JPH0251428A - Method of stabilizing iron(ii) compound - Google Patents

Abstract

PURPOSE:To stabilize iron(II) compd. by carrying or adsorbing the iron(II) compd. on rice bran. CONSTITUTION:The iron(II) compd. is carried or adsorbed on rice bran. As the rice bran, any of raw rice bran and de-fatted rice bran may be used. However, it is necessary to take care that as fresh and less rancid raw rice bran as possible is used when used as carrier, and the rancidity is not made progress when the product is stored, because raw rice bran has a large oil content and most of raw rice bran stored during a long time is rancid and has a bad influence upon a living body when it is taken in. The de-fatted rice bran has more superior stabilizing ability than the raw rice bran. Therefore, the de-fatted rice bran not going rancid and having stability for a long time period, is preferably used. As the iron(II) compd., any iron(II) compd. can be used, furthermore anhydrous iron(II) sulfate is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method for stabilizing iron (II) compounds, and more specifically, to stabilize iron (II) compounds by supporting or adsorbing iron (II) compounds on bran. ') Concerning methods for stabilizing compounds.

Conventional technology Iron is a trace component essential to living organisms, and among iron (II) compounds, iron sulfate (■) in particular has been used medically as a hematopoietic drug, used as a coagulant in water purification, and has a deodorizing effect for waste and urine treatment. It is also widely used as a mordant, reducing agent, preservative, etc. For example, Japanese Patent Publication No. 5B-31901 discloses the use of iron (II) sulfate as an antibacterial and antiseptic feed additive, and Japanese Patent Publication No. 60-50460 discloses the use of iron (II) sulfate as a deodorizing agent. However, iron (II
) It is known that compounds are unstable in the presence of water and easily absorb oxygen and change. Focusing on this property, Japanese Patent Publications Nos. 61-50013 and 61-41544 disclose the use as a preservative for foods and clothing, and as a freshness-preserving agent for foods.

If a method for making iron (II) compounds stably exist even in the presence of water is developed, it will not only be easier to handle iron (11) compounds as physiologically useful substances, but also increase their utility value and increase their use. The amount will also be expanded. Under the above circumstances, various methods for stabilizing iron (II) compounds have been studied. For example, in Japanese Patent Publication No. 61-59248, a small amount of ascorbic acid was added as a method for stabilizing an aqueous solution of an iron (II) compound, and in Japanese Patent Publication No. 60-142856, a complex of an iron (II) compound and ascorbic acid was added. No. 60-66753 contains ascorbic acid, iron (
II) Compounds and compositions of alum are disclosed, including iron (II) for physiological uses, food freshness preservation, deodorization and flame retardation, etc
) Disclose a functional composite material in which a porous base material is impregnated, coated or kneaded with a compound of phosphoric acid or oxocarboxylic acid, and use the iron(II) compound for the above-mentioned purposes more effectively. It shows what can be done. The present inventor also discovered that iron (II) compounds could be stabilized by adding a small amount of phytic acid or its salt, and filed a patent application. However, iron (I
I) When the compound is used as a feed additive or deodorizer, the composition must be as cheap as possible, harmless to living organisms, and stable for a long time, or conventional stabilization methods for iron(II) compounds must be However, it is difficult to say that these points are still fully satisfactory.

C. Problems to be Solved The present invention provides iron (II) compounds that are suitable for physiological use, particularly as feed additives and deodorants, are stable for long periods of time in the presence of water, and are harmless and inexpensive. II) It is aimed at providing a method for obtaining a composition of compounds.

23 Means for Solving the Problems In order to achieve the above object, the present inventor has conducted various studies and found that iron (n) compounds can be stabilized by supporting or adsorbing iron (II) compounds on bran. We found that By supporting or adsorbing iron (11) compounds to bran, iron (II) compounds are stabilized. There is no need to add certain fly ash or inorganic salts to stabilize the iron(n) compound; bran itself is used as a carrier, and it contains fiber, protein, oil, fat, vitamins, etc. and is widely used as a health food. Because of this, it is also useful as animal feed, and since it is harmless, it is extremely effective for bioutilization of iron (II) compounds, particularly for use in feed and animal odor deodorization. The bran may be either raw bran or defatted bran.Raw bran contains a large amount of oil and fat, and if it has been used for a long time, it is likely to have gone rancid. When using raw bran as a raw material, it is necessary to use fresh bran that has not gone rancid as much as possible, and care must be taken to prevent the product from becoming rancid during storage. However, there is almost no difference in the ability to stabilize iron (II) compounds between fresh raw bran and rancid raw bran, and when comparing raw bran and defatted bran, there is a difference between defatted bran and defatted bran. It is preferable to use defatted bran as a carrier because it has better stabilizing strength and is stable for a long time without becoming rancid.

As the iron (II) compound to be used, any iron (11) compound can be used as long as it is a salt of iron (II) ions, and it is particularly preferable to use anhydrous iron (II) sulfate. The stabilization of iron (II) compounds supported or adsorbed on bran (hereinafter simply referred to as bran) varies depending on the amount of bran used. That is, as the amount of bran used increases, the iron (rl) compound becomes more stable. The weight ratio of iron (II) compound standard is 10
00 or more, and if the amount of bran used is less than this, the iron(II) compound will not be sufficiently stabilized. Again 1
Even if a bran ratio of 0:10 or more is used, the usage will not increase, so the amount of iron(II) compound/bran used is preferably about 10 to 15% by weight. In order to support or adsorb iron(II) compounds on bran, a predetermined amount of finely powdered bran and finely powdered iron(II) is added.
I) Compound, if necessary, other carriers, such as acid clay, diatomaceous earth, magnesium silicate, activated carbon, zeolite, calcium carbonate, hydroxyapatite, other porous substances or Avicel (trade name, manufactured by Fukaisei, microcrystalline) While stirring and mixing organic substances used as excipients such as cellulose powder), starch, and cyclodextrin, add a predetermined amount of wood and, if necessary, water containing a surfactant to make a uniform slurry using the conventional method. After forming granules, they are dried under reduced pressure at a low temperature or at a temperature of 60 to 100°C. Iron on bran (■)
In addition to the methods described above, methods generally used for adsorption can also be used to support or adsorb the compound. In these treatment steps, substances useful to the living body 1, such as salts of zinc, copper, selenium, calcium, magnesium, etc., vitamins, hormones, amino acids, other drugs, cysteine hydrochloride, and other antiseptics are added. The addition of oxidizing agents is favorable and their addition does not require special techniques, the bran containing iron(n) compounds obtained in this way is stable and contains iron(II) for a long time. It exists as a compound and retains the functions of iron(11) ions.

E. The mechanism by which bran stabilizes iron (II) compounds is not clear.
Rice bran contains a considerable amount of phytic acid, which is a calcium salt of phytic acid, and it is reported in JP-A No. 62-48788 that phytic acid or phytic acid has antioxidant properties. Since amino acids have been reported to have antioxidant properties, it is assumed that phytin or protein present in bran forms a complex with iron (n) compounds, thereby stabilizing iron (n). be done. EXAMPLES The present invention will be specifically explained below with reference to Examples.

Example 1 Using the following amounts of various reagents, granules dried at 70°C for 3 hours in a 0.5-on lam bath were further heated with ventilation at 70°C for 9 hours, or granules dried at 70°C for 3 hours were further heated. 10
After heating with ventilation at 0°C for 8 hours, changes in color tone were investigated using the fact that anhydrous iron sulfate (■) turns green due to the presence of moisture. (Table 1) It is shown that the color tone of the heated granules is stabilized by the addition of bran (ocher) as in the case of addition of anhydrous iron (II) sulfate or ascorbic acid.

Example 2 Dissolve 4 g of anhydrous iron (II) sulfate in 40 ml of water and add 1 g of rice bran.
, 2 g, and 4 g were added, thoroughly stirred and filtered, and separated into a filtrate (A) and a precipitate (A). The obtained precipitate (A) was washed with water, and a washing liquid and a precipitate (B) were collected. The precipitate (B) was dried at 70°C to form a solid. Each color tone was as shown in the table below. Further, the filtrate (A) and the washing liquid were heated to the boiling point and observed for changes in color tone.

As controls, anhydrous iron sulfate (■) alone and ascorbic acid were used.

(Table 2) Changes in filtrate (A) caused by heating and boiling were as follows.

1. When the filtrate (A) of control (2) was boiled for 3 minutes, a brown precipitate was produced.

The same was true for the control (1) filter residue (A).

2. When the filtrate (A) of sample (1) was boiled for 3 minutes, a brown precipitate was produced and the supernatant liquid had a light brown color.

3. When the filtrate (A) of sample (2) was boiled for 3 minutes, a pale brown precipitate was produced, and the supernatant liquid had a light brown color. However, sample (1)
Thinner than in the case of .

4. When the filtrate (A) of sample (3) was boiled for 3 minutes, a greenish-white precipitate was produced, and the supernatant liquid had a green color.

From the above results, it can be concluded that anhydrous iron sulfate (II) or rice bran is stabilized, and that the weight ratio of anhydrous iron sulfate (II) to sugar is 1O to io, and that the anhydrous iron sulfate (■) is completely stabilized. iron(
II) It is thought that some kind of complex is formed between the compound and bran, indicating that the stabilizing ability of bran is superior to that of ascorbic acid.

Example 3 A well-mixed mixture of the compositions shown in the table below was heated to room temperature (20 to 2
5%) and left at 70'C, stability in the presence of water was observed from the perspective of color tone.

(Table 3) As is clear from the results, it is found that it is extremely stable even in the presence of water.

Example 4 5 m of water was added to 5 g of granules obtained by a conventional method with the composition shown in the table below.
1 was added, and the mixture was left at 70°C and room temperature to observe stability. The results are shown in the table below. (Table 4) As is clear from the results, the obtained granular R& product exhibits better stability even in the presence of water than when ascorbic acid is added.

Example 5 1mm pass, 0°5mm on, 7 with the composition in the table below
The amount of ammonia absorbed was measured for the granules dried at 0° C. for 3 hours. In each case, the amount of granules used in the measurement was OlIg, which was filled into a glass tube, passed through an ammonia-containing gas roomjl, and the ammonia concentration of the gas after passing through the sample was measured (North type gas detection tube, ammonia 0.5~ 30
% of SH type) The amount of ammonia gas absorbed was calculated. (Table 5) As is clear from the results in the table above, as in the case of ascorbic acid addition, the absorption amount was greater than that, indicating that the deodorizing function was maintained.

Example 6 1 m dried at 70°C for 3 hours with the composition shown in the table below
Fill a glass tube with 0.5 g of 0.5 mm granules, pass 100 mJL of gas containing methyl mercaptan through the sample, and measure the methyl mercaptan concentration of the gas that has passed through the sample (Kitagawa gas detection tube, methyl mercaptan 5 ~1
(40 ppm, SA type used) D, and the absorbed amount of methyl mercaptan was calculated from the difference with the concentration on the passing surface. (Table 6) As is clear from the results in the above table, it is shown that the deodorizing function of anhydrous iron sulfate (n) or anhydrous iron sulfate (II) supported or adsorbed on bran is maintained.

Example 7 Iron (II) chloride...209g, Bran...15, g, Avicel...20. g, water...351 m 1 mm bath 0.5 m mixed and granulated with a composition and dried at 70°C for 3 hours
The m-on granules have a greenish-yellow color and are heated to 70℃ for 8
Even after being left for a long time, it remained stable and maintained a greenish-yellow color. 70°C
The ammonia gas absorption ability of the granules dried in a 1 mm bath for 3 hours at 0.5 mm was examined. For a glass tube filled with 0.1 g of granules, a Kitagawa gas detection tube (
N) I30.5-30%, SH type) was used and measured in the same manner as in Example 5. The results were as follows.

Ammonia gas concentration before passing through the sample: 15.5% Ammonia gas concentration after passing through the sample: 8.2% Calculated absorption amount
8. In the case of OII exchange Example 5, it shows the same absorption capacity, and even in the case of iron (Ill!) other than iron sulfate (H), it is stable as in the case of iron sulfate (II), and retains the deodorizing function. I understand that.

1. Functions and Effects of the Invention The iron (II) compound exists stably in the coexistence of bran, and the functionality of the iron (II) compound is not impaired.

In addition, since bran is a substance used as a health food, it does not cause harm when used on living organisms. Therefore, the product of the present invention is suitable as a deodorizer and feed for animals.

Table 3

Claims (1)

[Claims] A method for stabilizing iron (II) compounds, which comprises supporting or adsorbing iron (II) compounds on bran.