JPH0866464A - Deodorant - Google Patents

Abstract

PURPOSE: To provide a deodorant which can effectively deodorize various malodor ranging from kitchen garbage, refrigerator, toilet, and the like in daily life to a general manufacturing plant, a breeding ground, a sewage treatment plant, and the like. CONSTITUTION: A deodorant includes manganese, zirconium, a copper metal or the compound. When the deodorant is used, gas including components causing a malodor such as hydrogen sulfide, methyl mercaptan, trimethylamine, and the like can be effectively deodorizing processed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorizing agent which treats a gas containing a malodorous component to deodorize or reduce the odor, and can meet a wide range of deodorizing needs from household use to industrial use.

[0002]

BACKGROUND OF THE INVENTION There are various sources of offensive odors, from food waste in daily life, refrigerators, toilets, etc. to general production plants, livestock farms, sewage treatment, etc. Also, there are many places in hospitals, hotels, restaurants, etc. that have a unique, if not stinking, odor. Ammonia, mercaptans, sulfides, amines, aldehydes, etc. are attracting attention as causative agents of these malodors or peculiar odors (hereinafter collectively referred to as "malodors"), but they are actually more complicated. , But not limited to these substances. In recent years, as the demand for a technique for removing these malodors has increased, research on the malodor removing technique has become popular, and for example, the following various methods have been proposed.

[0003] A masking method for eliminating an offensive odor by releasing an aromatic substance which is stronger than an offensive odor, an adsorption method for adsorbing an offensive odor causing substance by using an activated carbon or other adsorbent, and an acid or alkali neutralizing the offensive odor causing substance. And an acid neutralization method for removing the odor, an ozone deodorization method for oxidizing and decomposing ozone by adding ozone to the odor-causing substance, and a catalytic decomposition method using a platinum-based catalyst.

[0004]

However, each of the above-mentioned methods has serious drawbacks. For example, the masking method is not an essential method. The adsorption method is the most general-purpose method for household use that uses an adsorbent such as activated carbon or zeolite, but the adsorption amount is limited due to the saturated adsorption amount, and it is necessary to replace it when the adsorption reaches saturation. It cannot cope with strong odors. The acid / alkali neutralization method requires attention to the safety of chemicals and is limited to substances that can be neutralized.

Although the ozone deodorization method does not have the above-mentioned problems, unreacted ozone is not obtained because the odor-causing substance is not sufficiently removed by oxidative decomposition and ozone is extremely harmful even at a low concentration. There is a problem that it is necessary to remove the gas after the deodorization treatment and exhaust it. In addition, the oxidative decomposition method using a platinum-based catalyst requires a high temperature for burning and decomposing malodorous gas, which causes a problem in the cost of the catalyst.

The present invention has been made in view of the above circumstances, and proposes a deodorizing agent which exhibits a good deodorizing effect against various malodors at low temperature and has a long-lasting effect.

[0007]

The present inventors have completed the present invention as a result of extensive studies to solve the above problems. That is, the present invention relates to (1) a deodorant characterized by containing metallic manganese, zirconium, and copper or a compound thereof, (2) a usable temperature of 80 ° C. or lower, (1) described (3) A deodorizing method using the deodorizing agent according to (1) or (2) above.

The deodorant of the present invention has a high ability to adsorb and decompose various malodorous substances regardless of acidity, neutrality or basicity, and even if it is used or stored for a long period of time as never before. It has the characteristic that the effect does not change. The present invention will be described in detail below. The deodorant used in the present invention contains manganese, zirconium and copper metals or their compounds as essential components. The composition ratio of each component can be appropriately selected depending on the desired performance required, but the molar ratio of each component is converted to the ratio of each atom to be manganese: zirconium: copper = 1: 0.01 to 2.5: 0. 05-5, more preferably manganese: zirconium: copper = 1: 0.1
It is 1.5: 0.1-2.5. In addition, iron, cobalt,
Compounds such as nickel, silver, gold and palladium may be added, but when they are added, it is preferable to add them in the form of being mixed with or combined with manganese metal or a manganese compound.

Further, the deodorant of the present invention can be used by being supported or mixed on a commonly used porous carrier. Preferred carriers include silica, alumina, silica-alumina, natural zeolite, synthetic zeolite, diatomaceous earth, activated carbon, clay mineral and the like. The amount of the carrier used is arbitrary, but it is preferably 0 to 90% by weight in the mixture of the deodorant and the carrier.

When a compound of manganese, zirconium or copper is used as a raw material for the deodorant of the present invention, any compound can be used as long as it is a commonly available compound. Examples of these compounds include various inorganic salts, organic salts, and oxides. Specifically, in consideration of cost, availability, deodorizing performance, etc., the manganese compound is preferably an oxide such as manganese dioxide or manganese tetraoxide, a carbonate, a nitrate, a sulfate, an oxalate or a permanganate. Examples include manganate. Of these, potassium permanganate and manganese nitrate are particularly preferable. Preferred zirconium compounds include oxynitrates, nitrates, acetates, sulfates and oxides. Of these, particularly preferred is zirconium oxynitrate. Preferable examples of the copper compound include carbonate, nitrate, sulfate, acetate and oxide. Of these, particularly preferable is copper nitrate. These compounds may be used alone or in admixture of two or more.

The method for preparing the deodorant of the present invention is not particularly limited. For example, a mixed aqueous solution of each compound of manganese and zirconium is prepared and water is evaporated to obtain a solid. A solid product is obtained in the same manner as above from a separately prepared mixed aqueous solution of each compound of manganese and copper. Each of the obtained solids can be dried at a temperature of 200 ° C. or lower and mixed to form the deodorant of the present invention, but this mixture is preferably in air at a temperature of 200 to 500 ° C.
Bake for 5 to 24 hours. In the above, manganese,
Water can be evaporated from a mixture of aqueous solutions of zirconium and copper compounds, and the resulting solid matter can be dried and, if necessary, further baked to obtain the deodorant of the present invention. The temperature at the time of preparing each mixed solution is 15 to 85 ° C., and the pH is 1 to
10 is preferable. The amount of water used is not limited as long as it can completely dissolve each compound, but is usually 150 to 10000 parts by weight, preferably 300 to 5000 parts by weight, based on 100 parts by weight of each compound. Further, in the above-mentioned preparation method, when one or more of each compound is insoluble or hardly soluble in water, it may be mixed as an aqueous dispersion instead of an aqueous solution. In this case, one or two of each compound
When the manganese, zirconium, or copper metal is one or more of the seeds, the above-mentioned preparation method can be applied by using a powdery material. If necessary, the above-mentioned carrier may be dispersed in water and mixed with a mixed solution of each compound.

The deodorant of the present invention obtained as described above may be pulverized into a powder by a known method and used, but if there are restrictions in use, it may be formed into various shapes by a known method. It can be molded and used, and its shape is not particularly limited. For example, granules, pellets, honeycombs, plates,
It is also possible to use it by forming it into a cylindrical shape. Also,
It is also possible to add the above powder to paper, fiber, resin, etc., and form it into a sheet shape for use. Generally, when a powder is molded into pellets or the like, a binder (binder) is often used for facilitating the molding, but the deodorant of the present invention is not an exception, and is molded using a commonly used binder. It is possible to do so.

Preferred binders include bentonite, colloidal silica, minerals such as white clay, kaolin and water glass, or sodium alginate, glucose, dextrin, hydroxypropyl cellulose, carboxymethyl cellulose sodium salt, and glue, polyvinyl alcohol, polyvinylpyrrolidinone, etc. Examples of the binder include organic polymer-based binders and the like, but are not limited thereto, and any commonly used binder can be used. The amount of the binder used is usually 0 to 30 parts by weight with respect to 100 parts by weight of the powder.

Examples of the malodor causing substance to be deodorized in the present invention include hydrogen sulfide, methyl mercaptan, ammonia, trimethylamine, methyl sulfide, methyl disulfide, acetaldehyde, styrene, propionic acid, normal valeric acid, isovaleric acid, Normal butyric acid, formalin,
Acrolein, acetic acid, methylamine, dimethylamine,
Etc.

Although the deodorizing mechanism by the deodorizing agent of the present invention is not clear, when the malodorous gas is hydrogen sulfide in the reaction in a closed system, the oxygen in the reaction system decreases and sulfur is deposited as a product, or In the case of carbon-containing organic compounds such as trimethylamine and acetaldehyde, carbon dioxide is detected in the product, and it is considered that the main cause is oxidative decomposition of the malodorous component due to the catalytic action of the deodorant. Therefore, unlike the conventional adsorbents, it has a feature that it can be used for a long period of time and that it has a high decomposition activity and is effective for a strong malodor in a short time.

The deodorant of the present invention has a high deodorizing performance at low temperature and is therefore usually used at room temperature. However, depending on the malodorous gas, it may be used at a higher working temperature in order to exhibit its performance sufficiently. The use temperature of the deodorant of the present invention is preferably 80 ° C or lower. If the operating temperature exceeds 80 ° C., the heat energy cost for maintaining the temperature is required. With the deodorant of the present invention, deodorization proceeds with an appropriate balance of adsorption of malodorous gas and oxidative decomposition. The balance may be deteriorated and the deodorizing performance may be deteriorated.

[0017]

EXAMPLES The present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The removal rate in the examples refers to the ratio of the malodorous gas remaining after a certain period of time to the malodorous gas initially injected into the container.

Example 1 (A) Preparation of deodorant 13.5 g of manganese nitrate, zirconium oxynitrate 1
Dissolve 3.4 g in 400 ml of water at 50 ° C. with stirring.
The pH is adjusted to 7 with aqueous ammonia, the mixture is stirred at 80 ° C. for 1 hour, then transferred to an evaporation dish and evaporated to dryness on a water bath. On the other hand, 15.8 g of potassium permanganate and 12.1 g of copper nitrate were dissolved in 400 ml of water with stirring at 50 ° C., and then 5.2 g of finely powdered silica (silica aerosil) was added as a carrier, and the pH was adjusted to 7 with ammonia water. It is adjusted to 0.2 and the formed precipitate is filtered and washed with water. The precipitate is dried in a dryer at 110 ° C for 8 hours. The two solid products were mixed and crushed in a mortar,
It was fired for a time to obtain the deodorant of the present invention.

(B) Deodorant Evaluation Test (B-1) 0.2 g of the deodorant powder prepared above was placed in a glass container having a volume of 2 liters, and air having a humidity adjusted to 80% at 30 ° C. was flowed for 30 minutes. Then seal. While stirring the inside of the container kept at a constant temperature of 30 ° C with a magnetic stirrer, hydrogen sulfide so that the initial concentration becomes 2500 ppm,
Inject methyl mercaptan gas. After 15 minutes, the gas in the container was sampled and the concentration of each gas was measured by a gas chromatograph. As a result, both the hydrogen sulfide removal rate and the methyl mercaptan removal rate were 100%.

(B-2) 0.4 g of the deodorant powder prepared above was placed in a glass container having a volume of 2 liters, air having a humidity adjusted to 80% at 30 ° C. was allowed to flow for 30 minutes, and then the container was closed. While stirring the inside of the container kept at a constant temperature of 70 ° C. with a magnetic stirrer, trimethylamine and acetaldehyde gas are injected so that the initial concentration becomes 1000 ppm. After 120 minutes, the gas in the container was sampled and the concentration of each gas was measured by a gas chromatograph. As a result, the trimethylamine removal rate was 78% and the acetaldehyde removal rate was 97%. However, the removal rate after 24 hours was almost 100%.

Example 2 (A) Preparation of deodorant Manganese nitrate 417 g, zirconium oxynitrate 134
g, 121 g of copper nitrate are dissolved in 20 l of water at 50 ° C. with stirring, and 77 g of finely powdered alumina (alumina aerosil) is added as a carrier. Synthetic zeolite 3 in the aqueous solution
After adding 7 g and stirring for 30 minutes, a dry powder is obtained using a spray dryer. The powder was calcined at 260 ° C. for 16 hours. 300 g of the powder thus prepared and 100 g of activated carbon powder were sufficiently kneaded with 30 g of sodium carboxymethyl cellulose sodium salt in a small amount of pure water, and extruded from a die having a hole diameter of 4 mm by an extrusion molding machine. Immediately press the udon-shaped extruded product with a cutter for 3-10
It was cut into a length of mm and dried at 110 ° C. to obtain the deodorant of the present invention.

(B) Deodorant Evaluation Test The above deodorants were crushed in a mortar, and the removal rate of each malodorous gas was determined in the same manner as in Example 1. As a result, the hydrogen sulfide removal rate and the methyl mercaptan removal rate were each 10
The removal rate was 0%, the trimethylamine removal rate was 86%, and the acetaldehyde removal rate was 90%.

Example 3 (A) Preparation of deodorant 20.3 g of manganese nitrate, zirconium oxynitrate 1
Dissolve 3.4 g in 400 ml of water at 50 ° C. with stirring.
The pH is adjusted to 7 with aqueous ammonia, the mixture is stirred at 80 ° C. for 1 hour, then transferred to an evaporation dish and evaporated to dryness on a water bath. Further, 2.4 g of manganese nitrate and 12.7 g of ferric nitrate are dissolved in 300 ml of water at 50 ° C. with stirring. Adjust the pH to 7.5 with aqueous ammonia.
The mixture is stirred at 80 ° C for 1 hour, transferred to an evaporation dish, and evaporated to dryness on a hot water bath. Potassium permanganate (15.8 g), manganese nitrate (6.7 g) and copper nitrate (15.1 g) were added to 600 ml of water.
It is dissolved under stirring at 0 ° C., and 6.6 g of finely powdered silica (silica aerosil) is added. Adjust the pH to 7 with aqueous ammonia.
It is adjusted to 0 and the formed precipitate is filtered and washed with water. 1 deposit
Dry in a dryer at 10 ° C. for 8 hours. The three solids were mixed and pulverized in a mortar and baked at 300 ° C. for 8 hours to obtain the deodorant of the present invention.

(B) Deodorant Evaluation Test For each of the above deodorants, the removal rate for each malodorous gas was determined in the same manner as in Example 1. As a result, the hydrogen sulfide removal rate and the methyl mercaptan removal rate were 100%, the trimethylamine removal rate was 90%, and the acetaldehyde removal rate was 99%.

Example 4 0.2 g of the deodorant powder prepared in Example 1 was placed in a glass container having a volume of 2 liters, and air humidified at 30 ° C. and a humidity of 80% was allowed to flow for 30 minutes and then sealed. While stirring the inside of the container kept at a constant temperature of 30 ° C. with a magnetic stirrer, 60 ml of hydrogen sulfide is injected so that the initial concentration becomes 3%. After 60 minutes, the gas in the container was sampled and the gas concentration was measured by a gas chromatograph. as a result,
The hydrogen sulfide removal rate was 100%.

Comparative Example 1 Similar to Example 1, commercially available activated carbon was used to determine the removal rate for each malodorous gas. As a result, the hydrogen sulfide removal rate was 37%, the methyl mercaptan removal rate was 41%, the trimethylamine removal rate was 68%, and the acetaldehyde removal rate was 4%.
It was 5%.

Comparative Example 2 0.2 g of the deodorant powder prepared in Example 1 was placed in a glass container having a volume of 2 liters, and air which had been humidified to have a humidity of 80% at 30 ° C. was flowed for 30 minutes and then sealed. Hydrogen sulfide is injected so that the initial concentration becomes 3% while stirring the inside of the container kept at a constant temperature of 85 ° C. with a magnetic stirrer. After 60 minutes, the gas in the container was sampled and the gas concentration was measured by a gas chromatograph. As a result, the hydrogen sulfide removal rate was 95%. It is recognized that the deodorizing effect of hydrogen sulfide decreases with increasing temperature.

[0028]

EFFECTS OF THE INVENTION By using the deodorant of the present invention, a gas containing a wide variety of malodorous components such as hydrogen sulfide, methyl mercaptan, and trimethylamine can be efficiently deodorized for a long period of time, and used in a wide range of applications. it can. Further, the deodorant of the present invention has sufficiently high activity even at room temperature and can be widely used as a deodorant in general living environment.

Claims (3)

[Claims] 1. A deodorant containing metallic manganese, zirconium, and copper or a compound thereof. 2. The deodorant according to claim 1, which has a usable temperature of 80 ° C. or lower. 3. A deodorizing method using the deodorizing agent according to claim 1.