JPH06225927A - Removing agent for malodorous material - Google Patents

Abstract

PURPOSE:To provide an agent for removing malodorous material, especially aldehyde compounds efficiently without being affected by an atmosphere of moisture or the like. CONSTITUTION:This agent for removing malodorous material contains at least one selected from among an acid salt of halide of aniline, an acid salt of ester of aminobenzoic acid, an acid salt of sulfanylamide or a derivative thereof, an acid salt of aminoacetanilide and an acid salt of aminoacetophenone. The agent of the invention can be used in the form of supporting the above substance on a porous carrier and will not lower removing performing thereof with respect to changes in the atmosphere of moisture, temperature or the like, Especially, this can remove aldehyde compounds efficiently.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to exhaust gas from factories, cigarette odors, body odors, human odors, food odors from refrigerators, ammonia, hydrogen sulfide, acetaldehyde, etc. contained in automobile exhaust gas. The present invention relates to a deodorant effective for removing a malodorous substance, or an agent for removing a malodorous substance such as an adsorbent for treating these gases.

[0002]

2. Description of the Related Art A malodor produced in a living environment such as an automobile, a kitchen, a living room, an office is a complex odor in which various malodorous substances are mixed. For example, the odor in an automobile is a complex odor in which a cigarette odor, a sweat odor, an exhaust gas odor, a dust odor, and the like are mixed, and the components thereof are said to be in the thousands. Under the Odor Control Law,
Twelve kinds of components in these odors, namely, ammonia, methyl mercaptan, hydrogen sulfide, methyl disulfide, trimethylamine, acetaldehyde, styrene, propionic acid, normal butyric acid, normal valeric acid and isovaleric acid are designated as particularly important malodorous components. Has been done.

Conventionally, as a method of removing such a malodorous substance, a method of masking using an aromatic agent, a method of adsorbing and removing it with activated carbon, silica gel or the like have been adopted.

However, each of these methods has drawbacks. In the method of masking with an fragrance, the malodorous component is not fundamentally removed, and the fragrance itself may be a source of odor.
Further, in the method using physical adsorption by an adsorbent such as activated carbon or silica gel, the type of the adsorbent limits the type of malodorous component that can be adsorbed. For example, activated carbon has no effect on basic odors such as ammonia and trimethylamine.

Therefore, a chemical method is considered as a method for solving these drawbacks. This is a method of chemically removing a malodorous substance by a neutralization reaction, and can simultaneously remove both acidic odors such as acetaldehyde and hydrogen sulfide and basic odors such as ammonia and trimethylamine.
That is, the acidic odor is neutralized and removed by the basic adsorbent and the basic odor by the acidic adsorbent.

[0006] However, the basic adsorbent and the acidic adsorbent, due to their properties, react with each other and deactivate when they are simultaneously supported on the same carrier or dispersed in the same liquid at the same time. This is a drawback of the adsorbent that utilizes a chemical reaction.

Therefore, the inventors of the present invention, as a composite adsorbent for adsorbing and removing acidic odor and basic odor at the same time, an acidic salt of an aromatic amino acid, an acid, a transition metal compound, iodine,
Alternatively, a coexistence of an iodine compound as an active ingredient was considered (Japanese Patent Application Laid-Open No. 3-296434, Japanese Patent Application Laid-Open No. 5-296434).
23,588).

[0008]

By the way, even among malodorous components, aldehydes such as acetaldehyde are most perceived as odors. In particular, it is becoming important to remove aldehydes in places with high humidity such as a living room or a vehicle compartment during rainy season or rainy weather.

The above-mentioned composite adsorbent developed by the present inventors can adsorb and remove both acidic odor and basic odor at the same time, but it is not suitable for adsorbing and removing aldehydes in a high humidity environment as described above. Turned out to be insufficient.

The present invention has been made in view of the above-mentioned problems of the prior art, and provides a malodorous substance removing agent capable of removing malodorous substances without being affected by the atmosphere such as humidity and particularly efficiently removing aldehydes. The purpose is to provide.

[0011]

The malodorous substance removing agent of the present invention is an acid salt of a halide of aniline, an acid salt of an ester of aminobenzoic acid, an acid salt of sulfanilamide or a derivative thereof, and an acid salt of aminoacetanilide. And at least one selected from the group consisting of acid salts of aminoacetophenone.

[0012]

The odor eliminating agent of the present invention is an acid salt of a halide of aniline, an acid salt of an ester of aminobenzoic acid, an acid salt of sulfanilamide or a derivative thereof, an acid salt of aminoacetanilide, and an acid salt of aminoacetophenone. Since it contains at least one selected from the salt, it is possible to remove the malodorous substances contained in the gas such as exhaust gas even if the atmosphere such as humidity and temperature changes. Particularly, removal of aldehydes is efficient. The reason for this is not clear, but it is estimated as follows.

One of the reactions between the scavenger of the present invention and an aldehyde is presumed to be a nucleophilic addition reaction of a carbonyl group (C = O) to a partially positively charged carbon by a lone pair of electrons on a nitrogen atom. . That is, the scavenger according to the present invention releases H ⁺ (proton) from an acid forming its acid salt or a partially free acid, which is added to the carbonyl group (C═O) in the aldehyde structure to form a carbonyl group. The action of increasing the positive charge of carbon and promoting the nucleophilic addition reaction occurs.

Also, the ionization of the amino group in the scavenger (N
H ₃ ⁺ ) causes the localization of electrons, which also activates the ring and accelerates the ring substitution reaction. It is considered that these actions have a synergistic effect. In this way, it is considered that the malodorous substances such as aldehydes are chemically decomposed and removed.

The excellent performance of the scavenger of the present invention is due to the use of an acidic salt of a substance having an appropriate basicity necessary for promoting the above reaction. That is,
Electron withdrawal of halogen (in the case of halides of aniline), amide of sulfonic acid (in the case of sulfanilamide or its derivatives), acetamide group (in the case of aminoacetanilide), carbonyl group (in the case of ester of aminobenzoic acid and aminoacetophenone). The sexual substituent reduces the basicity of the amine and weakens its bond with the acid. Therefore,
The reactivity with the malodorous substance is increased and the ability to remove the malodorous substance is improved.

[0016]

The malodorous substance removing agent of the present invention can remove malodorous substances contained in gases such as exhaust gas even when the atmosphere such as humidity and temperature changes. Particularly, removal of aldehydes is efficient.

[0017]

Embodiments of the present invention will be described below.

The malodor removing agent of the present invention is an acid salt of a halide of aniline, an acid salt of an ester of aminobenzoic acid, an acid salt of sulfanilamide or a derivative thereof,
It contains at least one selected from aminoacetanilide acid salts and aminoacetophenone acid salts.

As the aniline halide,
(X is halogen such as fluorine, iodine, chlorine and bromine. Further, the positions of the functional groups attached to the benzene ring are o, m,
Any of p may be used. ) Is a substance as shown in.

[0020]

[Chemical 1]

As the ester of aminobenzoic acid,
(R is an alkyl group, and the position of the functional group attached to the benzene ring may be o, m, or p.).

[0022]

[Chemical 2]

The sulfanilamide or its derivative is a compound of formula 3 (R is hydrogen, a substituent having a homocyclic ring, a substituent having a heterocyclic ring, etc. Further, the position of the functional group attached to the benzene ring is Any of o, m and p may be used.)
It is a substance as shown in.

[0024]

[Chemical 3]

The aminoacetanilide is a substance shown in Chemical formula 4 (the position of the functional group attached to the benzene ring may be o, m or p).

[0026]

[Chemical 4]

The aminoacetophenone is a substance as shown in Chemical formula 5 (the position of the functional group attached to the benzene ring may be o, m or p).

[0028]

[Chemical 5]

As the acid salt of the above substance, the acid salt itself of the above substance can be used. Furthermore, starting from the above substance and adding an acid thereto, the amino group of the above substance can be ammonium ionized to form an acid salt.

The above-mentioned aniline halide, aminobenzoic acid ester, sulfanilamide or its derivative, aminoacetanilide, or aminoacetophenone does not have a carboxyl group which is likely to undergo molecular association as aromatic amino acids have. . When the molecules are associated with each other, the reactivity with respect to the aldehyde is lowered and the aldehyde removing agent does not exhibit sufficient performance.

Among the above substances, those having a basicity constant pKb of 9.4 or more (preferably around 10) are desirable.

Examples of the acid for forming the acidic salt include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and organic acids such as citric acid, malonic acid, malic acid and oxalic acid.

The use form of the malodorous substance removing agent of the present invention is not particularly limited, and the acid salt of the above substance may be used as it is as a powder or a solution having an arbitrary concentration. It is preferable that the acidic salt of the substance is supported in a dispersed state.

As the porous carrier, sepiolite, palygorskite, activated carbon, zeolite, activated carbon fiber,
Examples thereof include inorganic porous carriers such as activated alumina, sepiolite mixed paper, silica gel, activated clay, vermiculite and diatomaceous earth, and organic porous carriers such as pulp, fiber, cloth and porous polymer. Preferred are sepiolite, palygorskite, activated carbon, activated alumina, and zeolite. The type of carrier can be freely selected according to the type of malodorous substance to be adsorbed.

This porous carrier uniformly holds the acidic salt of the above substance which is the active ingredient in the pores of the structure, expands the contact area with the gas containing the malodorous substance, and the malodorous substance caused by the active component. Improve the removal performance. Further, the adsorbing ability of the porous carrier itself further improves the removal performance of the malodorous substance of the removing agent. For example, activated carbon adsorbs malodorous substances based on hydrocarbons, and sepiolite adsorbs malodorous substances based on lower fatty acids.

The shape of the porous carrier may be any of sheet, honeycomb, powder, granule, granule, plate and fiber.

When the acidic salt of the substance is supported on the porous carrier, the amount of the acidic salt of the substance supported is not particularly limited, but is 0.1 to 100 parts by weight of the carrier.
It is preferably in the range of 30 parts by weight. Within this range, the effect of removing malodorous substances can be achieved very efficiently. More preferably, it is in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the carrier.

In addition to the acidic salts of the above substances, a component effective in removing other malodorous substances may be added to the malodorous substance removing agent of the present invention. For example, JP-A-3-296434,
As disclosed in JP-A-5-23588, various compounds can be prepared by using an acidic salt of an aromatic amino acid, an acid, a transition metal compound such as a chloride of copper, an adsorption active ingredient such as iodine or iodide in combination. It can be a complex agent that removes the malodorous substances. In particular, a combination of the acidic salt of the substance according to the present invention, an acid, and iodine or iodide is excellent as a complexing agent. In this complexing agent, the acidic salts of the above substances according to the present invention remove aldehydes, the acid removes basic odors, and iodine or iodide removes sulfides. The odor can be removed. In addition, in this complex agent, when preparing an acid salt of the substance according to the present invention, that is, when an acid is added to the substance to form an acid salt, the acid salt of the substance and the acid are added by adding an acid in excess. Can coexist with.

Examples of the acid in the above-mentioned complexing agent include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, and organic acids such as citric acid, malonic acid, malic acid and oxalic acid. Examples of iodides include ammonium iodide, sodium iodide, potassium iodide and the like. Examples of the transition metal compound include chlorides, bromides, fluorides of copper, zinc, cobalt, nickel and the like.

When the active ingredient is loaded on the porous carrier in the composite agent, the loading amount of the active ingredient is 0.1 to 30 parts by weight per 100 parts by weight of the carrier. preferable. Further, more preferably, it is in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the carrier.

Next, the method for producing the malodorous substance removing agent of the present invention will be described.

When the malodorous substance removing agent of the present invention is loaded on a porous carrier, the loading method is not particularly limited, but preferably, the acidic salt of the above substance is finely pulverized to obtain a fine powder of the porous carrier. It is better to mix, mold and support. More preferably, it is dissolved in water or another soluble solvent, and the solution is impregnated into the porous carrier and loaded. As described above, when used in the form of a solution, the acidic salt of the above substance can be uniformly carried in a highly dispersed state on the porous carrier, and the removal performance can be maximized.

As described above, the agent for removing a malodorous substance according to the present invention has a high removal performance particularly for aldevides, and therefore, it can be used in various living environments such as automobiles, kitchens, living rooms, offices and toilets. It can be used as a remover for the odor containing the malodorous substance, and as an adsorbent for treating the gas containing these malodorous substances.

[0044]

EXAMPLES Examples of the present invention will be described below.

On the activated carbon fiber sheet (weight: 4.6 g),
7.8 g of an impregnating solution containing an acidic salt of the substance shown in Table 1 was uniformly impregnated with a spray, and then dried by heating at about 100 ° C. for 1 hour. Thus, the removing agent was prepared (Sample Nos. 1 to 5 in Table 1).

For comparison, an acid salt of glycine as an acid salt of an aliphatic amino acid, an acid salt of aniline as an acid salt of an aromatic amine having no electron-withdrawing substituent,
An acidic salt of p-aminophenol, an acidic salt of p-anisidine, or an acidic salt of p-aminobenzoic acid as an acidic salt of an aromatic amino acid is used as an active ingredient, and otherwise the same as the above, the removing agent for comparison. Was prepared (Sample N in Table 1
o. C1-C5).

The composition of the impregnating solution is shown in Table 1.

[0048]

[Table 1]

The adsorption performance of the prepared removing agent was evaluated as follows.

Remover (Sample No. 1, C1 to C5) 0.
5 g was placed in a gas impermeable bag. Next, the acetaldehyde aqueous solution was heated and vaporized, and 5 l of a mixture of the vaporized gas and conditioned air (25 ° C, 60%) was introduced into the bag. At this time, the amount of the acetaldehyde aqueous solution was changed to prepare four types having different gas concentrations. The bag was allowed to stand in a thermo-hygrostat kept at 25 ° C., and after about 24 hours, the concentration of gas remaining in the bag was measured by a gas chromatograph. From the result, the adsorption amount was obtained by using Equation 1, and an adsorption isotherm was created. Interpolation of adsorption isotherm, concentration 3ppm
The amount of acetaldehyde adsorbed at that time was determined and the performance was evaluated.
The result is shown in FIG.

[0051]

[Equation 1]

As is clear from FIG. 1, the removing agent of the present example (Sample No. 1) is the removing agent of the comparative example (Sample No. C).
1 to C5), the performance of removing acetaldehyde is superior, and in particular, p-chloroaniline having a basicity constant pKb of 10.01 has the maximum performance.

The basicity constant pKb in FIG.
Is defined by Equation 2.

[0054]

[Equation 2]

Next, changes in the adsorption performance of the remover when the humidity and temperature were changed were examined.

2 parts of the removing agent (Sample No. 1, C1 to C5)
90 ° C in 5%, 95% air for 90 hours or 60 ° C, 9
After exposure to 5% air for 63 hours, the adsorption performance of acetaldehyde was examined in the same manner as the above evaluation method (adsorption test). The temperature and humidity during the adsorption test were 25 ° C and 60%.
Is. The result is shown in FIG. FIG. 2 also shows a case where the current process is not performed (FIG. 1).

As is clear from FIG. 2, even if the atmosphere of humidity and temperature changes, the remover of this embodiment (Sample No.
It can be seen that 1) is superior to the removing agents of the comparative examples (Sample Nos. C1 to C5) and that the adsorption performance is not deteriorated.

Further, the following adsorption performance was also evaluated.

0.5 g of the remover (Sample Nos. 1 to 5) was put in a gas-impermeable bag. Next, a predetermined amount of aqueous acetaldehyde solution was vaporized by heating so that the concentration of acetaldehyde in the air was about 1000 ppm, and 5 l of a mixture with vaporized conditioned air (25 ° C, 60%) was introduced into the bag. This bag was allowed to stand in a thermo-hygrostat kept at 25 ° C., and the concentration of acetaldehyde over time was measured by gas chromatography. The result is shown in FIG.

As is clear from FIG. 3, the removing agents (Sample Nos. 1 to 5) of this example are excellent in the acetaldehyde removing performance.

[Brief description of drawings]

FIG. 1 is a diagram showing acetaldehyde adsorption performance of a removing agent in Examples and Comparative Examples.

FIG. 2 is a diagram showing acetaldehyde adsorption performance of a removing agent in Examples and Comparative Examples.

FIG. 3 is a diagram showing acetaldehyde adsorption performance of a removing agent in Examples.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Mitsumasa Horii Aichi Prefecture, Aichi-gun Nagakute-machi, Oita Nagakage 1 1st side street, Toyota Central Research Institute Co., Ltd. (72) Inventor Hiroaki Hayashi Aichi-gun, Nagakute-machi No. 41 Nagamichi Yokomichi 1 Toyota Central Research Institute Co., Ltd.

Claims (1)

[Claims] 1. At least one selected from an acid salt of a halide of aniline, an acid salt of an ester of aminobenzoic acid, an acid salt of sulfanilamide or a derivative thereof, an acid salt of aminoacetanilide, and an acid salt of aminoacetophenone. A malodorous substance remover characterized by containing a seed.