JPH10155882A - Deodorant - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a deodorant body that maintains a deodorizing effect at room temperature for various types of odors for a long period of time. SOLUTION: A copper oxide, a manganese oxide, a composite oxide of copper and manganese, or a platinum group metal for oxidatively removing mercaptan and a Y-type zeolite and a pentasil type for removing disulfide generated by oxidation of mercaptan, or Deodorant containing β-type zeolite. In addition, Y-type zeolites and pentasil-type or β-type zeolites effectively act on amines. As a result, it is effective against many odors, and does not generate an unpleasant odor at the time of deodorization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant used for equipment for heating, hot water supply, drying, cooking, refrigeration, or air conditioning.

[0002]

2. Description of the Related Art Conventionally, as a deodorizing method used for this kind of equipment, an adsorbent such as activated carbon or zeolite is placed in a deodorizer, and gaseous malodorous substances are adsorbed by the adsorbent to deodorize. Has been mainly used. In addition, a device having an ozone generating function is disposed in a deodorizer to oxidize and decompose malodorous components with ozone gas, or a catalyst is heated by providing an oxidative decomposition catalyst such as a noble metal near a heat source such as a flame or a heating element. A method of activating and oxidatively decomposing odorous substances is also employed.

[0003]

Activated carbon used as an adsorbent in the adsorption deodorization method does not have sufficient adsorption capacity for mercaptans and amines. For this reason, bromine impregnated carbon is used for removing mercaptans and sulfonated activated carbon is used for removing amines. However, since these adhering substances are water-soluble, there is a problem that when they are dissolved in water, not only the deodorizing ability is reduced, but also equipment around the deodorizing body is corroded. For this reason, the use in which impregnated charcoal can be used is limited to the case where there is no fear that the deodorant is exposed to water. In addition, zeolite, which is also an adsorbent, has insufficient mercaptan adsorption ability. For zeolites, Cu
For example, a method of partially oxidizing and removing mercaptan at room temperature by ion-exchange of a transition metal having an oxidizing ability, such as, for example, is also possible. However, due to the structure of zeolite, Cu
, The ability to remove mercaptans is limited.

[0004] Further, in the ozone deodorization, there is a problem that a special device is required to generate ozone, and an ozone decomposition catalyst must be provided so that unreacted ozone is not discharged out of the deodorizer. For this reason, a deodorizing method with a simple configuration is desired. On the other hand, in the deodorization method using an oxidative decomposition catalyst, since heating of the catalyst is necessary, it is difficult to apply the method to equipment for cooling such as refrigerators and cooling equipment.
In order to solve these problems, development of a deodorant having an effective deodorizing ability at room temperature for a long period of time is desired.

[0005]

The deodorant of the present invention comprises at least one selected from the group consisting of copper oxides, manganese oxides, and composite oxides of copper and manganese, Y-type zeolite, and pentasil-type. Alternatively, the deodorant of the present invention is characterized by containing a β-type zeolite, and is characterized by containing a platinum group metal, a Y-type zeolite, and a pentasil-type or β-type zeolite.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the deodorant of the present invention comprises at least one selected from the group consisting of copper oxide, manganese oxide, and a composite oxide of copper and manganese, or a platinum group metal, It comprises Y-type zeolite and pentasil-type or β-type zeolite. And copper oxide, manganese oxide, composite oxide of copper and manganese,
And platinum group metals such as Pt and Rh have the effect of efficiently converting mercaptan-based odors such as methyl mercaptan to disulfide at room temperature. Precious metals such as Pt and Rh can efficiently decompose mercaptans in a small amount by being supported in a highly dispersed manner on inorganic oxides having a high specific surface area such as alumina.

[0007] Disulfide generated by the oxidative decomposition of the mercaptan odor is also one of the odor components.
If only the oxidation catalyst is used, an unpleasant odor may be generated at the time of deodorization, which may have an adverse effect. Therefore, Y-type zeolite,
By adding the pentasil-type or β-type zeolite to the deodorant, disulfide can be adsorbed by these adsorbents, and the generation of off-flavors can be suppressed. Y-type zeolites, pentasil-type zeolites, and β-type zeolites can effectively remove amines such as trimethylamine, which are difficult to remove with copper oxides and manganese oxides. In particular, when the concentration of amine is low, Y-type zeolite is effective, and when the concentration is high, pentasil-type zeolite and β-type zeolite are effective. Therefore,
By adding the Y-type zeolite and the pentasil-type zeolite or the β-type zeolite, the amine odor can be effectively adsorbed under any conditions. Mercaptan can be decomposed with either a copper oxide or a manganese oxide. In particular, when both are contained, an excellent removal ability can be obtained. In this case, when the content of the copper oxide is 0.5 to 50 wt% in terms of CuO, and when the content of the manganese oxide is 3 to 70 wt% in terms of MnO ₂ ,
High performance is obtained for each.

The deodorized body of the present invention can be used as a filter by fixing powder to a material having good air permeability such as a nonwoven fabric, or as a molded body such as a honeycomb body using a binder, or a ceramic honeycomb. The substrate may be supported as a coating. In that case, if the content in the total weight of the adsorbent excluding the binder and the honeycomb substrate is the above content, the effect of the present invention can be expected. Among the above methods, it is particularly desirable to add a binder to the adsorbent of the present invention and use it as a molded body such as a honeycomb body. This makes it possible to obtain a compact and effective deodorant for a long period of time. In order to manufacture such a deodorized body, a structure having excellent mechanical strength and high odor adsorption ability can be obtained by kneading an adsorbent and a binder, molding by extrusion molding, and then drying. . As the binder, it is desirable to use an organic binder in which a polysaccharide such as methyl cellulose or a derivative thereof is dissolved in water. This is because the hydroxyl group, carbonyl group, amino group, and the like of the polysaccharide and its derivative have the ability to adsorb odor molecules, and the binder itself can also function as an adsorbent. Further, by using an inorganic binder such as silica sol, alumina sol, or titania sol, the mechanical strength of the deodorant can be improved. Further, the organic binder and the inorganic binder may be mixed and used.

[0009]

EXAMPLES Specific examples will be described below. << Example 1 >> 25 mixed aqueous solutions of copper nitrate and manganese nitrate
It was thermally decomposed at 0 ° C. to obtain a mixture of copper oxide and manganese oxide. This was pulverized to powder A. The ratio of copper and manganese was set to 30 wt% as CuO and 70 wt% as MnO ₂ . This powder A was crushed after pressure molding to obtain a pellet (sample A) of 1 to 2 mm.
0.02 g of this sample was charged into an adsorption test apparatus of a normal pressure flow type, and air containing 100 ppm of methyl mercaptan was added to the adsorption test apparatus.
The sample was circulated at a rate of 1 liter / min, and the change with time in the circulating gas concentration before and after the sample was examined by gas chromatography. The adsorption temperature was kept constant at 25 ° C. by placing the sample tube filled with the sample in a thermostat. The gas downstream of the sample contained methyl mercaptan and dimethyl disulfide, a partial oxidation product of methyl mercaptan, and the methyl mercaptan concentration increased with time. The amount of methyl mercaptan removed for 1000 minutes was determined by the above method, and as a result, 0.31 g was obtained.
-Methyl mercaptan / g-sample. The dimethyl disulfide generated during this period was 0.17 g-dimethyl disulfide / g-sample, and the dimethyl disulfide generation rate was 55%.

On the other hand, a sample B prepared by pelletizing H-ZSM-5, a kind of pentasil type zeolite, in the same manner, a sample C prepared by pelletizing Na-β zeolite, a kind of β type zeolite, and a Y type zeolite D, powder A, in which Na-Y type zeolite, which is a kind of
E, which is a pellet after sufficiently mixing H-ZSM-5 and H-ZSM-5 at a weight ratio of 1: 1, and a sample which is pellet after sufficiently mixing powder A and Na-β zeolite at a weight ratio of 1: 1. F, and powder A and Y-type zeolite in a weight ratio of 1:
Sample G obtained as pellets after sufficiently mixing at a ratio of 1 was subjected to a methyl mercaptan purification test in the same manner as in Sample A. Table 1 shows the results.

[0011]

[Table 1]

As is apparent from Table 1, methyl mercaptan can be effectively purified by copper oxide and manganese oxide, but disulfide is formed. Y-type zeolite,
By adding pentasil-type zeolite or β-type zeolite, it is possible to suppress generation of dimethyl disulfide.

Example 2 γ-Al ₂ O ₃ was impregnated with an aqueous solution of chloroplatinic acid and calcined at 500 ° C. to obtain γ-Al ₂ O ₃ carrying 1 wt% of Pt. Crush this,
Powder H was used. From an aqueous solution of palladium nitrate and an aqueous solution of rhodium nitrate, 1 wt% P
d-supported γ-Al ₂ O ₃ and 1 wt% Rh-supported γ-Al ₂
A powder of O ₃ was prepared. Powder H was pressure-molded into pellets (sample H), and a purification test of 10 ppm of methyl mercaptan was performed in the same manner as in Example 1. Further, Pd-supported γ-Al ₂ O ₃ , Rh-supported γ-Al ₂ O ₃ and unsupported γ-Al ₂ O ₃
-Al ₂ O ₃ was also examined for its ability to purify methyl mercaptan. Table 2 shows the results.

[0014]

[Table 2]

[0015] As shown in Table 2, it can be seen that methyl mercaptan can be effectively removed by the platinum group element. Next, the powder H and H-ZSM-5 were mixed at a weight ratio of 1: 1 and then pellets were prepared. After the powder H was mixed with the Na-β type zeolite at a weight ratio of 1: 1 Sample J as pellets and Sample K as pellets after mixing powder H and Na-Y type zeolite at a weight ratio of 1: 1
Was prepared. These samples were subjected to a methyl mercaptan purification test in the same manner as in Example 1. Table 3 shows the results.

[0016]

[Table 3]

As is clear from Table 3, methyl mercaptan can be purified by the noble metal, but dimethyl sulfide, one of the odor components, is formed. However, by adding Y-type zeolite, pentasil-type zeolite or β-type zeolite, it is possible to suppress the generation of disulfide.

Example 3 In order to examine the composite effect of copper oxide and manganese oxide and the optimum amount of addition, the following study was conducted. When preparing a mixed aqueous solution of copper nitrate and manganese nitrate in Powder A, a mixture of copper oxide and manganese oxide having different contents was prepared by changing the ratio of copper and manganese in various ways. First, the content of manganese oxide was constant at 20 wt% in terms of MnO ₂ , the content of Na-Y type zeolite was constant at 15 wt%, and the content of copper oxide was C
A sample was prepared in which the content was changed to 0 to 51 wt% in terms of uO and the content of H-ZSM-5 was changed accordingly.
For these samples, 100 p
pm methyl mercaptan purification test,
The relationship between the copper oxide content and the amount of purified mercaptan was investigated. Table 4 shows the results.

[0019]

[Table 4]

From Table 4, it can be seen that methyl mercaptan can be purified even when CuO is not contained, and CuO is 0.5 to 0.5%.
It can be seen that the purification amount is high when the amount is 50 wt%. next,
The content of copper oxide is 5 wt% in terms of CuO,
The content of Y-type zeolite is fixed at 10 wt%, and the content of manganese oxide is converted to MnO ₂ from 0 to 73 wt%.
And a sample in which the H-ZSM-5 content was changed accordingly. This sample was subjected to a 100 ppm methyl mercaptan purification test in the same manner as in Example 1 to examine the relationship between the manganese oxide content and the mercaptan purification amount. Table 5 shows the results.

[0021]

[Table 5]

[0022] From Table 5, methyl mercaptan cleaning even when not containing MnO ₂ is possible, particularly MnO ₂
Is 3 to 70% by weight, the purification amount is high.

Example 4 A powder L containing copper oxide and manganese oxide and Na-Y type zeolite were sufficiently mixed at a weight ratio of 1: 1 to prepare a sample L as a pellet. Further, the sample L of Na-Y type zeolite was converted to H-ZSM.
-5, Na-β zeolite, Na-A zeolite, 1
3X samples were prepared, and samples M, N, P,
Q. For the test, a 350 L box provided with a path for circulating air in the box and a circulation function was used. In this test apparatus, the air in the box efficiently passes the sample filled in the path. In the box, trimethylamine is set to a low concentration of 2 ppm and a high concentration of 100 ppm, and circulated through the above-mentioned route at 2 L / min. Examined. The adsorption temperature was kept constant at 25 ° C. Table 6 shows the results.

[0024]

[Table 6]

As shown in Table 6, Y-type zeolite, pentasil-type zeolite and β-type zeolite have excellent amine adsorption performance. In particular, when the amine concentration is low, Y
Zeolite has excellent amine adsorption performance, and when the concentration of amine is high, pentasil-type zeolite, β
It can be seen that the zeolite is effectively acting on the amine. That is, by adding the Y-type zeolite, the pentasil-type zeolite, or the β-type zeolite, the amine can be effectively removed under any conditions.

Example 5 The content of powder A containing copper oxide and manganese oxide was kept constant at 10 wt%, and the content of Na-Y type zeolite was changed from 8 to 82 wt%. A sample in which the content of -5 was changed was prepared, and the trimethylamine adsorption ability was examined in the same manner as in Example 4. Table 7 shows the results.

[0027]

[Table 7]

As shown in Table 7, when the amount of the Na-Y type zeolite is less than 10% by weight, the ability to adsorb a low concentration of amine is reduced, and the amine removing effect is not sufficient. Also,
If the content of H-ZSM-5 is less than 10 wt%, the adsorption performance of a high concentration of amine will be reduced, and the amine removing effect will not be sufficient.

Example 6 The content of powder A containing copper oxide and manganese oxide for purifying methyl mercaptan was 9
The sample R was 0 wt%, and Na-Y type zeolite was mixed at 10 wt% to prepare a pelletized sample R. In the same manner, the mordenite of Sample R was replaced with H-ZSM-5,
Samples S and T changed to Na-β type zeolite were prepared.
Using the same test method as in Example 4, the target odor was changed to 100 ppm of methyl mercaptan, and the occurrence of dimethyl disulfide was examined. As a result, when samples R, S, and T were used, no dimethyl disulfide was generated.

[0030]

As described above, according to the present invention, it is possible to obtain a deodorant having excellent adsorption ability for many odor components for a long period of time. In particular, amines have adsorption performance in a wide concentration range. Further, generation of disulfide during purification of mercaptan can be suppressed.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kunio Kimura 1006 Kazuma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 72) Inventor Yuko Tachibana 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.

Claims (4)

[Claims] At least one selected from the group consisting of copper oxide, manganese oxide, and a composite oxide of copper and manganese, a Y-type zeolite, and a pentasil-type or β-type zeolite
A deodorant comprising a zeolite. 2. A deodorant comprising a platinum group metal, a Y-type zeolite, and a pentasil-type or β-type zeolite. 3. The deodorized body has a copper oxide content of 0.5 to 50 wt% in terms of CuO and a manganese oxide content of 3 to 70 wt% in terms of MnO _2. The deodorant described. 4. The content of the Y-type zeolite in the deodorized body is 1
The deodorant according to claim 1 or 2, wherein the content of the pentasil-type or β-type zeolite in the deodorant is 10% by weight or more.