JP4782443B2 - Process for producing active water having active oxygen scavenging ability - Google Patents

Description

  The present invention relates to a novel active hydrogen-containing water having an ability to eliminate active oxygen, which is known to have a significant influence on physiological phenomena of animals and plants, and a method for producing the same.

  Since active hydrogen-containing water, that is, active hydrogen-containing water has the ability to scavenge active oxygen and is known to suppress the physiological adverse effects of active oxygen on animals and plants, Proposed a number of methods for producing water, for example, a method of subjecting ordinary unprocessed water to electrical or physical treatment such as electrolytic treatment and ultrasonic treatment, and chemical treatment with oxidizing agents and reducing agents. However, many of them are not recognized by the Food Sanitation Law.

  For example, among so-called electrolyzed water (electrolyzed with salt added to water), use of cathode-side water (alkaline water and, in one sense, containing active hydrogen) obtained by electrolysis using a diaphragm system Is not allowed under the Food Sanitation Law, so it cannot be officially used directly on food.

  That is, in order to produce active hydrogen-containing water and use it in foods without any legal problems, hydrogen designated as a natural additive is contained in water as active hydrogen by a physical method, or There is no other way than using raw materials approved by the Food Sanitation Law as processing aids.

The inventor of the present invention uses a palladium-based alloy that has previously occluded hydrogen to contact natural water to produce water containing active hydrogen, which is used for growing animals and plants (see Patent Document 1), and the quality of foodstuffs. A method used for improvement (see Patent Document 2) was proposed.
However, these methods require a special apparatus or use an expensive processing agent, so that it is inevitable that the operation is troublesome and the cost is high.

  Therefore, the present inventor conducted further research to overcome these drawbacks, and contacted the raw material water with activated water loaded with magnetized water-insoluble ferric oxide hydrate and, optionally, a noble metal catalyst. A method for producing hydrogen-containing water (see Patent Document 3) was proposed.

Japanese Patent No. 3059359 (Claims and others) Japanese Patent No. 3113653 (Claims and others) JP 2004-24941 A (Claims and others)

  The present invention has been made for the purpose of providing a novel method for producing active hydrogen-containing water more efficiently by using a treatment agent obtained more easily.

  The present inventor has unexpectedly studied a catalyst capable of efficiently generating active hydrogen-containing water by being supported on activated carbon instead of the previously developed magnetized non-aqueous ferrous dioxide hydrate. Was found to show comparable or better catalytic action, and based on this finding, the present invention was made.

  That is, the present invention provides a method for producing active hydrogen-containing water, characterized in that raw water is brought into contact with a magnetized manganese oxide-activated carbon composite or a noble metal catalyst additive thereof.

  The magnetized manganese oxide-activated carbon composite used in the method of the present invention can be formed, for example, by immersing activated carbon in a soluble manganese salt solution and heating it while irradiating microwaves at a resonance frequency in a magnetic field.

  The activated carbon used in this case is one that has been used as an activated carbon for adsorption in the past, and the one with less impure content is used. In particular, safety using plant-based wood flour, sawdust, coconut shell, pulp powder, etc. In principle, those that meet the safety requirements stipulated by the Water Supply Law or Food Sanitation Law.

  However, if desired, it can be obtained using mineral raw materials such as coal, petroleum residues, petroleum coke and petroleum pitch, and plastic raw materials such as phenolic resin, furan resin, urea resin, polyvinyl chloride, polyvinylidene chloride and polycarbonate. Can also be used. These activated carbons can be used after being activated with zinc chloride, phosphoric acid or the like, if necessary.

As the activated carbon has a pore size of 20～1000A, the specific surface area measured by the BET method 200 meters ² / g or more, preferably those of 500 to 1500 ² / g. This activated carbon is used as a granular material having an average particle size of 0.2 to 1.5 mm.

  Next, the soluble manganese salt is not particularly limited as long as it is soluble in water or a water-miscible organic solvent, but a divalent manganese salt is particularly preferable. Examples of such a manganese salt include manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, and manganese rhodanate. These manganese salts are generally colored light rosy, and the aqueous solution also has the same color.

  These soluble manganese salts are usually used as an aqueous solution having a concentration of 0.5 to 5 mol, preferably 1 to 3 mol. If necessary, water and a water-miscible organic solvent such as methanol, ethanol, acetone, ethylene glycol are used as a solvent. A mixture with ethylene glycol monomethyl ether acetate or the like can also be used.

If desired, a weak alkali such as ammonium carbonate can be added to the soluble manganese salt solution. When activated carbon is immersed in this soluble manganese salt solution, manganese ions Mn ²⁺ are adsorbed on the activated carbon. When a magnetic field is applied from the outside, Mn ²⁺ is a paramagnetic ion, causing electron spin resonance (ESR). Bonds strongly with activated carbon.

Next, when heated while irradiating with microwaves of resonance frequency, Mn ²⁺ is fixed on the activated carbon surface while maintaining the state in which electron spin resonance occurs, and is oxidized and insolubilized to form a manganese oxide-activated carbon composite. Let

That is, a device having both a function of changing the strength of a magnetic field by an electromagnet and a function of irradiating microwaves as used in an ESR measurement device, for example, gives a magnetic field of around 330 mT (millitesla) and within a maximum of 35 GHz. The Mn ²⁺ solution prepared in advance and activated carbon are brought into contact with each other while irradiating with a microwave having an appropriate resonance frequency, and the activated carbon surface and Mn are bonded and oxidized.

The conditions in this case need to be adjusted according to the characteristics such as the amount of free radicals as the activated carbon catalyst, that is, reactivity, but Mn ²⁺ is bonded to the activated carbon surface, and H ⁺ (proton) is converted from the acocomplex. Dissociation deprotonation proceeds. Even if the external magnetic field is removed at the stage where the pH has been increased to neutrality, the effect continues, so that the external magnetic field need only be applied at the initial stage.

  Therefore, after the pH rises to the neutral range, the external magnetic field and microwave irradiation are stopped, and further left for 24 hours or longer for aging. At this time, in order to promote the dehydration reaction, the film is heated to 40 ° C. or higher and lower than 100 ° C. at normal pressure and dried to finish fixing and processing.

This drying and fixing process varies depending on various conditions such as temperature, but usually requires 24 hours or more.
Further, even at the end of drying, manganese oxide corresponding to 10% or more of the initial activated carbon mass is generated, and thus the mass increases.
Furthermore, even when a magnetic field is measured by a simple method, a normal activated carbon has only 0.01 mT or less in a direct current magnetic field, but a manganese oxide-activated carbon composite has 0.02 to 0.05 mT or more. Have the above magnetic field.
Manganese oxide produced by these treatments is mainly manganese monoxide, but a small amount of manganese trioxide, manganese dioxide, etc. may be produced as a by-product depending on conditions.

  In the method of the present invention, active hydrogen-containing water can be produced by bringing raw material water into contact with the magnetized manganese oxide-activated carbon composite thus prepared. There is no restriction | limiting in particular as raw material water processed at this time, It can select arbitrarily from normal tap water, groundwater, river water, etc., and can be used.

  The active hydrogen-containing water obtained by the method of the present invention contains a significantly higher concentration of active hydrogen than the active water obtained by the conventional method. This is an electron spin resonance spectrum (hereinafter abbreviated as ESR spectrum). It can be easily confirmed by measuring.

  That is, after processing the raw water to generate hydrogen radicals, a trapping agent such as 5,5-dimethyl-1-pyrroline-N-oxide (hereinafter referred to as DMPO) is added as quickly as possible, and a refrigerant such as Freezing rapidly using liquid nitrogen, trapping hydrogen radicals, measuring the ESR spectrum, and quantifying it based on the relative intensity of the hydrogen radicals in the resulting spectral pattern.

  The active hydrogen-containing water obtained by the method of the present invention has, as a standard sample, the hydrogen radicals quantified in this way, the intensity of the peaks derived from the hydrogen radicals generated near the magnetic field strengths of 331.8 mT and 335.5 mT. The former of the peak intensity derived from manganese used has a high concentration of 0.03 or more, particularly 0.1 or more, and the latter has a high concentration of 0.04 or more, particularly 0.2 or more.

  On the other hand, in the case of active water obtained using a conventional method such as a palladium catalyst, the intensity of the peak derived from hydrogen radicals generated in the vicinity of 331.8 mT and 335.5 mT of the magnetic field measured by the same method is The former peak intensity is 0.023 and the latter is 0.035. In the case of active water produced using a normal water heater, absorption of hydrogen radicals is hardly observed.

  In general, hydrogen radicals are less reactive than hydroxy radicals and the like. Therefore, in order to completely capture hydrogen radicals, it is preferable to add a trapping agent such as DMPO as much as possible, that is, about 25% by mass.

  The absolute value of the intensity corresponding to each component of the electron spin resonance spectrum is the measurement conditions such as the type of detection device, microwave output, magnetic field sweep width, sweep time, magnetic field modulation, magnetic field strength, and the amount of trapping agent. The relative intensity of the peak derived from the hydrogen radical at a specific magnetic field strength of around 331.8 mT and around 335.5 mT with respect to the peak derived from manganese in the standard sample depends on the above factors. It always shows a constant value.

  Moreover, the active hydrogen-containing water obtained by the method of the present invention exhibits the effect of eliminating active oxygen. This can be confirmed by measuring the amount of generation using the fact that the active oxygen reacts with the reducing substance and is accompanied by a weak luminescence phenomenon. For example, this method is disclosed in, for example, 2001, published by John Willy & Sons, "Lumescence 2001", Vol. 16, pages 1-9, " Imaging of hydroperoxide and hydrozin peroxide-scavenging substances by photon emission in method Z A system active oxygen elimination light emission test can be performed, and the emission intensity of the Y component can be measured. In this method, X represents active oxygen, Y represents a scavenger (hydrogen donor), and Z represents a catalyst.

  Thus, in the method of the present invention, as a result of improving the electron supply capability by forming a magnetized manganese oxide-activated carbon composite, the dissociation of water is promoted, and a part of water molecules is The constituent hydrogen is reduced, becomes active hydrogen, is released into water, and active hydrogen-containing water is produced. When active oxygen is present, it reacts with active oxygen and is erased.

  In general, activated carbon originally has a dehydrogenating ability such as hydrocarbons, but its ability is never high, and dehydrogenation usually proceeds only in the presence of oxygen and other hydrogen acceptors. However, when various transition metals are supported, the dehydrogenation activity is remarkably improved, and the hydrogen adsorption capacity is increased several tens to several hundreds times that of the adsorbed metal due to a synergistic effect. Then, the adsorbed hydrogen molecules are dissociated on the metal surface to be in an atomic state and held on the activated carbon. Then, the hydrogen on the activated carbon rapidly dissociates through the metal into, for example, medium water to form active hydrogen-containing water.

  On the other hand, it is generally known that when a noble metal catalyst is supported on activated carbon, the catalytic action is remarkably improved. Therefore, it is preferable to carry a precious metal catalyst on the activated carbon for treatment of the present invention. As this noble metal catalyst, for example, platinum, palladium or silver is used. The amount of these noble metal catalysts supported is 0.07 to 3 ppm, preferably 0.1 to 1 ppm, based on the mass of the activated carbon.

  In the production of the active hydrogen-containing water by the method of the present invention, a magnetized manganese oxide-activated carbon composite or an activated carbon catalyst supporting this and a noble metal catalyst is packed in a column, and the raw water is SV value of 10 or more, preferably 20 By passing at a speed of ~ 30. At this time, instead of directly packing the activated carbon catalyst into the column, using a cartridge that can be detachably fitted into the column and filling the activated carbon catalyst therein, the capacity as a catalyst is reduced. This is advantageous because it can be easily exchanged.

  According to the present invention, the active hydrogen-containing water having a remarkably high active oxygen scavenging ability as compared with the active hydrogen-containing water obtained by the method using activated carbon carrying the conventional magnetized water-insoluble ferrous dioxide hydrate. Can be manufactured.

Next, the best mode for carrying out the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The active oxygen scavenging ability and the polyphenol content in each example were measured by the following methods.

(1) Active oxygen scavenging ability;
In a small test tube, 15 μl of 5,5-dimethyl-1-pyrroline-N-oxide (hereinafter abbreviated as DMPO), 35 μl of 5.5 mM diethylenetriaminepentaacetic acid and 50 μl of 2 mM hypoxanthine are mixed.
Next, add 50 μl of the sample solution to this, add 50 μl of xanthine oxidase solution (Boehringer Mannheim, 20 U / ml), and suck it into a special flat cell (manufactured by JEOL Ltd., approximately 130 μl volume) and set it in the ESR device. The spectrum is read and compared with an SOD standard solution (Toyobo Co., Ltd., 3000 U / mg) to obtain a measured value.
(2) polyphenol content;
5 ml of the Folin reagent is mixed with 5 ml of the sample, and after 3 minutes, 5 ml of 10% aqueous sodium carbonate solution is added and shaken to obtain a blue solution. Next, after standing at room temperature for 1 hour, the absorbance at 760 nm is measured, and compared with a calibration curve of a standard substance (gallic acid) prepared in advance, it is determined in units of mM.

Reference Example 1 (Production of magnetized manganese oxide-activated carbon composite)
After immersing 100 g of activated carbon (average particle size 1.00 mm, specific surface area 1350 m ² / g) in 500 ml of 1 molar aqueous manganese (II) chloride solution, 700 ml of 1 molar aqueous ammonium carbonate solution was added dropwise thereto, It is placed in a 323 mT DC magnetic field and heated at 60 ° C. for 30 minutes while irradiating with microwaves of resonance frequency. Next, the activated carbon was filtered off and heated at 100 ° C. for 10 hours to obtain 120 g of a magnetized manganese oxide-activated carbon composite (hereinafter referred to as composite catalyst) having a Mn content of 2.78 mg / g.

Reference Example 2 (Production of Fe-containing activated carbon)
The same operation as in Reference Example 1 was carried out except that 500 ml of a 1 molar ferric chloride aqueous solution was used instead of 500 ml of a 1 molar aqueous manganese (II) chloride solution, and an Fe content of 2.38 mg / g. 121 g of activated carbon (hereinafter referred to as a magnetic activated carbon catalyst) carrying magnetized water-insoluble ferric oxide hydrate was obtained.

  A glass column (25 × 500 mm) was filled with 300 g of the composite catalyst obtained in Reference Example 1 and washed with 600 ml of distilled water, and then tap water was passed at an SV value of 20, and 1000 ml thereof was collected. The active oxygen scavenging ability of this product was measured, and the results are shown in Table 1. For comparison, the active oxygen scavenging ability of untreated distilled water is also shown.

Comparative Example 1
Instead of the composite catalyst, the column filled with the magnetic activated carbon catalyst obtained in Reference Example 2 was used, and tap water was passed under the same conditions as in Example 1. The results are shown in Table 1.

  As can be seen from this table, according to the method of the present invention, active hydrogen-containing water having a much higher active oxygen scavenging ability than that obtained by the conventional method can be obtained.

  To 20 ml of active hydrogen-containing water obtained in Example 1, 0.5 g of commercial coffee powder was added and boiled for 1 minute. The polyphenol content in the coffee extract thus obtained was measured, and the results are shown in Table 2.

Comparative Example 2
The same amount of distilled water was used in place of the active hydrogen-containing water obtained in Example 1, and extraction was performed from commercially available coffee powder in the same manner as in Example 2. The polyphenol content in the coffee extract thus obtained was measured, and the results are shown in Table 2.

  As can be seen from this table, when the active hydrogen-containing water obtained by the method of the present invention is used, more polyphenols can be extracted from coffee.

  According to the method of the present invention, highly active active hydrogen-containing water that can be widely used for preservation of fresh food products, sterilization, drinking water, and animal and plant cultivation can be produced.

Claims (5)

A method for producing active water having active oxygen scavenging ability, comprising bringing raw material water into contact with a magnetized manganese oxide-activated carbon composite. A method for producing active water having active oxygen scavenging ability, comprising bringing raw water into contact with a noble metal catalyst additive of a magnetized manganese oxide-activated carbon composite. The method for producing active water having active oxygen scavenging ability according to claim 1 or 2, wherein the activated carbon has a specific surface area of 200 m ² / g or more. The method for producing active water having active oxygen scavenging ability according to claim 2, wherein the noble metal catalyst is platinum, palladium or silver. 4. The magnetized manganese oxide-activated carbon composite is formed by heating a soluble manganese salt-containing solution in the presence of activated carbon while irradiating with a microwave in a magnetic field. A method for producing active water having active oxygen scavenging ability .