JPH10165767A - Odor preventing method for deodorizer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an odor preventing method for a deodorizer not only improving the malodor preventing performance for the primary malodor and secondary malodor, but also regenerating the deodorizing performance for a deodorizer and removing the malodor of the deodorizer itself at the low regeneration temperature by making the deodorizer carry active manganese oxide on the surface of the deodorizer. SOLUTION: A deodorizer is immersed in an agueous solution containing 5-16wt.% of manganese nitrate in terms of Mn and drawn up therefrom and then excessive solution is blown off by air, and the deodorizer is impregnated uniformly with manganese nitrate and the manganese nitrate is carried thereon. The manganese nitrate carrying deodorizer is heated to dry and remove adhered water and crystallization water, and then decomposed and burnt at the temperature of 200-400 deg.C, and the carried manganese nitrate is converted into active manganese oxide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preventing the deodorant from emitting odor by uniformly dispersing and supporting active manganese oxide on the entire surface of the deodorant.

[0002]

2. Description of the Related Art Unpleasant odors can be removed by physical deodorizing methods using adsorbents or absorbents, physical deodorizing methods by electrostatic precipitating, chemical deoxidizing reactions by oxidation and neutralization reactions. There are an odor method, a sensory deodorization method using a masking agent, and a biochemical deodorization method using microorganisms.

Conventionally, adsorbents such as zeolite, silica gel, and alumina have been widely used in the physical deodorization method. Also, a method of catalytically decomposing an odorous gas or a harmful gas using an oxidative decomposition catalyst has been widely used.

On the other hand, a physical deodorizing method and a chemical deodorizing method are combined, or a deodorizing agent regeneration function is added, so that the deodorizing agent can be used for a long period of time without replacing the deodorizing agent during its life. Degradative deodorants have been developed.

[0005] However, when these adsorptive decomposition deodorants are used for a relatively long period of time, problems of odor due to odor of the deodorant itself, which has been inconspicuous in the past, and chemicals of odorous substances adsorbed by the deodorant are considered. The change causes a problem of causing an unpleasant odor.

JP-A-8-266866 discloses a deodorizing filter in which a deodorizing catalyst and a zeolite powder having a SiO ₂ / Al ₂ O ₃ ratio of 15 or more are supported on a catalyst carrier for a gas phase reaction. In this publication, an Mn-Cu-based deodorizing catalyst and SiO
A zeolite powder having a ₂ / Al ₂ O ₃ ratio of 15 or more is supported, the zeolite powder is supported on the core at a higher density than the surface of the carrier, and the deodorizing catalyst is on the surface of the carrier relative to the core. It is described that a deodorizing filter supported at a high density does not cause a new off-flavor even when used for a long period of time, and a hydrophobic zeolite removes malodorous components in the atmosphere or decomposition products thereof into a deodorizing catalyst. It is presumed that the adsorption in the vicinity of is useful for preventing the formation or release of secondary odor-causing substances. Further, Example 1 discloses a method for preparing a deodorizing filter in which a Mn-Cu-based deodorizing catalyst is supported on a carrier supporting hydrophobic zeolite by a slurry method.

[0007]

As described above, in order to prevent the odor of the deodorizing filter, a deodorizing filter comprising a Mn-Cu-based deodorizing catalyst and a zeolite having a silica / alumina ratio of 15 or more is used in the present invention. Proposed before the application, it focuses on the fact that hydrophobic zeolites help to prevent the formation or release of secondary malodorous substances.

However, by further supporting active manganese oxide on the surface of the deodorant, the deodorant itself hardly emits odor even if it absorbs a malodorous gas or a harmful gas. There has never been proposed any means for preventing the generation or release of the next odor-causing substance and preventing the generation of unpleasant odor even after long-term use.

[0009] The present inventors have come to emit an unpleasant odor due to the primary odor caused by the adsorption of the odorous gas or the harmful gas by the deodorant and the chemical change of the substance adsorbed by the deodorant over time. In order to improve the ability to prevent the generation of secondary odors, we conducted various studies and conducted intensive studies.As a result, active manganese oxide was further supported on the surface of the deodorant to produce primary odors and secondary odors. Not only improves the ability to prevent the generation of
It has been found that the deodorizing performance of the deodorant can be regenerated at a low regeneration temperature, and that the odor of the deodorant itself can be removed. The present invention has been made based on the above findings.

[0010]

According to the present invention, a deodorant is immersed in an aqueous solution containing 5 to 16% by weight, preferably 10 to 16% by weight, in terms of Mn, of manganese nitrate. Manganese nitrate is uniformly impregnated and supported in the deodorant, and the manganese nitrate-supported deodorant is heated to remove adhering water and crystallization water.
The present invention relates to a method for preventing odor of a deodorant, which is decomposed and fired at a temperature of 00 ° C. to convert the supported manganese nitrate into active manganese oxide.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The deodorant according to the present invention is not particularly limited, and may be a powder, a molded article or a deodorant carried on a carrier. As the deodorant, a physical deodorization method and a chemical deodorization method are combined, and both the functions of an adsorbent and an oxidation catalyst are performed.

The carrier material is not particularly limited, but it is preferable to use a porous carrier, which is generally a carrier through which a reaction gas can flow and has a small pressure loss. For example, inorganic carriers such as cordierite, alumina, silica alumina, titania silica, zeolite, sepiolite, and a zeolite-sepiolite mixture are suitable. The carrier may have a shape such as a honeycomb shape, a sponge shape, a mat shape, a woven fabric shape, a plate shape, a cylindrical shape, or a granular shape. In particular, a honeycomb structure or a three-dimensional network structure in which the flow of a reaction gas is easy. Is preferred. The cell shape of the honeycomb is arbitrary, and may be a polygonal shape such as a triangle, a square, a pentagon, or a hexagon, or a shape such as a corrugated shape. For example,
An aggregate of ceramic fibers (a honeycomb carrier manufactured by Nichias) as proposed in JP-B-59-15028, that is, silica fibers, alumina fibers, aluminosilicate fibers bonded to each other by a silicate gel,
Honeycomb structure composed by stacking sheet-like aggregates of ceramic fibers selected from inorganic fibers such as zirconia fibers in a honeycomb shape has low pressure loss, large geometric surface area and high water content, so it is active It is particularly preferable because many components can be supported.

As the adsorbent, alumina, silica-alumina, zeolite, sepiolite, a zeolite-sepiolite mixture or the like, which is usually used, can be used as a carrier, but other carriers having no adsorptivity can be washed with a washcoat method. It may be carried by a usual method such as

The oxidation catalyst is not particularly limited as long as it can oxidize and decompose the deodorized odorous gas component. Preferred catalyst components are platinum group elements composed of rhodium, palladium, ruthenium, iridium and platinum; transition metal elements composed of iron, cobalt, chromium and nickel; group I elements such as copper and silver; group VII elements such as manganese Group II elements such as zinc, and rare earth metals such as cerium and lanthanum;
One of these metals or a suitable combination thereof is used as a catalyst component. The catalyst component can be used in the form of an elemental metal, its oxide or a complex, and is used by being supported on a deodorant by a conventional method such as an impregnation method, a slurry method, a wash coat method, or the like.

Further, those obtained by subjecting these metal ions to ion exchange treatment with zeolite can be suitably used. For example, ammonia, dimethylamine, basic odor components such as amines such as trimethylamine, and hydrogen sulfide,
It is particularly preferable that a copper component having a particularly effective deodorizing performance against malodorous components such as methyl mercaptan is ion-exchanged and carried on a Y-type zeolite, and a hydrophobic component which is particularly excellent in the adsorption performance of aldehyde and dimethyl sulfite. A deodorant combined with a silicalite having performance has an excellent deodorizing effect and is an excellent deodorant which is hardly affected by humidity in the atmosphere.

The amount of the catalyst component carried varies depending on the catalyst component used and the malodorous gas component to be treated.
In the case of a platinum group element, it is 0.1 to 10 g / L, preferably 0.5 to 5 g / L, more preferably 1 to 2 g / L, and in the case of other base metal elements, it is 10 to 10 g / L. -100 g / l, preferably 20-70 g / l, more preferably 3
0-50 grams / liter. When a rare earth metal is used in combination, the rare earth metal is supported at 1 to 100 g / l, preferably 5 to 20 g / l.

In the method for preventing odor of a deodorant of the present invention, the above-mentioned conventional deodorant is immersed in an aqueous solution containing 5 to 16% by weight, preferably 10 to 16% by weight of manganese nitrate in terms of Mn. After lifting, the excess aqueous solution is blown off with air to uniformly impregnate and carry manganese nitrate. The deodorant loaded with manganese nitrate is heated and dried to remove adhering water and water of crystallization, and then decomposed and fired at a temperature of 200 to 400 ° C. to convert the manganese nitrate into active manganese oxide and convert the active manganese oxide into MnO _2. At least 10 grams, preferably 20 to 200 grams, more preferably 20 to 90 grams per liter of deodorant. When the amount of activated manganese oxide supported by the impregnation treatment is 10 g or less per liter of deodorant in terms of MnO ₂ , the effect of preventing odor is insufficient, and when it exceeds 200 g, the deodorant has a bad odor adsorption performance. Adversely affect

According to X-ray diffraction analysis, the obtained active manganese oxide is fine manganese dioxide particles which are mostly composed of crystalline. When the deodorant of the present invention is observed with an optical microscope, the crystalline manganese oxide becomes crystalline. The finely divided active manganese dioxide is uniformly dispersed and supported on the entire surface of the deodorant.

As described above, the deodorant of the present invention, which has been subjected to the odor preventing treatment of the deodorant and the active manganese oxide is further supported on the entire surface of the deodorant, is primarily capable of absorbing a malodorous gas or a harmful gas. It is difficult for the deodorant itself to emit odor, and it is possible to prevent the generation or release of the secondary odor-causing substance of the deodorant over time, and to prevent the generation of unpleasant odor even after long-term use. Further, according to the method for preventing deodorization of a deodorant of the present invention, since the deodorant is prepared by final treatment with an aqueous solution of manganese nitrate, the deodorant prepared by a slurry method using a conventional binder is used. Even in this case, since active manganese oxide is uniformly supported on the entire surface of the deodorant including the binder, generation of an unpleasant odor can be more effectively prevented.

Further, in order to sufficiently regenerate the conventional regenerating function of the deodorant, it is necessary to heat the deodorant to a temperature of 300 ° C. to 400 ° C. The deodorant whose surface is further impregnated and loaded with active manganese oxide can not only regenerate the deodorizing performance at a lower regeneration temperature of 150 to 300 ° C, preferably 200 to 250 ° C, but also remove the bad odor of the deodorant itself.

[0021]

The present invention will be described below in more detail with reference to Examples, Comparative Examples and Test Examples. However, the present invention is not limited at all by these examples.

Example 1 24 parts by weight of a pentasil type zeolite (silicalite S-115 manufactured by UOP) having a silica / alumina molar ratio of 250 parts by weight and 44 parts by weight of ion-exchanged water and Y having a silica / alumina molar ratio of 6 were used. Type zeolite (UOP LZY-84)
Was added with 12 parts by weight of a copper-substituted zeolite (hereinafter referred to as Cu-Y zeolite) obtained by ion-exchanging 6% by weight of copper in terms of Cu and 20 parts by weight of an alumina sol containing 20% by weight of alumina in terms of Al ₂ O ₃ , A slurry was prepared by mixing and pulverizing for 8 hours using a ball mill. A cordierite honeycomb carrier (Honeyserum manufactured by Nippon Insulators Co., Ltd .: 400 cells, 50 mm × 50 mm × 30 mm) was immersed in the slurry, pulled up, and the excess slurry was blown off with air, followed by drying at 150 ° C. for 1 hour. . The dried deodorant was calcined at a temperature of 350 ° C. for another hour. This operation was repeated once more to obtain 150 g of silicalite and 75 g of Cu per liter of deodorant.
A deodorant carrying -Y zeolite and 25 grams of alumina as a binder was prepared.

A manganese nitrate solution containing 15.4% by weight of Mn (manufactured by Tanaka Chemical Co., Ltd. [Mn (NO ₃ ) _2]
% By weight) with ion-exchanged water to obtain 10% in terms of Mn.
Prepare a manganese nitrate aqueous solution containing manganese nitrate by weight, immerse a deodorant in this manganese nitrate aqueous solution, pull up and blow air to remove excess manganese nitrate aqueous solution, and then dry at 120 ° C for 1 hour. Then, the dried deodorant is passed through air at 350 ° C. for 1 hour.
After calcination for an hour, deodorant A was obtained, in which active manganese oxide was additionally supported by 35 g in terms of MnO ₂ per liter of deodorant.

Comparative Example 1 The deodorizing agent used in Example 1 but not impregnated with manganese nitrate was designated as deodorizing agent a.

Comparative Example 2 In Example 1, 20 parts by weight of pentasil-type zeolite (silicalite S-115 manufactured by UOP) having a silica / alumina molar ratio of 250 parts by weight, Y-type zeolite having a ratio of 6 (UOP
Includes 10 parts by weight of Cu-Y zeolite obtained by ion-exchanging 6% by weight of copper in terms of Cu, 6 parts by weight of electrolytic manganese dioxide (FMH, manufactured by Tosoh Corporation) and 20% by weight in terms of alumina. Add 20 parts by weight of alumina sol,
In the same manner except that the slurry was prepared in the same manner as in Example 1, 150 g of silicalite, 75 g of Cu-Y zeolite, 45 g of electrolytic manganese dioxide in terms of MnO ₂ and 25 g per liter of deodorant were used. A deodorant b not impregnated with manganese nitrate supporting alumina as a binder was prepared.

Comparative Example 3 The procedure of Example 1 was repeated except that a silica sol containing 20% by weight of silica in terms of SiO ₂ was used instead of the alumina sol. Cu-Y zeolite,
And a deodorant c not impregnated with 25 g of manganese nitrate loaded with silica as a binder.

Comparative Example 4 In Example 1, a silica sol containing 20% by weight of silica in terms of SiO ₂ was used in place of the alumina sol, and the cordierite as an aggregate of ceramic fibers was used instead of the cordierite honeycomb carrier. Similarly, except that the slurry-supporting operation was once performed using a honeycomb carrier (Nichias honeycomb: 200 cells, 50 mm × 50 mm × 30 mm), 150 g of silicalite per liter of deodorant, 75 g, Cu-Y zeolite, and 25
A deodorant d not impregnated with manganese nitrate carrying silica as a binder was prepared.

Comparative Example 5 In Example 1, 44 parts by weight of ion-exchanged water, 12 parts by weight of silicalite used in Example 1, 14 parts by weight of electrolytic manganese dioxide (FMH manufactured by Tosoh Corporation), and copper carbonate (Japan) Deodorization was carried out in the same manner as in Example 1 except that 11 parts by weight of a chemical industry (including 63% by weight as Cu) and 20 parts by weight of the silica sol used in Comparative Example 4 were added. Deodorization without impregnating 75 g of silicalite per liter, 88 g of electrolytic manganese dioxide in terms of MnO ₂ , 44 g of copper oxide in terms of CuO and 25 g of manganese nitrate carrying silica as a binder Agent e was prepared.

Comparative Example 6 34 parts by weight of silicalite used in Example 1, Example 1
17 parts by weight of Cu-Y zeolite used in the above, 10 parts by weight of electrolytic manganese dioxide (FMH manufactured by Toso Co.), 25 parts by weight of alumina sol containing 20% by weight in terms of alumina, and 14 parts by weight of molding aid Add replacement water and mix
After kneading, extrusion molding was performed. Extruded 40
The 0 cell deodorant was dried at a temperature of 80 ° C. for 15 hours.
The dried deodorant is calcined for an additional hour at a temperature of 350 ° C. to give 196 grams of silicalite, 98 grams of Cu—Y zeolite, 61 grams of electrolytic manganese dioxide in terms of MnO ₂ and 29 grams of binder per liter of deodorant. A deodorant f containing alumina as-was prepared.

Comparative Example 7 In Example 1, pentasil-type zeolite (MFI manufactured by UOP) having a silica / alumina mole ratio of 40 parts by weight of ion-exchanged water was ion-exchanged with 5% by weight of copper in terms of Cu. 36 parts by weight of a copper-substituted zeolite (hereinafter referred to as Cu-MFI zeolite) and 20 parts by weight of an alumina sol containing 20% by weight in terms of alumina were added, and a slurry was prepared in the same manner as in Example 1, except that the slurry was prepared. A deodorant g not impregnated with 180 g of Cu-MFI zeolite per liter of deodorant and 20 g of manganese nitrate supporting alumina as a binder was prepared.

Comparative Example 8 In Example 1, pentasil-type zeolite (silicalite S-115 manufactured by UOP) having a silica / alumina molar ratio of 250 parts by weight in ion-exchanged water (44 parts by weight) was converted to Ag by 3%.
36 parts by weight containing silver by weight (hereinafter referred to as Ag-silicalite), and 20% by weight in terms of alumina
Deodorant 1 was prepared in the same manner as in Example 1 except that 20 parts by weight of silica sol containing
A deodorant h not impregnated with manganese nitrate supporting 180 g of Ag-silicalite and 20 g of silica as a binder per liter was prepared.

Example 2 In Example 1, the deodorant a of Comparative Example 1 was replaced with the deodorant b of Comparative Example 2, the deodorant c of Comparative Example 3, the deodorant d of Comparative Example 4, and the deodorant of Comparative Example 5. Agent e, deodorant f of Comparative Example 6, Comparative Example 7
Manganese nitrate aqueous solution treatment in the same manner as in Example 1 except that deodorant g of Comparative Example 8 and deodorant h of Comparative Example 8 were used,
Deodorizer B carrying 35 g of additional active manganese oxide in terms of MnO ₂ per liter of deodorant b, deodorant C carrying 35 g of additional active manganese oxide in terms of MnO ₂ per liter of deodorant c, MnO per 1 liter of deodorant d deodorant and the active manganese oxide 80 g and additionally loading with ₂ equivalent D, 35 grams of active manganese oxide deodorant e1 liters per MnO ₂ in terms additionally loading the deodorant E, active manganese oxide deodorant f1 liters per MnO ₂ in terms of F, deodorant g additionally supporting 40 g of
3 active manganese oxides per liter in terms of MnO ₂
A deodorant G additionally supporting 5 g and a deodorant H additionally supporting 35 g of active manganese oxide in terms of MnO ₂ per liter of deodorant h were obtained.

Example 3 In Example 1, the manganese nitrate aqueous solution containing 10% by weight of manganese nitrate in terms of Mn was replaced with 3 in terms of Mn.
Similarly, except that an aqueous solution of manganese nitrate containing manganese nitrate by weight of manganese nitrate and an aqueous solution of manganese nitrate containing 15% by weight of manganese nitrate in terms of Mn were used.
The active manganese oxide deodorant per liter MnO ₂ 6 grams of terms additionally loading the deodorant I and the active manganese oxide deodorants per liter MnO ₂ in terms of 50 g additionally loading the deodorant J were respectively obtained.

Evaluation Test Example 1 A sample deodorant was passed through a gas circulating air purifier using a sirocco fan installed in a conference room with a capacity of 42 N and a normal temperature and normal humidity, which smokes about 50 cigarettes a day. And the air purifier was operated for 12 hours in the daytime when people came in and out. After repeating this operation continuously for 30 days, the sample deodorant was taken out and put in a clean glass container, and the sample was evaluated based on the 6-grade evaluation shown in Table 1.
Odor was measured by human sensory evaluation. The sensory evaluation test
The odor from the deodorant (primary odor) caused by the primary adsorption of the sample deodorant, such as the tobacco odor and the odor in the conference room,
Substances adsorbed on the deodorant are changed to distinguish from secondary odors (secondary odors) such as acetic acid odor and mold odor, which are different from those that the deodorant adsorbs from inside the room, such as the tobacco odor and the odor in the conference room The results are shown in Table 2.

[0035]

[Table 1]

[0036]

[Table 2] Sample Primary odor Secondary odor A (Additional 35 g of MnO ₂ conversion to a) 0 B (Additional 35 g of MnO ₂ conversion to b) 0 C (Additional 35 g of MnO ₂ conversion to c) 0 1 D (additional support of 80 g in terms of MnO _{2 to} d) 0 E (additional support of 35 g in terms of MnO _{2 for} e) 0 0 F (additional support of 40 g in terms of MnO _{2 in} f) 0 0 G (35 g in terms of MnO _{2 in} terms of g) 0 H (additional support of 35 g in terms of MnO ₂ ) 0 1 I (additional support of 6 g in terms of MnO ₂ ) 22 J (additional support of 50 g in terms of MnO _{2 in} a) 0 a a 3 3 b 3 3 c 3 4 d 4 4 e 3 3 f 3 2 g 3 3 h 3 3

As is clear from Table 2, the deodorizing agent a, deodorizing agent c, deodorizing agent d, deodorizing agent g and deodorizing agent h of the comparative example not impregnated with manganese nitrate, and manganese nitrate before impregnating with manganese nitrate. Deodorant b, deodorant e and deodorant f containing all the odors from the deodorant (primary odor) due to the primary adsorption of the odor and the deodorant whose substance adsorbed on the deodorant has changed Has a sensory evaluation of 3 or more that clearly smells secondary odors (secondary odors) different from those adsorbed.
It is clear that the odor began to be generated by the aging. On the other hand, deodorant A, deodorant B, deodorant C, deodorant D, deodorant E, deodorant F, deodorant G, deodorant further impregnated with manganese nitrate by the method for preventing odor of a deodorant of the present invention. H and the deodorant J have undergone sensory evaluations of odorless or almost odorless, respectively, and the odorous gas or harmful gas of the deodorant impregnated with the aqueous solution of manganese nitrate by the odor preventive method of the present invention. The ability to prevent the generation of primary odors, which generate odors by adsorbing gas, and the generation of unpleasant odors, which generate unpleasant odors due to the chemical change of substances adsorbed by the deodorant over time. It has been proved that an unpleasant odor hardly occurs even when used for a long time. In addition, the deodorant I has undergone a sensory evaluation of 2 which slightly smells both the primary odor and the secondary odor, and the improvement of the prevention of odor generation is insufficient, but the amount of manganese nitrate impregnated is small. It is presumed to be caused by the above.

Evaluation Test Example 2 A stirring fan and 30 liters were placed inside a 60-liter test box.
Axial fan ventilation type deodorizer equipped with a sample deodorant cut into a size of 30 mm x 30 mm is installed and sealed, and tobacco (trade name: Mild Seven) is used with an axial fan suction type smoker.
After the test box was filled with two pieces of smoke, the agitating fan and the axial fan ventilation type deodorizer were operated for 20 minutes. Next, the sample deodorant to which the tobacco odor was adsorbed was taken out of the test box, and heated at 200 ° C. and 250 ° C.
Each of them was heated and regenerated at a temperature of 10 ° C. for 10 minutes. The sample deodorant obtained by repeating the odor regenerating operation five times was put in a clean glass container, and the odor was measured by a five-person sensory evaluation based on the six-point evaluation shown in Table 1 as in Evaluation Test Example 1. Table 3 shows the results.

[0039]

Table 3 Regeneration temperature 200 ° C Regeneration temperature 250 ° C Sample deodorant Primary malodor Secondary malodor Primary malodor Secondary malodor A 0 0 0 0 0 0 0 0 C 0 1 0 0 D 0 1 0 0 E 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 I 0 0 0 0 0 0 0 a 3 3 0 1 b 3 3 0 1 c 3 3 0 3 d 3 4 0 2e3202f2201g33301h3302

As is clear from Table 3, the deodorizing agent a, deodorizing agent c, deodorizing agent d, deodorizing agent g and deodorizing agent h of the comparative example not impregnated with manganese nitrate, and manganese nitrate before impregnation with manganese nitrate were used. The deodorant b, deodorant e, and deodorant f containing all have a sensory evaluation of 2 or more at a regeneration temperature of 200 ° C., at which the primary odor and the secondary odor are slightly odorous. It can be seen that at a temperature of ° C., regeneration was not sufficient. In addition, the deodorant of the comparative example, even at a regeneration temperature of 250 ° C., has a secondary odor different from that of the adsorbed deodorant in which the substance adsorbed on the deodorant has changed, and is not sufficiently regenerated. I understand. On the other hand, the deodorant I having a low manganese nitrate impregnated loading amount
Except for the deodorant A, deodorant B, deodorant C, deodorant D, and deodorant impregnated with an aqueous solution of manganese nitrate by the method for preventing odor of the deodorant of the present invention regenerated at a regeneration temperature of 200 ° C. E, deodorant F, deodorant G, deodorant H, and deodorant J have undergone sensory evaluations of odorless or almost odorless, respectively, and are impregnated with an aqueous solution of manganese nitrate according to the method for preventing odor of the deodorant of the present invention. It can be seen that the treated deodorant was sufficiently regenerated and the odor was removed. That is, by further impregnating the deodorant with an aqueous solution of manganese nitrate according to the method for preventing the deodorant of the deodorant of the present invention, the impregnated deodorant sufficiently removes the odor of the deodorant itself even at a low regeneration temperature of 200 ° C. Prove that it can be taken.

Evaluation Test Example 3 A stirring fan and 30 mm × 30 m were placed inside a 60-liter test box adjusted to a temperature of 25 ° C. and a humidity of 95% or more.
A sirocco fan ventilation type deodorizer equipped with a sample deodorizer cut out to mx 30 mm was installed and sealed, and then acetaldehyde was injected into the sample box, and the acetaldehyde concentration in the sample box was adjusted to 250 ppm, and the stirring fan and sirocco fan were used. Operation of the ventilated deodorizer was started. The acetaldehyde concentration 10 minutes after the start of the operation was measured by FID gas chromatography, and the acetaldehyde removal ratio with respect to the initial concentration was determined. Evaluation of acetaldehyde removal rate of sample deodorant not adsorbing tobacco odor In Test Example 2, the respective acetaldehyde removal rates regenerated and treated at 200 ° C. and 250 ° C. were determined as deodorization performance regeneration rates, and the results are shown in Table 4. Shown in

[0042]

Table 4 Deodorization performance regeneration rate (%) Sample deodorizer Regeneration temperature 200 ° C Regeneration temperature 250 ° C A 91 100 B 93 100 C 92 100 D 90 100 E 93 100 F 96 100 G 95 100 H 92 100 I 82 100 J 95 100 a 6882 b 70 88 c 69 81 d 74 80 e 73 90 f 73 86 g 67 82 h 68 85

As is evident from Table 4, an aqueous solution of manganese nitrate was obtained by the method for preventing odor of the deodorant of the present invention regenerated at a regeneration temperature of 200 ° C., except for the deodorant I, which has a low manganese nitrate impregnation amount. It can be seen that the deodorizing performance of the deodorant impregnated with the above was sufficiently recovered and recovered. That is, the deodorant is further impregnated with an aqueous solution of manganese nitrate, and the deodorant is regenerated at a low regeneration temperature of 200 ° C., so that not only can the odor of the deodorant itself be sufficiently removed, but also the deodorant can be sufficiently deodorized. The performance was also proved to be sufficiently restored.

[0044]

【effect】

1. The deodorant of the present invention is subjected to the method for preventing odor from being emitted, and the deodorant is impregnated with an aqueous solution of manganese nitrate to prevent the generation of unpleasant odor from the deodorant itself even after long-term use. be able to. 2. By performing the method for preventing deodorization of a deodorant of the present invention, not only can the deodorant performance of the deodorant be sufficiently regenerated and recovered at a low regeneration temperature, but also the odor attached to the deodorant itself can be removed. .

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Toshiya Nashida 1212 Yonomiya, Hiratsuka-shi, Kanagawa Prefecture JGC Universal Corporation

Claims (3)

[Claims] 1. A deodorant is immersed in an aqueous solution containing 5 to 16% by weight of manganese nitrate in terms of Mn, pulled up, blown off with excess aqueous solution with air, and uniformly impregnated and supported with manganese nitrate in the deodorant. After heating the manganese nitrate-supported deodorant to dry and remove attached water and water of crystallization, 200 to 40
A deodorizing treatment method for a deodorant, which comprises decomposing and firing at a temperature of 0 ° C. to convert the supported manganese nitrate into active manganese oxide. 2. The method according to claim 1, wherein the active manganese oxide is fine manganese dioxide particles composed mostly of crystalline. 3. The method according to claim 1, wherein 10 to 200 g of activated manganese oxide is supported per liter of deodorant in terms of MnO ₂ .