcium agent for foods and beverages.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the production of calcium preparations for foods and drinks, and more particularly, to the production of natural calcium sources such as shells and eggshells after baking (incineration) at low temperatures or after organic treatment. The present invention relates to the production of a conventionally unknown new calcium agent for foods and drinks by reacting with an acid.

The present invention is extremely advantageous from an industrial point of view because it does not need to be fired at a very high temperature unlike the conventional method, and according to the present invention, a calcium agent can be obtained without high-temperature heat treatment. In addition to being able to do so, it is similar to natural products and is particularly suited to the needs of naturally oriented consumers. Therefore, the present invention not only excels in the technical field of food and drink, but also provides an effective method for treating shellfish discarded in large quantities, and is also prominent in the technical field of pollution control. .

[0003]

2. Description of the Related Art Scallop shells, oyster shells, purple shells, eggshells, etc. are disposed of in large quantities, but most of them are not effectively used, and most of them are conventionally landfilled or dumped into the ocean. . However, with the development of the fishing industry in recent years, the amount of shells discarded is increasing, and the disposal thereof is becoming more serious. On the other hand, it has become difficult to secure landfill sites, and marine dumping has also been restricted, making disposal itself extremely difficult.

Attempts have been made to utilize this natural resource effectively, rather than discarding shells. For example, shells are fired at a high temperature of 1000 to 1200 ° C., and then reacted with an organic acid to form an organic acid. A method for producing calcium has been proposed (JP-B-56-53974).

However, in such a known method, in order to completely sinter calcium carbonate of natural shells into calcium oxide in a short time, 1000 to 1200
Must be sintered at extremely high temperatures,
At the prior art level, it was said that the intended purpose could not be achieved by low-temperature heat treatment. Furthermore, the use of unfired raw materials was contraindicated. This high temperature firing (incineration)
The treatment is performed for smoothing the reaction between the calcium oxide and the organic acid, which is performed later, and for removing the organic phosphorus and the like contained in the shell.

Therefore, in the conventional method requiring high-temperature firing (incineration), not only high energy is consumed, but the equipment must be reinforced to withstand the high energy, and the equipment cost is extremely high. And also poses a major problem in occupational safety. In this case, industrial mass production or mass treatment has its own limit, cost cannot be reduced, and the intended purpose cannot be achieved.

[0007]

SUMMARY OF THE INVENTION In view of the state of the art, the present invention achieves a completely different energy saving from the conventional method, reduces the production cost, and reduces the unit cost. This was done to develop a method.

[0008]

Means for Solving the Problems The present invention has been made to achieve the above-mentioned object, but the conventional method for producing organic acid calcium using shells, as described above, becomes a raw material. The process of baking shellfish or eggshell at a high heat of 1000-1200 ° C. to burn organic matter to form calcium oxide, and reacting it with an organic acid. (85
0 ° C. or higher) and burning organic substances.

Therefore, high-temperature sintering is indispensable, and low-temperature sintering (below 700 ° C.) does not achieve the intended purpose, and even non-sintering is rather contraindicated in the art. In the case of unfired or low temperature firing,
Deproteinization and deodorization of shellfish are important points,
At the same time, in the solution containing the remaining protein that cannot be removed, the reaction between the shell powder and the organic acid is carried out as shown in the following formula. This reaction is caused by foaming (mainly due to CO ₂ ). ) Increases, and it is fully expected that the reaction will not be carried out smoothly. 2RCOOH + CaCO ₃ → (RCOO) ₂ Ca + CO ₂
+ H ₂ O

[0010] In view of these points, it has been considered that unfired or low-temperature fired shells cannot be used as a raw material according to the conventional technical knowledge. The present inventors have dared to respond to such technical common sense, made a major change in the idea, focused on unfired or low-temperature firing, which had been contraindicated conventionally, and as a result of earnest research, as a result, The present inventors have clarified that the organic acid calcium salts can be industrially produced efficiently and energy-saving without firing, thereby completing the present invention. It is not an exaggeration to say that the present invention has made the impossible possible, but it is a revolutionary invention and a very excellent invention that fully satisfies all the patent requirements.

That is, according to the present invention, calcium-containing natural products such as shells and eggshells are unfired or fired at a low temperature (less than 700 ° C.), and then crushed to powder if necessary.
The point is that the organic acid calcium salt is produced by contacting and reacting with an organic acid to produce a calcium agent for food and drink. Hereinafter, the present invention will be described in more detail.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The natural calcium-containing material used as a raw material for carrying out the present invention is any natural calcium-containing material such as shells, eggshells, (weathered) corals and sea urchin shells. Can be used alone or in combination of two or more.
The shell may be either a bivalve or a conch,
For example, scallops, oysters, clams, clams, clams, red shellfish, pearl oysters, turtle shells, abalone, snails, barnacles, mussels and the like can be used in combination of one or two or more types. In many cases, the subsequent separation step is performed smoothly.

Of these shells, scallop and oyster shells, which are particularly easily discarded and readily available, are advantageously used as preferred raw materials for the purposes of the present invention. In the present invention, not only edible shells, but also non-edible undesired shells such as barnacles and mussels that have been exterminated and eliminated or removed can be used. It is excellent.

The shells used as raw materials are washed thoroughly to remove unnecessary substances. In this treatment, it is particularly important to remove organic matter from the calcium source as a raw material to produce calcium organic acid from unfired shells, and wash sand, algae, garbage, etc. attached to the shell surface with water. Then, if necessary, the substrate is dipped in a dilute acid such as dilute hydrochloric acid, and the acid concentration and the dipping time are adjusted depending on the degree of contamination.

Heating (40-50 ° C.) in winter
By doing so, unnecessary substances can be removed in a short time. The calcium raw material soaked in acid is washed away with water until neutral. After washing, air-drying or mechanical drying is performed. If necessary, this may be appropriately crushed or pulverized. When low-temperature sintering is not performed, this is treated with an organic acid as it is, and when low-temperature sintering is performed, low-temperature sintering (700 ° C.) is performed using a known sintering method such as an electric furnace, a gas furnace, a fluidized bed method, and a rotary kiln method. Less). Sterilization is efficiently performed by low-temperature baking, and production suitable for food and drink can be obtained from a sanitary point of view.

Next, these are treated with an organic acid. In this case, the size of the particles of these calcium raw materials may be appropriately determined, but the finer the particle, the faster the reaction. For example, the calcium raw material is roughly pulverized and then micro-pulverized to use a pulverized product having a mesh of 50 to 800 mesh, preferably about 100 to 600 mesh. In order to react the organic acid with these calcium raw materials, they may be brought into contact with each other, and are usually performed in an aqueous medium.

As a reaction with an organic acid, for example, a calcium raw material (preferably coarse to pulverized) is converted into an organic acid solution (an aqueous solution or an aqueous suspension, and if necessary, another solvent may be used). Good) and put it near neutrality, and the calcium raw material is slurried in water, and the organic acid solution is added dropwise thereto (if necessary, the solid organic acid is added). (It may be added directly).
Among these methods, from the viewpoint of workability, a method of adding a calcium raw material powder to an organic acid aqueous solution is useful because the reaction is quick.

The reaction is carried out at a temperature of from 60 ° C to 100 ° C. In the early stage of the reaction, the reaction is easily performed at a low temperature due to the high acid concentration, but the reaction becomes slower when approaching neutrality.
It is good to react near. Regarding the concentration at the time of the reaction, the dissolution of the organic acid calcium salts at 30 ° C. to 50 ° C. or less is preferred. Therefore, for calcium gluconate,
25%, 4-20% for calcium acetate, 10-60% for calcium lactate, 7- for calcium acid malate
45%, 5-30% for calcium citrate malate,
When the temperature falls within the range described above, the reaction becomes cloudy. At the end of the reaction, the reaction is stopped at pH 3-4.

According to the present invention, an uncalcined or low-temperature calcined calcium raw material powder is reacted in an organic acid solution to produce an organic acid calcium salt for food or drink. Unlike the case of using, a characteristic feature is that a trace amount of biological components such as protein, iron, and magnesium contained in natural calcium raw materials such as shells remain. Of these components, proteins containing biological components, in particular, are said to have the function of helping calcium absorption into the body. Therefore, compared to conventional high-temperature baked products, nutritional components are superior and production costs are reduced. The advantage that it can be obtained.

In the present invention, if it is intended to further increase the calcium concentration, it may be purified by one or a combination of two or more of various purification methods. For example, an acid treatment is used to control or remove proteins, or a gel filtration method, a polymer membrane filtration method, and a high-porous polymer ion exchange resin are used to remove various off-tastes and odors. A law or the like may be used. In addition, a chelate resin may be used for removing heavy metals.

Certainly, the conventional high-temperature calcination treatment is an effective means for exchanging calcium carbonate for calcium oxide. At this time, some heavy metals may be removed.
The merit of separate treatment with a chelate resin after the unsintered or low-temperature sintering treatment as in the present invention far exceeds the merit of the conventional high-temperature sintering treatment (for example, omission of the chelate resin treatment). Excellent in terms of quality.

In the present invention, the purification treatment may be performed, for example, as follows. If the protein precipitates after the reaction with the organic acid, an acid treatment may be performed. In addition, in order to remove foreign substances (sand, algae, dust, etc.), filtration and centrifugation are performed.
A clear organic acid calcium salt solution is obtained.

The clear solution thus obtained is subjected to gel filtration. Gel filtration is Sephadex G-2.
Either 5 or G-50 can be used, but G-25 has sharper division. The standard solution charge amount is 1/10 or less of the gel volume, and the flow rate is 0.1 to 10 times the gel volume.
Flow 0.3 / Hr as a guide. Calcium organic acid effluent is obtained at 1.5 volumes of gel volume. In this step, a high molecular organic material is removed, and this solution is passed through a solution in which a high-porous polymer resin having no ion exchange group and a chelate resin are connected.

As the porous resin, for example, HP series Amberlite XAD series (all trade names) manufactured by Mitsubishi Kasei Co., Ltd. can be used. In addition, as the chelate resin, CR series (trade name of Mitsubishi Kasei Co., Ltd.) can be used. For the purpose of deodorization and decolorization in the case of a high-porous polymer resin, heavy metals are selectively removed in the case of a chelate resin, and the flow rate is the same as the resin volume or twice the volume / Hr. The solution after deodorization, decolorization and removal of heavy metals is concentrated at about 60 ° C. using a reverse osmosis membrane.

As the reverse osmosis membrane, all known reverse osmosis membranes such as cellulose acetate, polyamide, denatured ring polymer, and water-soluble polymer cross-linked can be used. Cellulose acetate is generally used. Su membrane (Toray composite membrane:
Product name).

The concentration of the organic acid calcium is carried out using a reverse osmosis membrane. According to the present invention, since a reverse osmosis membrane can be used as described above, there is no need to install a large-sized device such as a vacuum concentrator as in the related art, and concentration can be performed with a small module. The obtained concentrated liquid can be used as it is or further concentrated and used as a liquid to paste-like calcium agent for food and drink.However, if this is cooled, crystals of the organic acid calcium are obtained. And can be used as a solid calcium preparation for food and drink.

In order to produce organic acid calcium using a polymer film, the reaction solution from which the above-mentioned protein and foreign substances have been removed is applied to a polymer film (commonly known as 10,000 to 50,000 Mw film) for 2 to 3 kg.
The pump is circulated at a pressure of about / cm ² to filter the organic acid calcium into the external solution. As the concentration of the internal solution increases and the filtration rate slows down, purified water is added to dilute the solution, and the whole amount of the organic acid calcium is circulated through a pump until the solution is discharged into the external solution. In the subsequent step of collecting the external solution and applying it to the above-described high-porous polymer resin and chelating resin, energy-saving organic calcium acid can be efficiently industrially produced in the above-described step.

Hereinafter, embodiments of the present invention will be described.

[0029]

Example 1 Scallop shells were washed with water to remove sand, algae and dirt. For heavily soiled shells, dilute hydrochloric acid 0.5
It was immersed in a ２2% solution for several minutes to several minutes to remove surface dirt. The washed calcium raw material was air-dried or machine-dried, and then pulverized to 100 to 600 mesh using a pulverizer.

500 g of the obtained powder was mixed with a 95% acetic acid solution 2
1 L of water was added to 000 g, and the mixture was gradually added while heating to 70 to 100 ° C. When foaming is large, add 1 octyl alcohol
The reaction was performed by adding ~ 2 drops. The pH showed 4.0. This solution was centrifuged (3000 RPM, 10 minutes) to obtain 3.3 L of a supernatant. Add this solution to Sephadex (column:
200 mm diameter x 2000 mm height) G-25 Pour into 25 L, and then flush with purified water to remove calcium acetate-containing part 4.
0 L was obtained. This was connected to 3 L of a high-porous polymer resin (Dyer ion HP-20) and 2 L of a chelating resin (Dyer ion CR-40), and the mixture was flown at 6 L / hr to obtain 47 L of colorless and odorless calcium acetate. While maintaining this solution at about 60 ° C., it was concentrated with a simple facility using a medium pressure membrane Su (manufactured by Toray Industries, Ltd.) to obtain 2 L of a concentrated solution.

The obtained concentrate was heated to 80 ° C., adjusted to pH 6.5 with calcium hydroxide, and cooled to obtain crystals.
Thus, 600 g of calcium acetate powder was obtained. The same treatment was performed using eggshell instead of scallop shell, and as a result, 650 g of calcium acetate powder was obtained.

[0032]

Example 2 Powder 500 obtained in the same manner as in Example 1
g of lactic acid, 1 L of purified water was added to 1800 g of lactic acid, and the mixture was heated and reacted. As a result, the pH was 3.5. The reaction solution was centrifuged to obtain 2900 cc of a supernatant. This liquid is overlaid with a polymer membrane (commonly known as a 50,000 flat membrane) in a multi-stage manner, 1-2 kg / cm ² , flow rate 10
By circulating the pump at ５０50 / m ² / Hr, it was discharged as a calcium lactate solution into the external solution. Internal fluid (circulating fluid)
Was gradually concentrated and became viscous, and purified water was added in an amount of the liquid that had flowed out, and filtration was performed on a polymer membrane for 24 hours. At this time, most of the calcium lactate was discharged into the external solution. Solution 8 at this time
L, and a crystal was obtained at 2,500 cc through the steps of a high-porous resin, a chelate resin and reverse osmosis in the same manner as in Example 1. 1 kg of calcium lactate powder was obtained.

[0033]

Example 3 Powder 500 obtained in the same manner as in Example 1
g was added to a solution prepared by dissolving 1340 g of L-type malic acid in 5 L of purified water and reacted. After the same treatment as in Example 1 was performed to obtain 4000 cc of the concentrated solution, the pH was adjusted to 3.0, and a crystallization treatment was performed.
I got

[0034]

Example 4 Powder 300 obtained in the same manner as in Example 1
g was added to a solution of 280 g of citric acid and 134 g of malic acid dissolved in 5 L of purified water and reacted. After performing the same purification treatment as in Example 2 to obtain 2800 cc of the final concentrated solution, the mixture was heated to 80 ° C., and the pH was adjusted to 6.7 with calcium hydroxide.
To obtain 350 g of calcium citrate malate powder.

[0035]

Example 5 The treatment solution of the polymer membrane obtained in Example 2 was subjected to a combined treatment of a passing solution of a porous resin and a chelate resin and washing, followed by vacuum concentration according to a conventional method. 15 kg were obtained.

[0036]

As described above, according to the present invention, an energy-saving organic calcium acid can be produced without using high temperature and high heat, and can be produced with industrially inexpensive equipment. In particular, since the gel or ion exchange resin, reverse osmosis membrane, or polymer membrane used can be used repeatedly and many times, it is expected to greatly reduce production cost or product unit price in the future.

Further, the calcium preparation for eating and drinking according to the present invention can be made into various dosage forms (concentrated liquid-paste-powder) (diluted in some cases). It can be added and mixed freely, and is extremely effective for enhancing calcium in foods and drinks.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C07F 3/04 A23L 2/00 F

Claims (6)

[Claims] 1. A method for producing a calcium agent for food and beverage, comprising contacting an organic acid with a calcium-containing natural product in a state of being unfired or after being subjected to a heat treatment at less than 700 ° C. 2. The method according to claim 1, wherein the calcium-containing natural product is a shell, coral, sea urchin shell, and / or eggshell. 3. The method according to claim 1, wherein the organic acid is acetic acid, gluconic acid, lactic acid, malic acid, fumaric acid, citric acid, succinic acid, and / or tartaric acid. 4. After the contact treatment with an organic acid, a purification treatment including an acid treatment method, a gel filtration method, a polymer membrane filtration method, an ion exchange resin treatment method, and a chelate resin treatment method is performed. The method according to claim 1. 5. The method according to claim 4, further comprising performing a reverse osmosis membrane treatment. 6. A calcium agent for food and drink produced by the method according to any one of claims 1 to 5.