JPH08191879A - Deodorant and manufaturing method thereof - Google Patents

Abstract

PURPOSE: To enable the developing of excellent adsorbing performance for all gases acidic, neutral or basic while allowing the maintaining of the performance for a long time by arranging an inorganic adsorbent and an activated charcoal while an amine is added to at least one thereof. CONSTITUTION: This deodorant has an amine added to at least one of an inorganic adsorbent 1 and an activated charcoal 2. The inorganic adsorbent 1 and the activated charcoal 2 are formed integral with a reinforcing fiber 3. The deodorant 5 is in the form of a paper, a deodorant paper. The inorganic adsorbent 1 herein used is a porous adsorbing body having polarity in general and can use one or two or more selected from among the group of a silica gel, activated alumina, zeolite and a clay-based adsorbent. The specific surface area of the inorganic adsorbent 1 is preferably at least 150m<2> /g or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an air cleaner for automobiles,
Deodorant used in household air cleaners, deodorant sheets, etc.,
In particular, it relates to a deodorant having an adsorption effect on all of acidic gas, neutral gas and basic gas, and a method for producing the deodorant.

[0002]

2. Description of the Related Art Conventionally, activated carbon and activated carbon molded into various shapes have been used as deodorants. Activated carbon has very good adsorption performance, but it has a problem that it is difficult to adsorb and remove low-molecular polar acid gas or basic gas. Therefore, in order to solve such a problem, conventionally, activated carbon impregnated with a chemical has been often used.

[0003]

[Problems to be Solved] However, most of the activated carbon impregnated with a chemical agent is not effective against basic gas when it is used for adsorption of acidic gas. Has a low adsorption effect. Also,
Japanese Examined Patent Publication No. 4-17696 discloses a combination of aniline-supported activated carbon with malic acid and iron-supported activated carbon,
A deodorant effective against neutral and basic gases is disclosed. However, the loading process is complicated and there is a problem in stability over time.

In view of such conventional problems, the present invention exhibits excellent adsorption performance for all acidic, neutral and basic gases, and is capable of maintaining the adsorption performance for a long period of time. An agent and a method for producing the same are provided.

[0005]

The present invention relates to a deodorant comprising an inorganic adsorbent and activated carbon, wherein at least one of the inorganic adsorbent and the activated carbon has an amine attached thereto. .

What is most noticeable in the present invention is that amine is attached to either or both of the inorganic adsorbent and the activated carbon. The inorganic adsorbent is generally a porous adsorbent having polarity. As such an inorganic adsorbent, for example, one or more selected from the group of silica gel, activated alumina, zeolite, and clay adsorbent can be used. Examples of the clay-based adsorbent include sepiolite and activated clay.
Among such inorganic adsorbents, acidic or weakly acidic substances such as silica gel and zeolite are particularly preferable. As a result, the inorganic adsorbent exhibits high adsorption performance for basic gas, and therefore the deodorant of the present invention can exhibit high adsorption performance for basic, acidic and neutral gases in a well-balanced manner. .

The specific surface area of the inorganic adsorbent is not particularly limited, but in order to obtain high adsorption performance, it is preferably at least 150 m ² / g or more, and more preferably 400 m ² / g or more.

The activated carbon is a non-polar porous adsorbent having a high specific surface area. Activated carbon is in the range usually specific surface area of a few hundred m ² / g to thousand several hundred m ² / g, in order to obtain a high gas adsorption performance, specific surface area, 1000 m ² / g
It is preferable that it is above.

The raw materials for activated carbon include wood, sawdust,
It is possible to use plant-based raw materials such as coconut shells, coal, heavy petroleum oil, or fossil fuel-based raw materials such as coal and petroleum pitch, which are thermal decomposition products thereof, or synthetic polymer-based raw materials.
As a method for producing activated carbon, there are methods such as gas activation methods such as steam activation, carbon dioxide gas activation and oxygen activation, and chemical activation methods such as zinc chloride, phosphoric acid, calcium chloride and potassium sulfide. However, in the case of the chemical activation method, it is necessary to purify the activated carbon after activation so that salt etc. does not remain.

There are various shapes of activated carbon such as powdered coal, crushed coal, granular coal, granular coal, and fibrous shape, and any of them has excellent adsorption performance. In particular, when it is mixed with an inorganic adsorbent and integrally molded, it is preferably in the form of powder or fiber.

Examples of the above amine include 3-aminopropyltrihydroxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane. , Dimethyltrimethyl-silylamine, or organosilicon amine consisting of N- (β-aminoethyl) -γ-aminopropyl-trimethoxysilane, or aniline, p-toluidine, p-ethylaniline or p-anisidine aromatic There is one or more selected from the group of amines.

It is preferable to add and mix a reinforcing material such as a reinforcing fiber to the above deodorant. As the reinforcing fiber,
Synthetic cellulose, pulp and the like can be used. The deodorant has, for example, a shape such as a sheet, paper, felt or the like. The deodorant is, for example,
It can also be supported on a carrier such as paper, sheet, honeycomb or urethane foam.

As a method for producing the deodorant, for example, an inorganic adsorbent is added to water, the mixture is stirred, activated carbon and an amine are added, the mixture is further stirred, and then the solid content in the water is removed. There is a method for producing a deodorant characterized by filtering, molding and drying.

That is, first, an inorganic adsorbent is added to water and stirred. As a result, the inorganic adsorbent is uniformly dispersed in the water. The amount of water should be such that the inorganic adsorbent can be sufficiently stirred. Next, activated carbon and amine are put into water in which the inorganic adsorbent is dispersed and mixed. Either activated carbon or amine may be added to water first.

A reinforcing material and a binder are preferably added to the water. As a result, the strength of the deodorant can be increased. Examples of the reinforcing material include synthetic cellulose. Examples of the binder include polyvinyl alcohol and the like. Next, the solid content in the water is filtered off. Means for filtering and molding may be any method as long as a molded product having a desired shape can be obtained, but from the viewpoint of easy operation, it is preferable to carry out wet molding in which filtering and molding are performed simultaneously.

[0016]

[Action and Effect] In the deodorant of the present invention, the amine is
When it is impregnated with a porous material composed of an inorganic adsorbent or activated carbon, the effect of adsorbing acidic gas such as aldehydes is remarkably enhanced. Activated carbon is a non-polar adsorbent with a high specific surface area, and therefore has a high neutral gas adsorption performance.

Since the inorganic adsorbent generally has polarity, it has high adsorption performance for polar gases such as acidic and basic. In addition, polar inorganic adsorbents have a high affinity with water. Therefore, the water adsorbed on the surface of the inorganic adsorbent acts to remove the basic gas. Therefore, the inorganic adsorbent also adsorbs water in preference to activated carbon. Therefore,
It is possible to suppress deterioration of activated carbon due to addition of water.
Therefore, the deodorant of the present invention has little deterioration in adsorption performance over time.

Therefore, regardless of whether it is polar or non-polar, it can exhibit high adsorption performance for all gases, and can absorb and remove all odorous gases which are odorous components of unspecified various kinds.
Therefore, the present invention is an excellent deodorant.

Next, in the method for producing a deodorant of the present invention, first, an inorganic adsorbent is added to water and mixed. Therefore, when activated carbon and amine are added and mixed thereafter, more amine is impregnated on the activated carbon, while the surface functional groups of the inorganic adsorbent are partially protected by hydration. Further, since the inorganic adsorbent, activated carbon and amine are mixed in water, the amine is uniformly impregnated on the inorganic adsorbent and activated carbon. Therefore, according to the manufacturing method of the present invention,
As described above, the excellent deodorant can be easily produced.

According to the present invention, a deodorant and its production which exhibit excellent adsorption performance for all of acidic gas, neutral gas and basic gas and can maintain the adsorption performance for a long time. A method can be provided.

[0021]

【Example】

Example 1 A deodorant according to an example of the present invention will be described with reference to FIGS. As shown in FIGS. 2, 4, and 5, the deodorant of this example has an amine adsorbed on the inorganic adsorbent 1 and the activated carbon 2. The inorganic adsorbent 1 and the deodorant 2 are integrally molded with the reinforcing fiber 3. The deodorant 5 is paper-like deodorant paper as shown in FIG.

The inorganic adsorbent 1 has a specific surface area of 450
Silica gel with m ² / g, pore size 70 Å, and particle size 75 μm or less was used. The activated carbon 2 has a specific surface area of 1200 m
A pitch-based activated carbon fiber having a pore size of ² / g and a pore size of 20Å was used. As the amine, 3-aminopropyltrihydroxysilane (hereinafter referred to as 3-APTS) was used.

Next, the outline of the method for producing the above deodorant will be described. First, silica gel was added to water and stirred (Fig. 3 (a)), and then activated carbon fiber and 3-APT were added.
Add S and stir (Fig. 3 (b)). Then, the solid matter is separated from this aqueous solution by filtration, molded and dried to obtain the above deodorant (FIG. (C)).

The above manufacturing method will be described in detail below. First,
As shown in FIG. 3 (a), 1.35 g of silica gel, 0.66 g of auxiliary fiber and 0.66 g of binder fiber are added to 550 ml of water.
g, 0.38 g, and stirred for about 1 minute with a mixer.
Synthetic cellulose was used as the auxiliary fiber. Polyvinyl alcohol was used as the binder fiber.

Next, as shown in FIG. 3 (b), 0.83 g of activated carbon fiber, 0.83
g, and stirred for another 30 minutes. Next, this aqueous solution was dehydrated on a wire mesh and wet-molded. Next, the molded body was dried with a drum dryer at 120 ° C. for 10 minutes,
As shown in (c), a paper-like deodorant was obtained.

Example 2 The deodorant of this example was replaced with the silica gel of Example 1 with a specific surface area of 650 m ² / g, a pore diameter of 22Å. Particle size 75μ
Silica gel of m or less was used as an inorganic adsorbent. Others are the same as in the first embodiment.

Comparative Example 1 As the deodorant of this comparative example, powdered activated carbon and activated carbon fibers similar to those used in Example 1 were used. No silica gel or amine was added. Others are the same as in the first embodiment.

Comparative Example 2 The deodorant of this comparative example was the same as the deodorant of Comparative Example 1 except that 3-A
PTS was added.

Comparative Example 3 The deodorant of this comparative example is formed by using aniline-impregnated activated carbon fiber and tartaric acid-impregnated powder activated carbon. The silica gel and 3-APTS used in Example 1 were not added. Others are the same as in the first embodiment.

Example 3 In this example, the gas adsorption performance of the deodorant was measured. In the measurement, first, a glass container of about 5 liters was filled with a single component gas having an initial concentration (C ₀ ), and 0.25 g of the deodorant for measurement was used at a flow rate of about 0.5 liter / min.
It was circulated for a minute, and the gas concentration (C) in the glass container at that time was measured. Then, the gas removal rate (J) was calculated by the following formula.

J (%) = (1−C ₀ / C) × 100 As the above-mentioned single component gas, acetaldehyde, toluene,
Ammonia was used. Initial concentration (C ₀ ) of each single component gas
Is acetaldehyde 60ppm, toluene 800pp
m, 80 ppm of ammonia. For acetaldehyde and toluene, a gas chromatograph (made by Shimadzu)
GC-9A), and ammonia was measured with a detector tube (3La manufactured by Gastec). The measurement system is 2
Hold at 5 ° C. As the deodorizing agent for measurement, as shown in Table 1, the paper-like deodorizing agents according to Examples 1 and 2 and Comparative Examples 1 and 2 described above were used. The measurement results are shown in Table 1.

As is known from the table, the deodorants of Examples 1 and 2 showed high removal rates for all of acetaldehyde, ammonia and toluene. In particular, it showed excellent adsorption performance for acetaldehyde and ammonia, which was significantly higher than that of Comparative Example 1. The adsorption performance of toluene, which is a neutral gas, was slightly lower than that of other single-component gases. However, since the general olfactory threshold of neutral gas is high, there is no practical problem in using it as a deodorant. Further, the deodorant of Example 1 had a significantly higher ammonia adsorption performance than Comparative Example 2.

The deodorant of Example 2 was slightly inferior to the deodorant of Example 1 in the acetaldehyde removal rate, but was superior to the deodorant of Comparative Example 1 in the performance of removing acetaldehyde and ammonia.

The reason why the deodorants according to Examples 1 and 2 according to the present invention exhibit higher adsorption performance as described above than the deodorants according to Comparative Examples 1 and 2 is considered as follows. To be That is, in the deodorants of Examples 1 and 2, as shown in FIG. 4, the silica gel, which is the inorganic adsorbent, is impregnated with the amine, 3-APTS. This 3-AP
TS is physically fixed to the pores of silica gel or chemically fixed to the hydroxyl group (--OH group) on the surface by covalent bonding. The first at the end of this amine
The primary amino group adsorbs acidic gas such as acetaldehyde. This adsorption effect is considered to be due to a kind of neutralization. In addition, a large number of hydroxyl groups (--OH
The group) has a weak acidity and therefore has an action of adsorbing a basic gas such as ammonia.

Also, as shown in FIG. 5, 3-APTS is attached to the activated carbon fiber which is the activated carbon. This 3-APTS adsorbs an acidic gas such as acetaldehyde. Furthermore, since the activated carbon fiber has a high specific surface area and is a hydrophobic adsorbent, it adsorbs a neutral gas (toluene or the like) which is a nonpolar gas well.

Therefore, it is considered that the deodorants according to Examples 1 and 2 of the present invention can exhibit excellent adsorption performance for all of acidic gas, neutral gas and basic gas.

[0037]

[Table 1]

Example 4 In this example, the change with time of the adsorption performance of the deodorant was measured. In the measurement, the deodorant for measurement was stored in a thermo-hygrostat at a temperature of 25 ° C. and a humidity of 60% for 50 days, a required amount was taken out, and the gas removal rate was measured by the same method as in Example 3. As the deodorizing agent for measurement, the deodorizing agents of Example 1 and Comparative Example 3 described above were used. The measurement results are shown in Table 2.

As can be seen from the table, at the initial stage of storage, the deodorants of Example 1 and Comparative Example 3 all exhibited high adsorption performance for acetaldehyde and ammonia. After 50 days, the deodorant of Example 1 showed a slight decrease in adsorption performance. It is considered that this is because the adsorbent is a kind of amine, and the moisture was preferentially adsorbed on the silica gel, and the deterioration of the adsorption performance of activated carbon was suppressed.

On the other hand, the deodorant of Comparative Example 3 had a remarkable deterioration in adsorption performance over time. It is considered that this is because the aniline and tartaric acid as the binders in Comparative Example 3 were gradually neutralized through the water adsorbed on the activated carbon as the carrier. From the measurement results of this example, it was found that the deodorant according to the present invention had excellent stability of adsorption performance over time.

[0041]

[Table 2]

[Brief description of drawings]

FIG. 1 is a perspective view of a deodorant of Example 1.

FIG. 2 is an explanatory diagram of a deodorant of Example 1.

FIG. 3 is an explanatory view showing a method for producing a deodorant of Example 1.

FIG. 4 is an explanatory diagram showing the adsorption performance of an amine-containing inorganic adsorbent in the deodorants of Examples 1 and 2.

FIG. 5 is an explanatory view showing the adsorption performance of amine-impregnated activated carbon in the deodorants of Examples 1 and 2.

[Explanation of symbols]

 1. . . Inorganic adsorbent, 2. . . Activated carbon, 3. . . Reinforcing fiber, 5. . . Deodorant,

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication B01D 53/81 B01J 20/22 ZAB A

Claims (6)

[Claims] 1. A deodorant comprising an inorganic adsorbent and activated carbon, wherein at least one of the inorganic adsorbent and the activated carbon has an amine attached thereto. 2. The deodorant according to claim 1, wherein the inorganic adsorbent is one or more selected from the group consisting of silica gel, activated alumina, zeolite, and clay-based adsorbent. . 3. The deodorant according to claim 1 or 2, wherein the specific surface area of the inorganic adsorbent is 150 m ² / g or more. 4. The method according to claim 1, wherein
A deodorant characterized in that the specific surface area of the activated carbon is 1000 m ² / g or more. 5. The method according to any one of claims 1 to 4,
The amine is 3-aminopropyltrihydroxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane,
Dimethyltrimethyl-silylamine, or N- (β-
Aminoethyl) -γ-aminopropyl-trimethoxysilane, organosilicon amine, or one or two selected from the group of aniline, p-toluidine, p-ethylaniline, or aromatic amine consisting of p-anisidine.
Deodorant characterized by being more than one kind. 6. An inorganic adsorbent is added to water, the mixture is stirred, then activated carbon and an amine are added, the mixture is further stirred, and then the solid content in the water is filtered off, molded and dried. A method for producing a deodorant, comprising: