JP2557506B2 - Iron salt compound and its aqueous solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is used for a wide range of applications such as healthy growth of animals and plants, promotion of biological activity, preservation of freshness of foods, antiseptic, mildewproofing, water purification, rustproofing and the like. The present invention relates to a divalent iron salt compound.

[Prior Art] Conventionally, as disclosed in JP-A-59-190226, a ferric iron salt is added to a large amount of a strong alkaline aqueous solution or a divalent iron salt is added to a large amount of a strong acid aqueous solution. Regarding divalent and trivalent iron salts obtained by charging, when this is dissolved in water, the water is converted into a special nonionic reaction system to suppress various ionic reactions found in ordinary water systems. It is known to exert a special action and effect that can be said to be miraculous with respect to the application target. That is, it is known to bring about physiological effects such as antiviral action, anticancer action, and immune action in the living body, and also have antiseptic action, metal corrosion inhibiting action, salt damage removing action, soil damage removing action, and the like. There is.

[Problems to be Solved by the Invention] Although it is a divalent and trivalent iron salt having excellent properties as described above, the divalent iron salt is particularly susceptible to an oxidative action, and is effective when one month has passed from the time of production. There was a problem that it was halved and the original excellent characteristics could not be maintained.

An object of the present invention is to solve the above problems and provide a divalent iron salt composition capable of maintaining the above-mentioned excellent properties of the divalent iron salt for a long period of time.

Means for Solving the Problems The present invention for solving the above problems comprises a divalent or trivalent iron salt, a reducing substance as described below, and an amino acid as described below. Is an iron salt formulation.

When using this iron salt formulation, it is preferable to prepare an iron salt aqueous solution by dissolving it in water. In addition, it is preferable to support the above-mentioned iron salt formulation on the inorganic substance by immersing the inorganic substance in the iron salt aqueous solution.

[Detailed Description of Means] As the divalent iron salt, ferrous chloride (FeCl ₂ ), ferrous sulfate (FeSO ₄ ), ferrous nitrate (Fe (NO ₃ ) ₂ ), ferrous phosphate Inorganic salts such as (Fe ₃ (PO ₄ ) ₂ ), ferrous formate (Fe (HC
OO) ₂ ), ferrous acetate (Fe (CH ₃ COO) ₂ ), ferrous propionate (Fe (CH ₃ CH ₂ COO) ₂ ), ferrous oxalate (FeC)
₂ O ₄ ), ferrous tartrate (FeC ₄ H ₄ O ₆ ), ferrous fumarate (F
In addition to organic acid salts such as eC ₄ H ₂ O ₄ ) and ferrous lactate (Fe (CH ₃ CHOHCOO) ₂ ), reaction mixtures of trivalent iron salts with the following reducing substances can also be used. . The trivalent iron salts include ferric chloride (FeCl ₃ ) and ferric sulfate (Fe ₂ (SO ₄ )
₃ ), ferric nitrate (Fe (NO ₃ ) ₃ ), ferric phosphate (FeP
O ₄ ), ferric ammonium sulfate (Fe ₂ (NH ₄ ) ₂ (SO ₄ )
₄ ) Inorganic salts such as ferric formate (Fe (HCOO) ₃ ), ferric acetate (Fe (CH ₃ COO) ₃ ), iron citrate (FeC ₆ H ₅ O ₇ ), iron stearate (Fe An organic acid salt such as (C ₁₇ H ₃₅ COO) ₃ ) can be used.

As the amino acids, glycine, alanine, leucine, tyrosine, threonine serine, proline, tryptophan, methionine, cystine, monoamino monocarboxylic acids such as cysteine, aspartic acid, monoaminodicarboxylic acids such as glutamic acid, lysine, arginine,
Examples thereof include diaminomonocarboxylic acids such as histidine. The amino acids are preferably added in an amount necessary to react with the divalent iron salt to form an organic complex or the like.

Here, the chemical structure of each amino acid described above is shown in Table-A below. As is clear from Table-A, most of the above-mentioned amino acids have a terminal structure represented by the following formula (1).

-CH (NH ₂ ) COOH… (1) Examples of the reducing substance include aldehydes such as formaldehyde, acetaldehyde, formic acid and benzaldehyde, saccharides such as sucrose, glucose and lactose, ascorbic acid, α-tocopherol, metals such as iron, zinc and copper. The reducing substance is preferably added in an amount necessary to maintain the divalent iron salt in a divalent state or reduce the trivalent iron salt to be divalent.

Examples of the inorganic material as the carrier include metals such as iron, zinc and copper, zeolite, ceramics, inorganic salts and the like. Among these, zeolite and porous ceramics are particularly preferable.

[Action] The iron salt composition of the present invention exhibits various excellent action effects similar to those of the conventional divalent and trivalent iron. For example, when applied to animals and plants of the iron salt formulation of the present invention, the biological activity is promoted,
Growth is promoted. When applied to foods, etc., they are less likely to rot and their freshness is maintained for a long time. In addition, it has a function of modifying and purifying soil, water, and air, and has functions of preventing static electricity, reducing frictional resistance, strengthening concrete, and melting snow.

It is not clear why the iron salt composition of the present invention retains various excellent actions and effects similar to those of the conventional divalent and trivalent irons and can maintain such actions and effects for a long period of time.

However, it is considered that when the reducing substance is added to the divalent or trivalent iron salt, the iron ions are kept in a substantially divalent state, and it is in a state in which it is difficult to be oxidized as much as possible. . It is considered that the iron salt composition is chemically stabilized by further adding an amino acid thereto, without impairing the original excellent effect of divalent iron.

In particular, with respect to divalent or trivalent iron salts, in the iron salt formulation in which only one of the reducing substance or the amino acid is blended, the excellent action and effect of the divalent iron salt are obtained. It cannot be maintained for a long time. From this fact, it is considered that the reducing substance and the amino acid have some kind of synergistic action.

When the iron salt composition of the present invention is used as an aqueous solution, the aqueous system becomes a nonionic reaction system that suppresses various ionic reactions as seen in ordinary aqueous systems. It is considered that the action is effectively exhibited.

The inorganic substance treated by immersing it in an aqueous solution of the iron salt formulation exerts actions such as water purification, air purification, and gasoline reforming.

EXAMPLES Examples 1 to 23 of divalent iron salt aqueous solutions embodying the present invention and Examples 1 to 23 in which they are applied to various applications will be described below.

 First, formulation examples 1 to 3 will be described.

(Formulation Example 1) 1 part of ferrous sulfate hydrate was added to 1 part of water, and aspartic acid of 0.1 to 3.0 mol and sucrose of 0.1 to 3.0 mol were added at 60 ° C.
After stirring for 3 hours, a black-brown aqueous solution was obtained.

(Formulation Example 2) In water 1, 0.1-3.0 mol of glycine and 0.1-3.0 mol of lactose were added to 1 mol of ferric chloride hydrate, and the mixture was stirred at 60 ° C for 3 hours to obtain a blackish brown aqueous solution.

(Formulation Example 3) Glutamic acid (0.1 to 3.0 mol) and glucose (0.1 to 3.0 mol) were added to 1 mol of ferric chloride hydrate in 1 part of water.
The mixture was stirred at 0 ° C for 3 hours to obtain a blackish brown aqueous solution.

With respect to the divalent iron salt aqueous solutions of the above-mentioned formulation examples 1 to 3, even after half a year from the time of preparation, the special effects of the divalent iron salt aqueous solutions described below were not lost. This is a synergistic action that the addition of amino acids forms an organic complex of divalent iron salt, making it a chemically stable substance, and the addition of reducing substances prevents the oxidation of divalent iron salt as much as possible. It is thought to be due to. This is because the action of the divalent iron salt cannot be maintained for a long time even if either the amino acid or the reducing substance is lacking.

Next, Examples 1 to 23 in which the divalent iron salt aqueous solution described above is applied to various uses will be described.

<Example 1> (Promotion of biological activity of seeds) Paddy rice seeds were soaked in the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) for about 24 hours and then sowed. did. The yield of rice at the time of harvest was 12 bales per 10 ares in the treated area where the seeds subjected to this treatment were sown, whereas the control area in which the untreated seeds were sown was only 8 bales. The increase was confirmed. The yield of rice when treated with the divalent iron salt aqueous solution of Formulation 2 was 10.3 bale,
The yield of rice when treated with the divalent iron salt aqueous solution of formulation example 3 is
It was 8.5 bales. Further, the divalent iron salt aqueous solution has an iron content of 10 ^-6 to 10
^-It is applicable in the range of ^-21 molarity. In this case, the yield of rice tended to increase as the concentration of the divalent iron salt aqueous solution increased.

<Example 2> (Soil modification) The divalent iron salt aqueous solution of the above-mentioned formulation example 1 (diluted with an iron content of 10 ^-12
20 was evenly sprayed on 500 m ² of soil and left for 2 months. When the phosphate absorption coefficient was measured two months later, untreated control plot 930 was shown against treated plot 620, and soil modification was observed. The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron, and preferably 10 ⁻¹² to 10 ⁻¹⁵ molar concentration of iron.

<Example 3> (Improvement of survival rate at the time of planting) When transplanting trees (50 bayberry), roots were divalent iron salt aqueous solution of the above-mentioned formulation example 1 (diluted to prepare iron concentration 10 ^-15 molar concentration). After being soaked for about 24 hours, it was transplanted. Observation of the survival rate after that showed that the survival rate of the treated tree was 100%, whereas the survival rate of the untreated tree was 85%.
Incidentally, the divalent iron salt aqueous solution can be applied within the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron, and the effect can be recognized within the range of immersion time of 1 to 30 hours.

<Example 4> (Maintaining freshness of fish) The tuna immediately after being caught is stored for 20 days at 0 ° C while being immersed in the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) of the above-mentioned formulation example 1. did. While the color and body color of tuna gills dipped in this aqueous solution were extremely fresh even after 20 days, the color of tuna gills dipped in ordinary water faded and the meat quality deteriorated. Was there. This is K
When evaluated by the value, the tuna treated with the above aqueous solution had a K value of 23, while the tuna treated with normal water had a K value of K.
The value was 64. The divalent iron salt aqueous solution has an iron content of 10 ^-6 to 10
^-It is applicable in the range of ^-21 molarity.

<Example 5> (Preservation of live fish) Said formulation example 1 together with salt of seawater concentration in a 1 t live fish tank
Of the divalent iron salt solution (prepared by diluting iron to a concentration of 10 ⁻¹⁵ mol), and 200 horse mackerels were put therein and left for 7 days. None of the horse mackerels stored in this aqueous solution died, but 3 out of 200 horse mackerels stored in saline with normal seawater concentration.
0 died. The divalent iron salt aqueous solution can be applied within the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 6> (Maintaining the freshness of vegetables) After dipping the spinach in the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar) by the above-mentioned formulation example 10 for 10 minutes,
It was completely drained, packed in a plastic bag and left at 20 ° C for 7 days. The spinach soaked in this aqueous solution did not discolor even after 7 days, but the spinach soaked in normal water completely turned black. Note that the divalent iron salt aqueous solution has an iron content of 10
It is applicable in the range of ^-6 to 10 ^-21 molar.

<Example 7> (Promotion of animal growth) Mice were raised by feeding 20 ml of the divalent iron salt aqueous solution of Formulation 1 (diluted to have a molar concentration of iron of 10 ^-15 ) per day. After 10 days, the trout bred with this aqueous solution gained 30% more body weight than the mice bred with normal water.
The divalent iron salt aqueous solution can be applied within the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 8> (Improvement of cosmetic paste) To 50 g of hand cream, 1 ml of the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) of Formula 1 was added, and the feel of cosmetic paste on the skin was felt. Was evaluated. The hand cream to which this aqueous solution had been added remarkably improved the makeup paste, and the skin stains were reduced to the extent that it could be confirmed by continuous use once a day for one month. The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 9> (Improvement of health) 100 infants were randomly selected, and 50 of them were treated with the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar) of ^Formula 1 above. Beverages of 100 ml per day were continuously made for 3 months.
When the incidence rate of colds in the winter of that year was investigated, the incidence rate of the group to which this aqueous solution was drunk was 5%, whereas the incidence rate of the group not to drink was 25%. The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 10> (Deodorization) In the dried fish manufacturing plant of the horse mackerel which gives off a strange odor, the above-mentioned formulation example 1
When the divalent iron salt aqueous solution (1) was sprayed (prepared to have an iron content of 10 ^-15 molar), the offensive odor was significantly reduced immediately after that. The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 11> (Preservation of food) The divalent iron salt aqueous solution of the above-mentioned formulation example 1 (diluted iron content: 10 ^-15
Kamaboko was produced using the salt recrystallized using (adjusted to a molar concentration). Kamaboko using this salt did not rot after being stored at 25 ° C. for 20 days, whereas Kamaboko using normal salt rotted on the 7th day. The same effect was confirmed when the above salt was used in the production of raw noodles. Further, the divalent iron salt aqueous solution has an iron content of 10 ^-6 to 10
^-It is applicable in the range of ^-21 molarity.

<Example 12> (Mold-proofing of wall surface) A water-based paint (20 kg) mixed with 200 ml of the divalent iron salt aqueous solution (prepared by diluting iron to a concentration of 10 ^-15 molar) of the above-mentioned formulation example 1 was applied to the wall surface of the bathroom. However, no mold was found even after 6 months had passed. On the other hand, mold on the wall surface of the bathroom coated with the usual water-based paint was observed after two months. The divalent iron salt aqueous solution can be applied within the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 13> (Rust prevention of metal) The divalent iron salt aqueous solution of the above-mentioned formulation example 1 (diluted iron content 10 ^-15
Prepared to a molar concentration of 100 ml) and added 24 mg of raw iron pieces to an aqueous solution containing 100 mg of hydroxylamine as an antioxidant.
After soaking for a period of time, it was soaked in 1% saline and the subsequent state was observed. The raw iron pieces once immersed in the above aqueous solution did not cause rust even after being left for 30 days, whereas the untreated raw iron pieces caused rust after 7 days. The divalent iron salt solution had an iron content of 10 ^-10
It can be applied in the range of up to 10 ^-21 molar concentration, and the effect is recognized when the immersion time in the above aqueous solution is in the range of 1 to 30 hours.

<Example 14> (Reform of tap water) The divalent iron salt aqueous solution of the above-mentioned formulation example 1 (diluted with an iron content of 10 ^-15
A material was prepared using a ceramic that had been immersed in a molar concentration) for 24 hours, and tap water (Nagoya City) was passed through this material. As a result, tap water that passed through this material was irritating for more than a year and had a mild taste. The divalent iron salt aqueous solution can be applied within the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 15> (Wastewater treatment) Iron pieces and copper pieces were dipped in the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) for 24 hours, and then these metal pieces were used at home. It was put into the gray water. As a result, it was confirmed that the effluent was not turbid and the transparency was significantly improved, and that the effluent was purified numerically as shown in Table 1 below. The divalent iron salt aqueous solution has an iron content of 10 ⁻⁶ to 10 ^−21.
It is applicable in the range of molar concentration, and the effect is recognized when the immersion time in the above aqueous solution is in the range of 1 to 30 hours.

<Example 16> (Oil reforming) When 0.1 ml of the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) of the above-mentioned formulation example 1 was added to gas oil 1, the boiling point of gas oil was 2 ° C. It fell and the combustibility improved. On the other hand, no decrease in boiling point was observed when ordinary water was similarly added to light oil. The divalent iron salt aqueous solution has an iron content of 10 ⁻⁶ to 10 ^−21.
It is applicable in the range of molarity.

<Example 17> (Improvement of fuel consumption) After immersing 300 to 500 g of iron pieces and copper pieces in the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) of the above-mentioned formulation example 24 for 24 hours, These metal pieces were put into a gasoline tank of a car. As a result, the mileage per liter was improved by 23% compared to before the metal pieces were charged, and the effectiveness was confirmed for at least 6 months or more. Note that the divalent iron salt aqueous solution contains iron
It is applicable in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration, and the effect is recognized when the immersion time in the above aqueous solution is in the range of 1 to 30 hours.

<Example 18> (Modification of air) The zeolite was immersed in the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) of the above-mentioned formulation example 24 hours, dried, and then filled with this zeolite. An air filter obtained from the above was prepared, and a plant (spinach) was cultivated in the air passed through this air filter. As a result, the plants cultivated in the air passed through the air filter were 50% by fresh weight after one month compared with the plants cultivated in the normal air.
% Increase was recognized. The divalent iron salt solution had an iron content of 10 ^-6.
It is applicable in the range of 10 to ²¹ molar concentration, and the effect is recognized when the immersion time in the aqueous solution is in the range of 1 to 30 hours.

<Example 19> (Antistatic) Divalent iron salt aqueous solution of the formulation example 2 (diluted with an iron content of 10 ^-15
(Prepared to have a molar concentration) was applied to a vinyl film. As a result, the frictional electrification voltage of the vinyl film was remarkably lowered to 5,000 V before application and 120 V after application. The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 20> (Reduction of frictional resistance) The divalent iron salt aqueous solution of the above-mentioned formulation example 2 (diluted iron content: 10 ^-15
When 1.0 ml (prepared to have a molar concentration) was added to the silicone lubricating oil 10, the frictional resistance of the lubricating oil was 30% of that before addition.
Reduced. The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 21> (Reinforcement of concrete) The divalent iron salt aqueous solution of the above-mentioned formulation example 2 was diluted with 1 t of water used for kneading concrete (prepared to have an iron content of 10 ^-15 molar concentration).
1 was added to mix the concrete. As a result, the concrete mixed with the above-mentioned aqueous solution had a compressive strength improved by 50% as compared with the concrete mixed with only ordinary water. The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 22> (Snow melting) The divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) 1 of Formulation Example 2 was evenly sprayed on 1 m ^{2 of the} road surface during snowfall. The snow melting speed of A clear difference in the amount of snowmelt was observed on the road surface sprayed with this aqueous solution compared to the road surface not sprayed. (No wind and clear weather between 1 pm and 3 pm. Average temperature during this period is 7 ° C)
The divalent iron salt aqueous solution can be applied in the range of 10 ⁻⁶ to 10 ⁻²¹ molar concentration of iron.

<Example 23> (Similarly to snow melting on the road surface) When the asphalt was melted and kneaded, 1 ton of asphalt to which the divalent iron salt aqueous solution (prepared to have an iron content of 10 ^-15 molar concentration) 1 was added was used. I paved the road surface. As a result, a clear snow-melting effect was recognized on the road surface as compared with ordinary asphalt as in Example 22.

As described in Examples 1 to 23, by using the divalent iron salt aqueous solution of the Formulation Examples 1 to 3, promotion of biological activity of seeds, soil modification, improvement of survival rate during planting, Preservation of freshness of fish and meat, preservation of live fish, preservation of freshness of vegetables, promotion of animal growth, improvement of makeup paste, improvement of health, deodorization, food preservation, anti-mold on walls, anti-corrosion of metals, modification of tap water It is extremely effective in a wide range of applications such as quality, wastewater treatment, oil modification, fuel efficiency improvement, air modification, antistatic, friction resistance reduction, concrete strengthening, and road snow melting.

Although the reason why the divalent iron salt aqueous solution exerts such an excellent effect is not clear, in the aqueous solution containing the divalent iron salt formulation prepared as described above, various kinds of compounds found in ordinary aqueous systems are used. It is considered that it has a special effect of suppressing the ionic reaction and converting the water into a non-ionic reaction system.

[Effects of the Invention] As described in detail above, according to the present invention, by the action of having a divalent iron salt, the promotion of biological activity, the promotion of growth, the preservation, the modification or purification of soil, water, air, etc., the charging It has excellent effects such as prevention and reduction of frictional resistance. In particular, the combined use of the amino acids and the reducing substance has an excellent effect that the effect of the divalent iron salt can be maintained for a long period of time.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C01G 49/00 C01G 49/00 C02F 1/50 531 C02F 1/50 531S C09K 3/16 101 C09K 3 / 16 101 3/18 3/18 17/02 17/02 C10L 1/12 6958-4H C10L 1/12 C23F 11/18 C23F 11/18

Claims (6)

(57) [Claims] 1. A divalent or trivalent iron salt, at least one reducing substance selected from the group consisting of aldehydes, saccharides, ascorbic acid, α-tocopherol, iron and zinc; glycine, alanine and leucine. , Tyrosine, threonine, serine, proline, tryptophan, methionine,
An iron salt composition comprising at least one amino acid selected from the group consisting of cystine, cysteine, aspartic acid, glutamic acid, lysine, arginine and histidine. 2. A divalent or trivalent iron salt, at least one reducing substance selected from the group consisting of aldehydes, saccharides, ascorbic acid, α-tocopherol, iron and zinc, and {-CH (NH ₂ ) An iron salt compound comprising an amino acid having a terminal structure represented by the chemical formula: COOH}. 3. The aldehyde is formaldehyde,
The iron salt composition according to claim 1 or 2, which is at least one compound selected from the group consisting of acetaldehyde, formic acid, and benzaldehyde. 4. The iron salt composition according to claim 1, wherein the saccharide is at least one compound selected from the group consisting of sucrose, glucose and lactose. 5. An iron salt aqueous solution obtained by dissolving the iron salt composition according to any one of claims 1 to 4 in water. 6. An iron salt mixture-supported material obtained by immersing an inorganic material selected from iron pieces, copper pieces, zeolite and ceramics in the iron salt aqueous solution according to claim 5.