JP2003094072A - Water quality improving agent and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water quality improving agent having a low oxidation- reduction potential at low cost by utilizing aquatic waste such as shells having difficulty in disposing of by eliminating defects such as not to have little effects on the prevention of oxidation of metals and cleaning of vegetables in a conventional method for manufacturing reduced water having the low oxidation- reduction potential which is suitable for drink water, or the like, by adding potassium to natural zeolite and baked shells and re-firing them. SOLUTION: The method prevents calcium carbonate in the shells from decomposing and a conchiolin layer therein from deoxidizing, and imparts conductivity as a glassy carbon matter in a strong reducing atmosphere. Thus, the method improves the water quality by absorbing an electromagnetic wave from an atmospheric electric field and discharging the electrolysis energy by itself.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technology for converting and utilizing calcium-based hard waste, which cannot be decomposed or incinerated among marine-based wastes and is accumulated in a dump year by year, which is troublesome for disposal. is there. That is, the amount of seafood waste such as shells reaches hundreds of thousands of tons per year, and most of them are discarded as unused and are considered as environmentally harmful waste such as odor. The present invention relates to a water quality improver and a method for producing the same, which intends to greatly advance one field of waste treatment technology by providing a technology for producing a high value-added water quality improver by utilizing these resources.

[0002]

2. Description of the Related Art Regarding the above-mentioned waste treatment technology, the necessity has been recognized for several years, and some of the following prior arts have been proposed and patent applications have been filed. The first conventional technique is to produce alkali-reduced water as disclosed in Japanese Patent Laid-Open No. 2000-7418, which is a method for producing a ceramic by producing alkali-reduced water using natural zeolite, husks and potassium oxide as raw materials. , Its purpose is to use natural zeolite and powder of heat-treated shells such as oyster shells and potassium oxide.
This is a method for producing alkali-reduced water by using a ceramic molded into a spherical body by using various kinds of materials. Then, the composition thereof is obtained by adding 3% of K ₂ O to a mixture of natural zeolite and oyster shells baked at 1100 ° C. and molding with an organic binder.
The product which was heated and calcined at ℃ to 840 ℃ had a pH of 10.9 and an O.C.
R. P-225 mV is obtained. In detail, shells such as natural zeolite and oyster shells are placed in a rotary kiln for 1100
The powder is heated and baked at 30 ° C. for about 30 to 50 minutes to form a powder of about 5 to 10 microns, and then 3% of a powder of potassium oxide is mixed with the powder. 3 mm to 5 mm on a rotating drum using a binder
It is formed into a spherical body of a certain degree, and then the spherical body is fired in an electric furnace at 350 ° C. for 2 hours, further heated to 840 ° C. for about 24 hours. Since the present invention is manufactured as described above, the effect that the alkaline reduced water can be easily produced by simply putting the ceramic in water is raised, and by using potassium oxide, the reaction rate of the ceramic is less than that of the conventional one. It is three times or more, and the alkaline reduced water can be obtained in a short time.

Another example of the first prior art is Japanese Patent Laid-Open No. 11-4.
3365, silver nitrate, MgO, K ₂ O, Na ₂ O, CaO
FeO or the like is added and the mixture is fired again at 700 ° C to 1100 ° C. R. As for P, water of -100 mV to +100 mV is obtained. In summary, the present invention provides a granular ceramic for reduced water, which can easily produce reduced water having a low redox potential suitable for beverages and the like, and a method for producing the same. The composition is such that natural zeolite and shellfish are used as main raw materials, and silver nitrate, magnesium oxide, potassium oxide, sodium oxide, selenium oxide and ferric oxide are added to the raw materials and the mixture is fired under predetermined conditions. As the effect of this conventional technology, since the granular ceramics are granulated, the oxidation-reduction potential is high, so-called oxidizing water is obtained as drinking water, plant growth promotion, spoilage prevention and freshness preservation of animals and plants, and rust prevention effect. It is possible to obtain a ceramic that can be easily converted into reduced water having a redox potential suitable for.

A second conventional technique is Japanese Patent Laid-Open No. 2001-2001.
As shown in 26508, an antibacterial agent is produced, which is the production of an antibacterial agent by burning shells at 700 ° C to 2500 ° C in a nitrogen gas atmosphere. The problem is to provide an antibacterial agent which can be produced in large quantities at low cost and has a high antibacterial effect, using a natural material which is not ingested by the human body as a raw material. The structure is such that the shell powder of cinnamon oysters is used as a raw material, and this shell powder is fired in an inert gas atmosphere at a final temperature of 700 to 2500 ° C. In addition, as a result, the method for producing this antibacterial agent and the antibacterial agent obtained by this method exhibit high antibacterial activity by being produced by firing shell powder such as octopus shells in an inert gas atmosphere. . Specifically, O-15
It has a bactericidal effect at a low concentration against Escherichia coli such as No. 7, Staphylococcus aureus, Pseudomonas aeruginosa, fungus, Salmonella, Pibrio parahaemolyticus, and viruses as well as viruses at low concentrations.

A third conventional technique is disclosed in Japanese Patent Laid-Open No. 7-29007.
As seen in 0, it is a decolorizing and deodorant for foods. That is, the shell is heated and dried to form a gap between the pearl layer and the crystal layer, treated with hydrochloric acid, and CaCO ₃ + 2HCl → CaCl ₂
The reaction is + H ₂ O + CO _{2 in} the course of drying to leave an acid content, and when water is added, the reaction proceeds again. When the decolorizing and deodorizing agent according to this conventional technique is added to water, carbon dioxide is generated due to the reaction between the residual acid retained in the pearl layer and the calcium compound contained in the pearl layer or the ground shell, so It is possible to deodorize and decolorize the object to be treated (food etc.) due to the reducing property of carbon dioxide.

[0006]

However, considering the above-mentioned prior art, the first prior art is to combine the shell and natural zeolite and utilize the ion-exchange property of zeolite. Lower. The effect is caused by the elution of potassium, which is a strong reducing ion added later, because the component of the shell does not play a major role, it is a technology for producing mineral-reduced water, and it has little long-term sustainability. The second conventional technique is a technique for producing an antibacterial agent by baking at 700 ° C. or higher in an atmosphere of an inert gas such as nitrogen gas, and the effect is the active mineral component of the protein layer. It is extremely difficult in terms of equipment technology to heat-treat to 900 ° C. in the autoclave while stirring, and it is manufactured with a large cost burden.
Therefore, this conventional technique, along with technically unsolved difficulties,
It has a big drawback that it is very unlikely to be economically viable. In the third conventional technique, shells are heat-dried and treated by adding 0.5% to 1.0% hydrochloric acid to the pearl layer gap, and after the reaction, the reaction proceeds and the nascent dioxide Carbon is generated and deodorizes due to its reducing property, but there is a problem in the sustainability of long-term effects. Further, it has a drawback that its reducing property is weak. The present invention eliminates and improves the above-mentioned various drawbacks and problems of the prior art and develops a new technique which is completely different from these and improved. That is, electromagnetic waves are absorbed from the atmospheric electric field to spontaneously generate electrolysis energy, and at the same time, elution of reducing ions is promoted. It is an innovative new technology. The redox potential (ORP) is higher than ever, and the purpose is to develop and provide a new technology that supplies a water quality improving agent that is practically effective and at the lowest cost by maximizing the utilization of waste. This is a problem to be solved.

Therefore, the problem to be solved by the present invention will be described more concretely. The theoretical concept of the present invention is to first heat calcium carbonate which is the main component of the shell without decomposing, and in the hard protein conchiolin that is a minor component, strontium present in nanometer size,
A bio-mineral such as zinc, iron, manganese, magnesium, and potassium is enclosed in amorphous carbon to form a composite body that is a composite of magnetic materials. It absorbs electromagnetic waves from the atmospheric electric field and takes in energy to create a composite interface. It utilizes an interface charge due to a potential difference to induce an electrolysis action and lowers the redox potential (ORP). R. P + 350 mV to 500 mV of general-purpose water was treated to give a pH of 8.0 to 11.0 and an O.V. R. P-100m
The purpose is to obtain alkaline reduced water from V to -500 mV.

The first problem to be solved is a method for suppressing the decomposition of calcium carbonate. When the weight loss on heating of shells is measured, it is only 2.5% to 3.0 between 400 ℃ and 800 ℃.
%, During this period due to protein degradation, 8
It rapidly decreases when the temperature exceeds 00 ° C, and 4 when it reaches 900 ° C.
It becomes 5% to 46%, and is almost decomposed into calcium carbonate. When calcium carbonate is decomposed to produce CaO, it is digested when put in water to become Ca (OH) ₂ .
Since it is not preferable as a water treatment agent, it must be stable in the form of particles or pieces in water. The second problem to be solved is carbonization of the conchiolin layer, which is a hard protein contained in the shell in an amount of 5% to 10%. 800 ° C in an oxygen-free atmosphere in order for the protein to be carbonized into glassy carbon
The above is necessary, and the atmosphere must be such that it does not oxidize especially at the start of decomposition from 400 ° C. The third problem to be solved is that it is required to be hard-baked to be granular or molded into a specific shape depending on the purpose of use. It is also necessary that the effect has long-term sustainability and that the pH is stable.

[0009]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention has the following epoch-making means which have not been found in the prior art. The first feature is that shells containing one or more of oysters, pearl oysters and scallops are embedded in plant fiber and / or powder containing one or more of wood chips, fir shells and straw, and in a reducing atmosphere. In the above, it is calcined at a temperature of 400 ° C. or more and 1100 ° C. or less, the calcium carbonate in the shells is not decomposed, and the hard protein conchiolin in the shells is amorphous carbon. It is a water quality improving agent. The second feature is that shells containing at least one of oysters, pearl oysters, and scallops are made into small pieces, which are soaked in a dilute sulfuric acid solution having a pH of 1 or less to produce wood chips, fir shells, and straws. It is a Mizutsu improving agent which is buried in a plant fiber and / or powder containing the above and is fired at a temperature of 400 ° C to 1100 ° C. The third feature is that shells containing at least one of oysters, pearl oysters, and scallops are made into small pieces and embedded in plant fibers and / or powders containing at least one of wood chips, fir shells, and straws. 400 ° C or higher to 1100 ° C
That is, it is a water quality improving agent that is obtained by immersing a product that has been fired at the following temperature in a dilute sulfuric acid solution and washing with water. 4 more
The second characteristic is that 10 to 30% by weight of powder obtained by finely pulverizing shells containing at least one of oysters, pearl oysters and scallops to 150 μm or less, and one or more of fir shells, buckwheat husks and wood chips are smoked in a reducing atmosphere. A homogeneous mixture of 5 to 10% by weight of burned or carbonized carbonaceous material and 60 to 85% by weight of clay (anhydrous basis) is granulated, and then one or more of wood chip powder, fir shell and straw. Is a method for producing a water quality improver in which the water quality improver is embedded in a plant fiber and / or a powder containing and baked at a temperature of 600 ° C. or higher and 1100 ° C. or lower.

The contents of the present invention will be described in more detail in relation to the above problems and means. The first problem, the suppression of the decomposition of the calcium carbonate component, as shown in claim 1, was not very effective at suppressing the reaction of CaCO ₃ → CaO + CO ₂ above 900 ° C even if it was buried in wood flour or husk. ,
The 800 ° C. calcined product did not decompose and did not disintegrate in water, but the pH was 10.0, R. P had the effect of setting -150 mV. Furthermore, the pH of the baked product at 900 ° C is 11.0.
It became ~ 11.8 and dissolved in water in one day, but O.I. R. P had an effect of -250 mV. The theory of action will be supplementarily described with respect to claim 2. This means is to prevent the decomposition of CaO decomposed from calcium carbonate in water in some form to prevent an increase in pH, and to react the small granular shells with dilute sulfuric acid to react CaCO ₃ + H ₂ SO ₄ → C
aSO ₄ + H ₂ O + CO ₂ and CaSO ₄ +4 in the heating process
It becomes C → CaS + 4CO, which is made into calcium sulfide that is sparingly soluble in water. It elutes in trace amounts in water and Ca (HS) ₂
And Ca (OH) _{2 is obtained} , and a bactericidal effect is expected, but a temperature of 800 ° C. or higher is required for the calcium sulfide formation reaction. Next, the theory of action of claim 3 is that Ca decomposed by reacting a shell with dilute sulfuric acid or phosphoric acid solution immediately after firing is decomposed.
O is CaSO ₄ or Ca ₃ (PO ₄ ) 2.
CaSO ₄ helps stabilize the pH, and Ca ₃ (PO ₄ ) ₂ is an ion-exchange substance which is a characteristic of apatite and adsorbs and fixes chlorine, fluorine and the like.

The second problem is the condition that the carbide of the hard protein conchiolin layer becomes conductive glassy carbon that adsorbs electromagnetic waves from the atmospheric electric field. The conchiolin layer is a hard protein, and its decomposition is high at 400 ° C, but since the decomposition of cellulose such as wood flour and chaffs begins at 350 ° C, the decomposition begins after the reducing atmosphere is created. Becomes The electromagnetic absorption effect is 2.4
The state of heat generation in a microwave oven of GHz was observed. 800 ° C
In the following cases, absorption heating was performed, but the heat generation was small, and when it exceeded 800 ° C, it became a red hot state at 900 ° C.

Further, the third problem is that the shell is finely pulverized and sintered with clay as described in claim 4. The shell content is 10% due to molding and sintering conditions
It was above 30%. In addition, the reaction immediately after firing is that the biomineral components potassium, phosphorus, and active silica contained in rice husks, buckwheat, wood chips, etc. in the raw material composition react at 600 ° C. after dehydration of the crystallization water of clay, and at low temperature. A sintering reaction occurs. It is difficult to finely pulverize rice husks, buckwheat noodles, etc. in the raw state, and it is easy to use those that have been burned at about 300 ° C in advance, and those that are originally generated as "charcoal" when burned as a buried material are used. In addition, C that is decomposed and produced from the shell containing 10% to 30%
aO reacts with clay and stabilizes. In particular,
The effect of clay is that the iron component of the slag rock and mudstone clay containing iron oxide components of 5% or more is reduced in the carbonization atmosphere to FeO, Fe.
It became a ferrite of ₃ O ₄ and formed a magnetic substance to enhance electromagnetic wave absorption.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The shells which are the resources used in the present invention are oysters, scallops, pearl oysters and the like, which have high productivity as shells. Depending on the purpose of use, the reduced water may have a pH or O. R. There is a permissible limit of P, and the shape of the product when used is selected according to the method of use such as the novel product of claims 1 to 3 and the manufacturing method of claim 4, but all the heat treatments are metal cans. It is carried out at a temperature of 400 ° C to 1100 ° C by being buried in rice husks, wood flour, etc. Further, the carbonaceous material such as rice husk produced in the can after firing is used as a part of the composition raw material of claim 4. By calcining the shells in a reducing atmosphere, calcium carbonate in the shells is not decomposed and the hard protein conchiolin in the shells becomes amorphous carbon. That is the biggest feature.

(Example) The shells used were as follows.
A crushed oyster shell was used. CaCO ₃  9
Sr800 containing 4.5% and 5.0% conchiolin layer
ppm, Mg1050 ppm, Na6100 ppm, F
e, Mn 18ppm and SO₃With 2200 ppm
is there. (Example-1) A shell was crushed into pieces of 5 mm to 10 mm.
Put the fish in a 2 liter stainless steel can into the chaff.
It was buried and baked at 800 ° C. for 1 hour. pH 7.2,
O. R. Tap water of P + 470 mV in a 1 liter container
After adding 1 g of the burned material, the O.I. R.
P is -147 mV to 150 mV, pH is 10.0
To 10.5. After 3 days, the pH was 11.
5, O.I. R. It became P-200 mV. (Example-2) Shells were crushed into pieces of 5 mm to 10 mm.
3% H₂SO_FourSoaked in aqueous solution for 24 hours
After letting it out, take out the water and drain it to a 2 liter stainless steel can.
It is buried in chaff and burned at 800 ℃ for 1 hour.
It was pH 6.7, O. R. 1 tap water of P + 560mV
Put it in a liter container and put 1g of burned material for 20 minutes.
Later O. R. P is -170 mV, pH is 9.6 ~
9.8, pH 30.5, O. R. P
It became -220 mV. (Example-3) Shells were crushed into pieces of 5 mm to 10 mm.
Things are buried in chaff in a 2 liter stainless steel can
And burned at 900 ° C for 1 hour to obtain 3% H₂SO_Fourwater
Put it in the solution and take out the reaction-treated product for 3 hours.
It was washed with water and dried. pH 6.7, O. R. P + 560
Put mV of tap water into a 1 liter container and add 1g of sump.
20 minutes after putting the R. P is -150 mV, pH
Is 8.6 to 8.7, and after 3 days, O.I. R. P-
It was 210 mV and pH 9.0-9.5. (Example-4) The shell was made into a fine powder of 150 microns or less.
20%, crushed charcoal carbide to less than 500 microns
7% of the dried ones and 73% of the dried Kouiwa clay 73% by weight
Mix with, add 20% of water and granulate to a sphere of about 10 mm.
It is buried in a 2-liter stainless steel can for 97
Firing was performed at a temperature of 0 ° C to 1000 ° C for 1 hour. pH 6.
5, O.I. R. For 1 liter of P + 520 mV tap water
1 g of the sample was added, and after 20 minutes, the O. R. P is -1
The pH was 20 mv and the pH was 8.2.
R. P-370 mV, pH becomes 9.5-9.6, and 1
O. even after a week. R. P-280 mV to 350 mV, p
High reducibility of H9.5 to 9.6 was maintained. In addition, the above
After processing once, remove the sample and continue with water only
When the sex was measured, it was ± 0 after 7 days. Since
As above, the pH of the present invention is 8.0 to 11.
0, O. R. Produces alkaline reduced water of P-100mv or less
I was able to

[0015]

1) Most of the conventional alkali-reduced water is weakly alkaline, so that it has a weak rust preventive effect and a short duration, but the alkali-reduced water according to the present invention maintains a high reducibility for a long time. Therefore, a remarkable effect that the anticorrosive effect of metals and the washing and sterilizing power are strong can be obtained. The conventional product has a particularly long-term sustainability of the effect that electrolyzed water or magnetically treated water loses its effect due to cluster formation again in several hours, but the product of the present invention is characterized in that the effect is sustained for at least several days. Is. 2) Alkaline ionized water and reduced water are expected to be great for health drinks, agricultural use, and rust prevention of metal products in recent years, but currently used electrolyzed water requires processing costs such as equipment investment and energy consumption. Is expensive and is not sustainable, costing about 500 yen per 1000 kg of water, but the present invention can be supplied at a very low cost along with a great environmental and economic effect of recycling shells. Great effect.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Jou Ijo             2-14 Koyodai, Takanezawa-machi, Shioya-gun, Tochigi Prefecture             14 (72) Inventor Ryoji Shibuya             3-11-7 Gemdai, Takanezawa-machi, Shioya-gun, Tochigi Prefecture (72) Inventor Tsuneyoshi Shibuya             Yamagata City Yamagata Prefecture Hira Shimizu 143 6 F-term (reference) 4D024 AA02 AB11 BA11 BB01 DA04

Claims (4)

[Claims] 1. A shell containing at least one of oysters, pearl oysters and scallops is embedded in a plant fiber and / or powder containing at least one of wood chip flour, fir shell, and straw, and in a reducing atmosphere,
Water quality that is calcined at a temperature of 400 ° C. or more and 1100 ° C. or less, without decomposition of calcium carbonate in the shells, and the hard protein conchiolin in the shells is amorphous carbon Improver. 2. A shell containing at least one of oysters, pearl oysters and scallops is made into a small piece, which is soaked in a dilute sulfuric acid solution having a pH of 1 or less to contain one or more pieces of wood chips, fir shells and straw. Immersed in plant fiber and / or powder, 400 ℃ or more ~
A water quality improver characterized by being fired at a temperature of 1100 ° C. or lower. 3. A shell containing at least one of oysters, pearl oysters and scallops is made into small pieces, and embedded in a plant fiber and / or powder containing at least one of wood chip flour, fir shell, and straw, and the temperature is 400 ° C. or higher. ~
A water quality improving agent, characterized in that a product calcined at a temperature of 1100 ° C. or lower is immersed in a dilute sulfuric acid solution for reaction, and washed with water. 4. 10 to 30% by weight of powder obtained by finely pulverizing shells containing at least one of oysters, pearl oysters and scallops to 150 μm or less, and one or more of fir shells, buckwheat husks, and wood chips powder in a reducing atmosphere. A homogeneous mixture of 5 to 10% by weight of burned or carbonized carbonaceous material and 60 to 85% by weight of clay (anhydrous basis) is granulated, and then one or more of wood chip powder, fir shell and straw. A method for producing a water quality improving agent, which comprises immersing in a plant fiber and / or a powder containing the above and firing at a temperature of 600 ° C. or higher to 1100 ° C. or lower.