JP4795782B2 - Strong acid water impregnated deodorant product - Google Patents

Description

  The present invention relates to a deodorizing product that adsorbs and deodorizes ammonia, which is a cause of human odor, and an alkaline odor gas typified by trimethylamine, which is a cause of decaying odor, by a chemical neutralization reaction In order to eliminate strong acid water containing sulfate ions produced by sulfur-oxidizing bacteria (genus Thiobacillus), which is produced when the odor of sulfur compounds typified by hydrogen sulfide is deodorized in a biological deodorization device using microorganisms. Effective use as a odor product.

  Conventionally, various deodorizing products that absorb and deodorize environmental odors have already been commercialized. These commercialized deodorization methods include those that use physical adsorption that is adsorbed on activated carbon, etc., those that use chemical adsorption that adsorbs odorous substances through chemical reactions, and those that generate another odor and feel bad odors. A masking technique or the like that has the effect of making it difficult is used. In particular, chemisorption is used as an effective deodorizing technique because it does not re-release once it reacts unless a reversible reaction occurs.

Among chemical adsorption, neutralization reaction with highly reactive acid / alkali is one of the most basic methods. Specifically, a method of adsorbing an acidic malodorous substance to an alkaline substance or an alkaline substance to an acidic substance. The method of adsorbing malodorous substances is used.
The malodor control law enacted in 1971 stipulates 22 typical malodors along with their respective odor indices. Among these, alkaline odors include ammonia and trimethylamine. These are deodorized by being absorbed and neutralized by an acidic aqueous solution. For example, Japanese Patent Application Laid-Open No. 2003-105385 proposes a method for absorbing alkaline odorous materials by adjusting pH to 4 to 6 as a cleaning composition. No. 213850 proposes a method of absorbing an alkaline odor by making gas-liquid contact with a 5% aqueous sulfuric acid shower.

  Synthetic sulfuric acid is widely used as an acidic agent because it is an inexpensive substance, but there are concerns about burns due to its strong dehydrating action, and it is not so popular as a deodorant from the viewpoint of safety. Currently. Moreover, although synthetic sulfuric acid can be diluted and pH can be made 1-2, and also less than 1, simultaneously, oxidation-reduction potential (ORP) will be 750 mV or more, and there exists a concern about the influence with respect to a biological body. Generally, the ORP tends to increase as the pH decreases.

  Recently, acidic electrolyzed water obtained by electrolyzing saline has been widely used. The pH of acidic electrolyzed water is about 2 to 3.5, and hypochlorous acid derived from chloride ions is generated during electrolysis, and the antibacterial action due to this is utilized. However, it is difficult to maintain the pH for a long period of time, and the pH rapidly rises upon contact with organic matter, etc., so that the adsorption ability of the alkaline odor substance by the acid / alkali neutralization reaction is low. In addition, OPR has a pH of 2 to 3.5 and a high value of 1000 to 1150 mV, and there is a concern that the degree of influence on the living body is even greater.

JP 2003-105385 A Japanese Patent Laid-Open No. 7-213850

As described above, conventionally used acidic water has a low OPR if it has a low pH, and is harmful to the human body, or acidic water that does not harm the human body has a low adsorption capacity. There was a trend.
An object of the present invention is to provide a compact and simple deodorizing product that exhibits a safe and powerful environmental deodorizing function against an alkaline odor. Furthermore, this invention exists in utilizing effectively the strong acid water which was conventionally neutralized waste liquid process as a thing without utility value as a deodorizing product.

The present invention solves the above-mentioned problems. Specifically, the present invention is a strong acid water produced when a odor containing a sulfur compound is deodorized in a biological deodorization apparatus using microorganisms, and a molar amount of sulfate ions. number, accounting for over 80% of the total number of moles of anion containing, pH is 1.4 or less, and strong water redox potential is below 650 mV (hereinafter, referred to as "bio-strong acid water".) the a deodorant product water-retentive material consisting of a strong acid water-impregnated bodies impregnated into (microorganisms except when carried), deodorant products of the present invention, be used as a deodorizing material for the odor of alkaline Can do.

  The strong acid water used in the present invention is discharged when an odor containing a sulfur compound is treated in a biological deodorization apparatus using microorganisms. The strong acid water obtained by such a method is characterized in that the contained anion is mainly composed of sulfate ions, of which 80% or more of sulfate ions out of the total number of ion moles, preferably 90%. % Or more. Other anionic components that contribute to strong acidity include chloride ions, fluoride ions, phosphate ions, nitrate ions, etc. In particular, chloride ions and fluoride ions have volatility and are consumed. When used as an odorant, there is a concern that the surrounding metals and the like may be corroded by volatilization, and therefore, the number of moles is preferably less than 10%, and more preferably less than 5%. In order to make sulfate ion 80% or more and make chloride ion or fluoride ion less than 10%, the strong acid water obtained by using microorganisms is physically or chemically treated to produce chloride ion or fluoride. A method of removing ions is common, and a method of removing chloride ions and fluoride ions from odors containing sulfur compounds can also be used.

For example, Japanese Patent Application No. 2005-241193 describes a more detailed production method of strong acid water obtained by a method of discharging a odor containing a sulfur compound in a biological deodorization apparatus using microorganisms. .
That is, the fill layer microbial support material is filled, it and a watering means for sprinkling pH1.4 following water into the packed bed, and the odor gas including watering and sulfur-based odor components in the packed bed Are circulated in a counter-current direction to deodorize odor gas and recover acidic water.

  In addition, it is necessary to design a compact and simple deodorant product, which is one of the objects of the present invention, to have a pH of 1.4 or less in the biostrong acid water used in the present invention. According to the invention of No. 241193, the pH of water spraying in the former stage deodorizing apparatus in the biological deodorization treatment is 1.4 or less, preferably 0.6 to 1.4, and the pH of watering in the latter stage deodorizing apparatus is 0. A strong acid water having a pH of 3 to 0.8 and a pH of 1.4 or less coming out of each corresponds to the biostrong acid water of the present invention.

In addition, in the case of bioacidic water, the ORP is less than 650 mV, which is a significant feature compared to a conventional synthetic sulfuric acid aqueous solution. When the ORP exceeds 650 mV, the influence on a living body such as a human body becomes strong and cannot be used in the present invention.
Usually, when strong acid water is prepared by diluting synthetic sulfuric acid, the ORP increases in inverse proportion to the pH, and when the pH is around 1, the ORP is 750 mV or more. On the other hand, in the hot spring water known as an acidic spring that people use for bathing, although the pH is 1-2, the ORP is as low as about 100 to 600 mV, and the strong acid water used in the present invention is the hot spring water. Therefore, it can be said that there is almost no adverse effect on the human body.

  The reason for the low ORP of bioacidic water is unknown, but natural acidic hot spring water is mainly composed of sulfuric acid produced by sulfur oxidation by the same thiobacillus genus as bioacidic water, and is presumed to be due to this common factor. Yes. The lower the ORP is, the higher the safety for a living body such as a human body, and it can be said that the safety of the present invention using bioacidic water is higher than that of synthetic sulfuric acid, although it is the same sulfuric acid.

In this invention, it uses as a deodorizing material in the state of the strong acid water impregnation body which made the above-mentioned bio strong acid water penetrate | infiltrated the water retention substance.
As the water-retaining substance used in the present invention, a water-permeable and liquid-retaining substance can be used. Specifically, a fiber structure, a foamed structure, a gel-like substance, or the like can be used. Among these, examples of the fiber structure include knitted fabrics, woven fabrics, non-woven fabrics, and sponge-like three-dimensional molded products. Examples of the foam structure include a foam molded product obtained by foaming an acid-resistant resin and an inorganic porous material represented by a lump of diatomaceous earth. The gel-like material can be used if it is water-permeable, and its material is hydrophilic resin such as polyvinyl alcohol resin and acrylic acid resin, and recently used in disposable diapers and the like. Examples include highly water-absorbing resins. However, since it is impregnated with strong acid water, when used as a deodorant product for a certain period or longer, a polyester-based or polyolefin-based resin or fiber having high acid resistance is preferable as a raw material.

In the present invention, the water-retaining substance may be granular or a larger block.
The strong acid water impregnated body of the present invention removes bad odors by placing them on a desk or shelf, or by placing them in a breathable bag and placing them in a place where alkaline odors must be trapped and deodorized. I can do it. As the amount of impregnation, an amount of 0.05 to 0.999 cc is optimal for 1 cubic centimeter of the impregnated body after impregnation.

And in order to raise deodorizing efficiency, it can also be set as the deodorizing apparatus which combines the strong acid water impregnation body of this invention and an airflow introduction fan, and makes a gas contact an impregnated body positively. Of course, the strong acid water impregnated body of the present invention can be sealed and opened only when necessary to maintain the deodorizing effect. Of course, when strong acid water is removed by evaporation or malodorous component removal ability is reduced by adsorption of malodorous components, it is naturally possible to replenish new biostrong acid water.
The deodorizing substance of the present invention can be installed in rooms and places where it is required to remove malodors caused by alkaline malodorous substances (that is, ammonia odor and amine odor). For example, toilets, nursing facilities, seafood, meat, etc. It can be installed in the workplace where it is handled, and it will not cause harm if it is accidentally touched by people or animals.

  EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

In addition, the number of moles of sulfate ions, the pH value, and the oxidation-reduction potential in the total number of moles of contained anions defined in the present invention are measured by the following methods.
[The number of moles of sulfate ions in the total number of moles of contained anions]
Measurement was performed under the following conditions using a Dionex ion chromatograph DX-120.
Separation column: IonPac AS12A,
Guard column: Ion Pac AG12A,
Eluent: 2.7 mmol / L Na ₂ CO ₃ /0.3 mmol / L NaHCO ₃ ,
Detector: Electrical conductivity detector, Flow rate: 1.5 mL / min,
Suppressor: ASRS (external mode / current value 50mA)
[PH value]
It was measured based on the JIS K0102 12.1 (1998) glass electrode method.
[Redox potential]
River water quality test method (draft) Based on Ministry of Construction (1997), measurement was performed using 3.33 MKCl-Ag / AgCl as a reference electrode.

Example 1
Strong acid water was obtained from the second deodorization device of the biological deodorization device of the Okayama City 3 town hygiene facility association.
This strong acid water is obtained by the method described in Japanese Patent Application No. 2005-241193. This strong acid water has a pH of 0.6, an oxidation-reduction potential (ORP) of 620 mV, and the number of moles of sulfate ions occupies 93% of the total number of moles of anions contained.
1 mL of this bio-strong acid water was impregnated into a 1.5 cm cube of a nonwoven fabric molded body made with Kuraray Co., Ltd. Sophista (core-sheath composite fiber of polyester and ethylene vinyl alcohol copolymer). .

When this strong acid water impregnated body was put into a Tedlar bag, 3 L of 500 ppm of ammonia was injected, and the internal ammonia concentration was measured after 24 hours. The internal gas was discharged from the Tedlar bag, and 3 L of 500 ppm of ammonia was injected while the impregnated body was built in. After 24 hours, the internal ammonia concentration was measured again. The same operation was repeated 13 times. At the 13th time, 13 ppm of residual ammonia was detected, indicating that the state was close to saturation.
Thereby, since this impregnated body adsorbed 500 ppm of ammonia 3 L × 13 = 39 L, the ability to adsorb 19.5 m ^{3 of} ammonia 1 ppm (the regulated concentration of ammonia in the residential area regulated by the Odor Control Law) Turned out to be.

Comparative Example 1
Commercially available synthetic sulfuric acid was diluted to obtain diluted sulfuric acid having pH = 0.6. This strong acid water had an ORP of 780 mV, and the sulfate ion content was 99% in the total number of moles of all anions contained. Although this strong acid water shows the same ammonia adsorption performance as in Example 1, the ORP value is high, and there is concern about the effects of touching a living body such as a human body, so it was determined that it cannot be used as a deodorant product.

Claims (4)

Sulfate ions account for 80% or more of the total number of contained anions, pH is 1.4 or less, and redox potential is 650 mV or less. Deodorized product consisting of a strong acid water impregnated body. The deodorized product according to claim 1, wherein the strong acid water is a strong acid water produced when a odor containing a sulfur compound is deodorized in a biological deodorization apparatus using microorganisms. The deodorant product according to claim 1 or 2, wherein the water-retaining substance is any one of a fiber structure, a foam structure, and a gel. The deodorant product according to any one of claims 1 to 3, which is used in a place where an alkaline odor gas composed of an amine compound is generated.