JP2551702B2 - Method for producing deodorant - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION This invention relates to a process for the preparation of deodorant.

[0002]

2. Description of the Related Art Generally, smoke and waste liquid from factories, cigarettes and raw sewage, kitchen garbage, and the like are sources of offensive odors and offensive odors, and there are various types thereof. At home, odors from toilets, kitchens, pets, cigarettes, etc. cause discomfort, frustration, headaches, and the like. In particular, when the air conditioner is operated, it is often kept in a closed room, so countermeasures against these malodors and offensive odors are a big problem.

Examples of such substances that cause offensive odors and unpleasant odors in daily life include amines such as trimethylamine, which is a perishable odor of fish and meat, ammonia of toilet odor,
Examples thereof include hydrogen sulfide which is a rotten odor of eggs and milk, rotten odor of vegetables and garbage, manure odor, mercaptans such as methyl mercaptan which is a pickled odor, and disulfides. Conventionally,
As the deodorant, for example, there is a deodorant solid composed of a gas adsorbing substance capable of deodorizing by physically adsorbing an odor substance such as a porous body of activated carbon or ceramics.

In addition, the inventors have recently been using Fe,
It has a skeleton made of a three-dimensional mesh-like sintered body of one or more metals selected from the group consisting of Mn, Cr, Ni, Zn, Al, and Cu, and the surface of the skeleton is Deodorant solid comprising a porous body covered with a reaction product (complex) of the metal and oxypolybasic acid (hereinafter, this may be referred to as "metal-oxypolybasic acid-based porous body"). Was developed. This deodorant solid can be deodorized and removed by subjecting odorous substances to chemical reactions such as oxidation, reduction and neutralization.

[0005]

However, the above-mentioned metal-
Deodorant solids consisting of oxypolybasic acid type porous materials show excellent deodorizing effect on odor substances with high chemical reactivity such as amines, ammonia and hydrogen sulfide, but mercaptans and disulfides However, there is a problem that the deodorizing effect is not sufficient for a sulfur-based odor substance having poor chemical reactivity such as.

Also, there is a problem in that it is often difficult to deodorize sulfur odors such as mercaptans and disulfides with respect to the deodorant solids composed of the above-mentioned gas adsorbing substances. In view of such circumstances, this invention provides a method capable of producing easily and efficiently odors in general, in particular sulfur-lifting one deodorant excellent deodorizing effect on odor around the living This is an issue.

[0007]

In order to solve the above problems, the inventors have made various studies. As a result, the present invention was completed by confirming the following by experiments. That is, it is generally known that sulfur molecules are easily bonded to each other. Therefore, if a metal sulfide containing a sulfur component having an active S ₈ structure is carried on a deodorant solid such as the above-described gas adsorbent or metal-oxy polybasic acid type porous body, That is, the active sulfur component in the metal sulfide reacts with and binds to the sulfur-based odorous substance, whereby the sulfur-based odorous substance can be absorbed and removed to deodorize.

Therefore, the deodorant obtained by the present invention contains a sulfur component having an active structure of S ₈ and has a mass number m / e = 256 by mass spectrometry.
The deodorant solid is made to carry a metal sulfide whose peak (m: mass number of ions, e: charge number of ions) of which can be confirmed. The method for producing a deodorant according to the present invention contains a sulfur component having an active S ₈ structure,
Mass number m / e = 256 by mass spectrometry
(M: mass number of ions, e: charge number of ions) A metal sulfide whose peak can be confirmed, an organic substance having a plurality of alcoholic hydroxyl groups in one molecule, and water, and the metal sulfide. And the proportion of organic substances are 0.5 to 10% by weight and 1 to 20% by weight, respectively, with respect to the entire processing liquid.
The deodorant is obtained by treating the deodorant solid with the treatment liquid of

The method for producing a deodorant according to the present invention also contains a sulfur component having an active S ₈ structure, and a mass number m / e = 256 by mass spectrometry.
(M: mass number of ions, e: charge number of ions) A metal sulfide whose peak can be confirmed, a dispersant, a thickener and a binder, and water, and the metal sulfide and the dispersion. The compounding ratio of the agent, the thickener and the binder is 0.5 to 10% by weight, and 0.1 to 2% by weight, respectively, with respect to the entire treatment liquid.
The deodorant may be obtained by treating the deodorant solid with treatment liquids of 0.5 to 10% by weight and 1 to 30% by weight.

The metal sulfide used in the present invention contains a sulfur component having an active S ₈ structure, and has a mass number m / e = 256 (m: mass number of ion, e: ion mass) determined by mass spectrometry. It is limited to those where the peak of the number of charges can be confirmed. As a generally commercially available metal sulfide, a mixture obtained by heating a mixture of a metal sulfate and carbon without heating the air, or melting a metal powder and sulfur in a crucible. However, these metal sulfides are not suitable for the present invention because they do not contain an active sulfur component having an S ₈ structure and have a low effect of absorbing and removing a sulfur-based odor substance.

The method for obtaining a metal sulfide containing an active sulfur component having a S ₈ structure is not particularly limited, but for example, hydrogen sulfide (H ₂ S) gas may be added to an aqueous solution of a metal salt such as a metal sulfate. (Bubbling) to generate a precipitate of a metal sulfide (hereinafter, referred to as "hydrogen sulfide gas bubbling method") and the like. Active S
Specific examples of the metal sulfide containing a sulfur component having _eight structures (hereinafter, simply referred to as “metal sulfide” unless otherwise specified) are not particularly limited, but include, for example, C
uS, PbS, ZnS, FeS, NiS, CoS, etc. are mentioned, and these 1 type (s) or 2 or more types can be used.

FIG. 1 shows one chart showing the results of mass spectrum analysis of copper sulfide CuS obtained by the hydrogen sulfide gas bubbling method, which is an example of the metal sulfide used in the present invention. 11 ≦ m / e ≦ 2 in the first half
It is a figure which shows the range part of 60, and FIG. 2 is a figure which shows the range part of 261 <= m / e <510 of the latter half following this. As shown in FIG. 1, a peak at m / e = 256 indicating the presence of a sulfur component having an active S ₈ structure was detected. As shown in FIG. 2, no peaks above m / e = 261 were detected.

The deodorant solid used in the present invention is not particularly limited, but examples thereof include the above-mentioned gas adsorbing material made of porous material such as activated carbon and ceramics, and metal-oxy polybasic acid type porous material. Examples include porous substances. These may be used alone or in combination of two or more. The metal-oxy polybasic acid-based porous material is not particularly limited, but can be produced, for example, by the method described below.

First, Fe, Mn, Cr, Ni, Zn, A
One or two or more metals selected from the group consisting of 1 and Cu are wet pulverized into powder having an average particle diameter of 10 μm or less. This metal powder is kneaded with a binder such as carboxymethyl cellulose, and this kneaded product is applied to the skeleton surface of urethane foam. The urethane foam coated with the kneaded material is heated to about 1200 ° C. to eliminate and remove the urethane foam, and the coated metal powder is sintered to form a three-dimensional mesh-shaped sintered metal sintered body. Get the body. Next, the obtained sintered metal porous body is dipped in an aqueous solution of oxypolybasic acids for about 15 to 30 minutes and then dried to have a skeleton made of a sintered body of a three-dimensional mesh-like metal. A porous body is obtained in which the surface of the skeleton is covered with the reaction product of the metal and the oxypolybasic acid.

The amount of the metal sulfide supported on the deodorant solid is not particularly limited, but in order to obtain sufficient deodorant performance for the sulfur-based odorous substance, the metal sulfide is added to the deodorant solid. It is preferably 0.01% by weight or more and 10% by weight or less. When the supported amount of the metal sulfide is less than 0.01% by weight, the deodorizing performance against sulfur-based odor is lowered, and when it exceeds 10% by weight, the deodorizing performance of the deodorant solid itself is impaired. Because there is a fear.

The form of the deodorant obtained by the present invention includes, for example, tablets, granules, powders, blocks, plates and the like, and is not particularly limited. Moreover, the size and particle size of the deodorant are not particularly limited. The metal sulfide is preferably supported locally and unevenly distributed, rather than being supported on the entire surface of the deodorant solid.

The method for obtaining the deodorant of the present invention includes, for example, a method of treating a deodorant solid with a treatment liquid containing a metal sulfide, which will be described in detail later. It is not limited and other methods may be used. As another method, for example, a method of applying an adhesive or the like to a part of the surface of the deodorant solid and then directly adding a metal sulfide as a fine powder and adhering the metal sulfide, etc.

The method for producing a deodorant by treating a deodorant solid with a treatment liquid containing a metal sulfide will be described in detail below. The treatment liquid containing the metal sulfide is not particularly limited, but the dispersion liquid that disperses the metal sulfide in water using water as a dispersion medium and the deodorization of the treatment liquid by increasing the viscosity of the treatment liquid It is preferable to have both a thickening function for facilitating adhesion to the volatile solid and a binding function for increasing the adhesive force between the metal sulfide and the deodorant solid during drying.

The treatment liquid is not particularly limited, but examples thereof include two types A and B having the compositions described below. —Treatment Liquid A— This treatment liquid contains a metal sulfide, an organic substance having a plurality of alcoholic hydroxyl groups in one molecule, and water.

The organic substance having a plurality of alcoholic hydroxyl groups in one molecule can simultaneously impart the functions of dispersing, thickening and binding with one substance. Specific examples of such organic substances are not particularly limited, and examples thereof include one or more of polyethylene glycol (PEG), carboxymethyl cellulose (CMC), polyvinyl alcohol, glycerin and the like. Among these,
Particularly, PEG and CMC are preferable.

The mixing ratio of the metal sulfide and the organic compound in the treatment liquid A is 0.5 to 10% by weight of the metal sulfide and 1 to 20% by weight of the organic substance with respect to the entire treatment liquid. It is preferable. When the amount of the metal sulfide compounded is less than 0.5% by weight, the deodorizing performance against sulfur odor is low, and when it exceeds 10% by weight, a treatment liquid in which the metal sulfide is dispersed cannot be prepared or treated. Since the viscosity of the liquid becomes too high, it becomes difficult to treat the deodorant solid with the treatment liquid, and the amount of metal sulfide carried becomes too large, which may impair the deodorant performance of the deodorant solid itself. Is. If the amount of the organic compound is less than 1% by weight, the above-mentioned dispersion,
Each function of thickening and binding cannot be sufficiently imparted, and it becomes difficult to support the metal sulfide on the deodorant solid. This is because when the amount of the organic substance blended exceeds 20% by weight, the organic substance may cover the surface of the deodorant solid and impair the deodorant performance of the deodorant solid itself.

-Treatment Liquid B-This treatment liquid contains a metal sulfide, a dispersant, a thickener and a binder, and water. The dispersant is not particularly limited, and examples thereof include commercially available surfactants, specifically, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyhydric alcohol fatty acid ester, and the like. The dispersant may be used alone or
Used in combination with multiple species.

The thickener is not particularly limited,
For example, the above-mentioned organic substances having a plurality of alcoholic hydroxyl groups in one molecule may be mentioned. The thickeners may be used alone or in combination of two or more. As a binder,
Although not particularly limited, examples thereof include commercially available emulsions and latexes, specifically vinyl acetate emulsions, acrylic emulsions, SBR latexes and the like. The binder may be used alone or in combination of two or more kinds.

The mixing ratio of the metal sulfide, the dispersant, the thickener and the binder in the treatment liquid B is based on the whole treatment liquid.
0.5 to 10% by weight of metal sulfide and 0.1 to 2 of dispersant
% By weight, 0.5 to 10% by weight thickener, 1 to 3 by binder
It is preferably 0% by weight. The reason why such a mixing ratio is preferable is the same as in the case of the treatment liquid A described above.

When an organic substance having a plurality of alcoholic hydroxyl groups in one molecule is used as a thickener, the organic substance has a function of dispersing and binding in addition to the thickening function by one substance as described above. Since it can also be added to the treatment liquid, if necessary, this organic substance can also serve as a thickener, a dispersant, and a binder, and a different type of dispersant and binder from the organic substance can be used. The use of a binder may be omitted. In this case, the composition of the processing liquid is the same as that of the processing liquid A described above.

The method for preparing the treatment liquid containing the metal sulfide is not particularly limited, but the metal sulfide is preferably finely ground (for example, a particle size of 1 μm or less). The crushing method is also not particularly limited. Using a treatment liquid containing a metal sulfide, the method for treating the deodorant solid is not particularly limited, for example, a dipping method,
Examples include a method in which a treatment liquid is attached to a deodorant solid by a spray method or the like and then dried. Conditions such as temperature and time of treatment are not particularly limited.

The immersion method will be described as an example. For example, the treatment is performed as follows. Immerse the deodorant solid in the treatment liquid whose temperature is adjusted to 25 ° C so that the whole is immersed,
After 5 to 30 minutes have passed, it is pulled up and lightly shaken to drain water. Then, using a dryer, it is dried at 70 ° C. for about 3 hours.

[0028]

When a metal sulfide containing a sulfur component having an active S ₈ structure is supported on a deodorant solid, the metal sulfide is defeated against a sulfur-based odor substance which the deodorant solid is not good at. The active sulfur components in the reaction react with each other to bond with each other, thereby making it possible to absorb and remove the sulfur-based odorous substance without deteriorating the deodorizing performance of the deodorant solid itself, thereby enabling deodorization. As a result, it becomes possible to efficiently deodorize all the odors in daily life.

Further, the metal sulfide is contained and dispersed,
By treating the deodorant solid with a treatment liquid of a specific composition that has both thickening and binding functions, an excellent deodorant in which metal sulfide is supported on the deodorant solid can be easily and efficiently prepared. It will be possible to obtain.

[0030]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples. -Examples 1 to 6-Copper sulfide CuS or lead sulfide PbS (both manufactured by Nakarai Chemical Co., Ltd.) obtained by a method of bubbling hydrogen sulfide gas into an aqueous solution of copper sulfate or lead sulfate is a fine powder having a particle size of 1 μm or less. Used as a metal sulfide, an aqueous treatment liquid having the composition shown in Table 1 below was prepared.

The temperature of this treatment liquid was adjusted to 25 ° C., and a deodorant solid consisting of activated carbon powder was soaked in the whole so as to be immersed in the whole. After 30 minutes, it was pulled up and lightly shaken to drain it. It was Then, using a dryer, at 70 ℃ 3
By drying for about an hour, a powdery deodorant was obtained. -Examples 7 to 8-First, a deodorant solid composed of an iron-ascorbic acid-based porous body was prepared as follows.

Iron powder having an average particle size of 10 μm is kneaded in an aqueous solution of carboxymethyl cellulose (CMC), and the kneaded product is 200 mm × 200 mm × 10 mm having a pore size of about 1 mmφ.
Was applied to the surface of the skeleton of the urethane foam. By heating this urethane foam coated with the kneaded material at 1200 ° C., the urethane foam disappears and the coated iron powder is sintered to obtain a sintered porous body having three-dimensional communicating holes. Obtained. The obtained three-dimensional reticulated iron sintered porous body was dipped in an aqueous solution of L-ascorbic acid having a concentration of 1 mol / water 1 liter for 30 minutes and then dried to obtain a three-dimensional reticulated iron. A deodorant solid having an iron-ascorbic acid-based porous body having a skeleton made of a sintered body and the surface of the skeleton covered with a reaction product of iron and L-ascorbic acid was obtained.

Separately, copper sulfide Cu obtained by bubbling hydrogen sulfide gas into an aqueous solution of copper sulfate
A fine powder of S (manufactured by Nakarai Chemical Industry Co., Ltd.) having a particle size of 1 μm or less was used as a metal sulfide to prepare an aqueous treatment liquid having the composition shown in Table 1 below. Using this treatment liquid, the deodorant solid consisting of the iron-ascorbic acid type porous body obtained above was used in Example 1 above.
The block-like deodorant was obtained by treating in the same manner as in the above.

Comparative Example 1 A deodorant solid consisting of activated carbon powder was used as a deodorant without being treated with a treatment liquid. -Comparative Example 2-The deodorant solid composed of the iron-ascorbic acid-based porous body obtained in Examples 7 to 8 was used as a deodorant as it was without being treated with a treatment liquid.

Comparative Example 3 Particle size 1 of copper sulfide CuS (manufactured by Wako Pure Chemical Industries) obtained by a method of melting copper powder and sulfur in a crucible (crucible method).
An aqueous treatment liquid having a composition shown in Table 2 below was prepared by using fine powder having a particle size of μm or less as a metal sulfide. Using this treatment liquid,
The deodorant solid composed of activated carbon powder was treated in the same manner as in Examples 1 to 6 to obtain a deodorant.

[0036]

[Table 1]

[0037]

[Table 2]

The deodorizing performance of each of the deodorants obtained in the above Examples 1 to 8 and Comparative Examples 1 to 3 was evaluated by the following method using the apparatus shown in FIG. As shown in the figure, first, the upper and lower two-stage mesh 2 containing the deodorant 1 in the upper stage was set in an acrylic chamber 3 having a volume of 40 liters, and methyl mercaptan was injected as a malodorous gas. In order to make the methyl mercaptan concentration in this chamber 3 uniform, after stirring for several minutes in the direction of arrow A by the circulation fan 4, the initial concentration (C ₀ ) of methyl mercaptan was measured by the gas detection tube 5 and found to be about 100 ppm. Met.

Next, the odor in the direction of arrow B with respect to the deodorant 1
Operate the blower fan 6 so as to accelerate it, and
It was left for 0 minutes. Then, the gas detector tube 5
Concentration of lucaptan (C₁) Is measured and methyl mercapta
Gas remaining rate [= C₁/ C ₀× 100 (%)]
Was. The results are shown in Table 3 below.

[0040]

[Table 3]

As shown in Table 3, the deodorants according to Examples 1 to 8 are remarkably superior in deodorizing power to methyl mercaptan as compared with the deodorants according to Comparative Examples 1 to 3. confirmed.

[0042]

According to the method for producing a deodorant according to the present invention,
Lever, odor General around life can be particularly obtained with high easily efficiently lifting one deodorant excellent deodorizing effect on sulfur-based odors.

[Brief description of drawings]

FIG. 1 is an example of a metal sulfide used in the present invention, copper sulfide CuS obtained by a hydrogen sulfide bubbling method.
2 sheets of one chart showing the results of mass spectrum analysis of
It is a figure which divides into two and shows the range part of 11 <m / e <260 of the first half.

FIG. 2 261 ≦ m / e ≦ 510 in the latter half of the above chart
It is a figure which shows the range part of.

FIG. 3 is a schematic diagram showing an apparatus used for evaluating deodorizing performance of a deodorant in Examples and Comparative Examples.

[Explanation of symbols]

 1 deodorant

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kozo Hayashi 1048 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works, Ltd. (72) Inventor Sato Okumoto 1048, Kadoma, Kadoma, Osaka Prefecture 56) References JP-A-5-96158 (JP, A)

Claims (3)

(57) [Claims] 1. A mass number m / e = containing a sulfur component having an active structure of S ₈ by mass spectrometry.
The metal sulfide includes a metal sulfide whose peak of 256 (m: mass number of ions, e: charge number of ions) can be confirmed, an organic substance having a plurality of alcoholic hydroxyl groups in one molecule, and water. The compounding ratio of the organic substance and the organic substance is 0.5 to 10% by weight and 1 to 20% of the total amount of the processing liquid, respectively.
A method for producing a deodorant, which comprises obtaining a deodorant by treating a deodorant solid with a treatment liquid in a weight percentage. Wherein organic matter, according to claim 1 is polyethylene glycol and / or carboxymethyl cellulose
A method for producing the deodorant described. 3. A mass number m / e = containing a sulfur component having an active structure of S ₈ by mass spectrometry.
A metal sulfide whose peak of 256 (m: mass number of ions, e: charge number of ions) can be confirmed, a dispersant, a thickener and a binder, and water, and the metal sulfide,
The dispersant, the thickener, and the binder are mixed in proportions of 0.5 to 10% by weight, 0.1 to 2% by weight, 0.5 to 10% by weight and 1 to 30% by weight, respectively, with respect to the entire treatment liquid. A method for producing a deodorant, which comprises obtaining a deodorant by treating a deodorant solid with the treatment liquid of