JPH08243383A - Hydrphobic deodorant and method for regenerating same - Google Patents

Abstract

PURPOSE: To obtain a deodorant exhibiting deodorizing ability independently of moisture in gas to be treated even in an environment at high humidity and capable of restoring deodorizing performance by regeneration by heating. CONSTITUTION: This hydrophobic deodorant consists of a carrier, an adsorptive layer of hydrophobic zeolite formed on the carrier and a catalytic compsn. consisting of manganese dioxide and copper oxide carried on the adsorptive layer. The ratio of silica to alumina in the zeolite is >=100. This deodorant is regenerated after use by heating to 100-500 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention exhibits a high deodorizing ability even in a high humidity environment for adsorbing, decomposing and removing various malodorous substances generated when kitchen refuse (raw garbage) is heated or fermented. The present invention relates to a hydrophobic deodorizing material, and further relates to a heat regeneration treatment method thereof.

[0002]

2. Description of the Related Art A foul odor is generated when kitchen waste (garbage) discharged from various kitchens for home or business use is heated or fermented. As such malodorous substances, various compounds such as ammonia, nitrogen compounds such as amines, alcohols, aldehydes, organic acids such as acetic acid, hydrogen sulfide, sulfur compounds such as mercaptan, dimethyl sulfide, and dimethyl disulfide can be used. Mention may be made of substances.

Conventionally, various proposals have been made to remove these malodorous substances by using an adsorption deodorant or a catalyst.

For example, in JP-A-6-711168, Al ₂ O ₃ is 20 to 65% by weight, SiO ₂ is 5 to 55% by weight, and manganese oxide is 5 to 50% by weight in terms of MnO. Disclosed is a deodorizing material, which is constituted by a molded body containing 2 to 50% by weight of copper oxide in terms of CuO. Further, it is taught that these materials can be adhered to a ceramic carrier, and it is a deodorizing material capable of removing various odors generated in a refrigerator, and particularly capable of removing methyl sulfide with high efficiency. Is stated.

Japanese Unexamined Patent Publication (Kokai) No. 6-26671 discloses a non-precious metal of chromium, nickel, iron, cobalt, copper, zinc, manganese, or the entire monolith-type catalyst molded body forming part.
A catalyst comprising a transition metal selected from a noble metal and / or an oxide thereof is 20 to 80 WT% and SiO ₂ is 10 to 65.
WT%, Al ₂ O ₃ 0.2 to 15 WT%, MgO 1 to
A catalyst molded body containing 25 WT% is disclosed, and it is described that in a monolith type that does not cause an increase in pressure loss with time, deterioration in catalyst activity performance with time is prevented and stable quality is always maintained. ing.

Japanese Unexamined Patent Publication No. 7-16465 discloses manganese dioxide in an amount of 10 to 70% by weight, activated carbon and / or activated carbon fiber in an amount of 25 to 85% by weight, copper, iron, nickel, cobalt, vanadium, platinum and gold. 3 to 20 of at least one oxide selected from the group consisting of oxides
A deodorizing member characterized by containing it by weight% is disclosed, and it is described that it exhibits excellent deodorizing performance without generation of a secondary bad odor from the deodorizing member. However, there is no mention of a method of reusing a deodorizing member whose deodorizing performance has been lowered by using it and repeatedly using it.

[0007]

Conventionally, it has been known that activated carbon, activated alumina, silica gel, zeolite or the like is used as an adsorbent, and as described above, various deodorizing materials have been proposed before the present application. Therefore, a deodorizing material combining alumina, silica, manganese oxide, and copper oxide is also known before the present application.

However, since the garbage treatment involves generation of a large amount of water, conventional adsorbing deodorants cannot cope with such a large amount of water, so that the adsorbing ability is rapidly lost and a sufficient deodorizing effect cannot be exerted. . Therefore, there is a demand for the development of a hydrophobic deodorizing material capable of maintaining a high deodorizing treatment ability even in this high humidity environment.

[0009]

Means for Solving the Problems As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that a deodorizing treatment is carried out at room temperature by absorbing and reacting a malodorous substance generated during the treatment of garbage. Found that a catalyst that effectively uses reactions such as physical adsorption, chemical adsorption, and sweetening is indispensable. Furthermore, even in a high-humidity environment, the deodorizing treatment ability is exerted without being affected by moisture in the treated gas. We have succeeded in developing a hydrophobic deodorizing material that can recover the deodorizing performance by heating and regenerating.

That is, the present invention relates to a carrier, an adsorption layer formed on the carrier, which is made of a hydrophobic zeolite having a silica / alumina ratio of at least 100, and a catalyst made of manganese dioxide and copper oxide, which is supported on the adsorption layer. component,
And a hydrophobic deodorizing material.

The present invention also provides a carrier, an adsorption layer formed on the carrier, which is made of a hydrophobic zeolite having a silica / alumina ratio of at least 100, and a catalyst made of manganese dioxide and copper oxide, which is supported on the adsorption layer. The present invention relates to a method for regenerating a hydrophobic deodorizing material, which comprises subjecting a hydrophobic deodorizing material comprising components to a heating regeneration treatment at a temperature of 150 to 500 ° C.

One component of the hydrophobic deodorizing material of the present invention is a carrier, and the carrier material is not particularly limited, but a porous carrier is usually used, and the reaction gas can flow and pressure loss is reduced. It is preferable that the carrier is few. For example, inorganic carriers such as cordierite, alumina, silica-alumina, titania silica, zeolite, sepiolite, and zeolite-sepiolite mixture are suitable. The carrier can have a honeycomb shape, a sponge shape, a mat shape, a woven cloth shape, a plate shape, a cylindrical shape, a granular shape, or the like, but particularly a honeycomb structure or a three-dimensional net structure in which the reaction gas can easily flow. Is preferred. The cell shape of the honeycomb is arbitrary,
It may have a polygonal shape such as a triangle, a square, a pentagon, a hexagon, or a corrugated shape. For example, Japanese Patent Publication Sho-59-
Assembled of ceramic fibers (Hanicle carrier) as proposed in 15028, that is, selected from inorganic fibers such as silica fibers, alumina fibers, aluminosilicate fibers, zirconia fibers, etc., which are bonded to each other by silica gel. A honeycomb structure constituted by laminating sheet-shaped aggregates of ceramic fibers in a honeycomb shape has a large pressure surface area, a large geometric surface area, and a high water content, and thus can support a large amount of active ingredients. preferable.

Another component of the hydrophobic deodorant material of the present invention is zeolite having excellent hydrophobicity (water resistance) which constitutes the adsorption layer for malodorous substances.

The hydrophobic zeolite that can be used in the present invention is
A natural zeolite such as chabazite, mordenite, erionite, faujasite and clinoptilolite, a synthetic zeolite such as zeolite A, zeolite X, zeolite Y, zeolite L, omega zeolite and ZSM-5, and a silica / alumina ratio. It is preferable that the alumina is treated so as to be at least 100.

More preferred is crystalline silica containing almost no alumina. That is, silicalite, with silicalite being most preferred. Since silicalite contains almost no alumina, it has a very small ion exchange capacity, and is hydrophobic and organic. Typical silicalite the following composition _{formula: R 2 O: 0~1.5M 2 O} : <0.05Al 2 O 3: 40~7
0SiO ₂ (In the formula, R represents a tetraethylammonium ion,
M represents an alkali metal cation. ).
This silicalite can also be pyrolyzed by firing to remove organic cations. In the present invention, silicalite before firing or silicalite after firing can be used. As described above, silicalite does not contain alumina, but actually alumina as an impurity contained in the raw material at the time of production may remain in silicalite as the final product. Such small amounts of alumina do not affect the properties of silicalite. Preferred silicalites that can be used in the present invention have a silica / alumina ratio of at least 100, usually 150 or more, preferably 250 or more. For more details on the production and properties of silicalite, see JP-A-54-72795, JP-B-56-40084, and Nature, Volume 271, 5645, issued February 9, 1978.
, Pages 512-516, "Silicalite, a novel hydrophobic crystalline silica molecular sieve".

The amount of the adsorption layer supported on the carrier is 15 to 40% by weight, preferably 20 to 35% by weight, more preferably 25 to 30% by weight, based on the hydrophobic deodorant.
If the loading amount is less than 5% by weight, the malodorous component adsorption effect is poor, and if it exceeds 40% by weight, not only is it difficult to prepare a slurry solution for loading, but also the strength is not obtained and the adsorption layer peels off. Cheap.

Another component of the hydrophobic deodorant material of the present invention is a catalyst component, which is composed of manganese dioxide and copper oxide. The manganese dioxide and the copper oxide may be supported as individual oxides, or may be supported in the form of a composite oxide. The supported amount of manganese dioxide is 5 to 25% by weight, preferably 10 to 20% by weight, calculated as MnO _{2 with} respect to the hydrophobic deodorizing material. If it is less than 5% by weight, the deodorizing effect cannot be expected, and if it exceeds 25% by weight, it is difficult to carry it, and strength is not obtained, and peeling easily occurs. The supported amount of copper oxide is CuO with respect to the hydrophobic deodorant.
2 to 20% by weight, preferably 3 to 15% by weight,
More preferably, it is 3 to 10% by weight. If it is less than 2% by weight, the deodorizing effect cannot be expected, and if it exceeds 20% by weight, it is difficult to carry it, and strength is not obtained, and peeling easily occurs.

Mercaptan, which is one of the malodorous substances, is hardly physically adsorbed in the adsorption layer, and deodorization by physical adsorption is substantially impossible. However, the catalyst component composed of manganese dioxide and copper oxide is converted into dimethyldisulfide having a low odor intensity, and the converted dimethyldisulfide is easily adsorbed and removed by the adsorption layer.

Ethyl alcohol and acetaldehyde produced by the garbage treatment have a low odor intensity by themselves, but after being adsorbed by the deodorizing material, they react with time to change into acetic acid. Acetic acid has a high odor intensity and produces a strong malodor even in a small amount. The physical adsorption of acetic acid in the adsorption layer is insufficient, and deodorization by chemisorption by the catalyst component of the present invention is necessary.

By continuously performing the deodorizing treatment, a malodorous substance is occluded in the hydrophobic deodorizing material of the present invention by physical adsorption or chemical adsorption, and the deodorizing performance is deteriorated. The hydrophobic deodorizing material having a reduced deodorizing performance is treated at 150 to 500 ° C, preferably 200 to 350 ° C, more preferably 250 to 3 ° C.
It was found that the heating and regeneration treatment at a temperature of 00 ° C. makes it possible to recover the deodorizing performance, and it is possible to perform the heating and regeneration treatment of the deodorizing material having a reduced deodorizing performance. Regeneration temperature is 15
If the temperature is lower than 0 ° C, the odor cannot be sufficiently removed, and if the temperature is higher than 500 ° C, the catalyst component may change its shape or the carrier may be adversely affected. In addition, extra heat energy is required, which is economically disadvantageous. Ammonia, which is one of the malodorous substances, is decomposed into nitrogen and water by heat regeneration treatment. At this time, the catalyst components manganese dioxide and copper oxide act effectively as denitration catalysts, and harmful NOx is hardly generated. Acetate, one of the other malodorous substances, and other malodorous hydrocarbons are oxidatively decomposed into water and carbon dioxide.

Further, one of the malodorous substances, mercaptan, is converted into dimethyldisulfide having a low odor intensity and stored therein. This dimethyldisulfide is
It is decomposed into sulfur monoxide and sulfur dioxide by heat regeneration treatment. Sulfur monoxide and sulfur dioxide produced by this heat regeneration treatment are stored in the hydrophobic deodorizing material of the present invention and are not released from the deodorizing material. That is, since harmful SOx is not released, the environment is not polluted. The original deodorizing performance is hardly affected, although the oxidizing performance is slightly lowered by the absorption of sulfur monoxide and sulfur dioxide.

By the way, in the heating regeneration treatment, before the temperature of the deodorizing material reaches the activation temperature of the catalyst component (about 150 ° C. or higher), some of the malodorous substances stored in the deodorizing material are desorbed. Some are released. 100 to 500 heat-regenerated exhaust gas containing these malodorous substances released from the deodorizing material before the catalyst component reaches the activation temperature and harmful components not decomposed by the catalyst component of the deodorizing material.
It is preferable to carry out the oxidative decomposition treatment with an oxidation catalyst heated to an activation temperature of ℃, preferably 250 to 300 ℃.
A typical active component of the oxidation catalyst is a platinum group metal, preferably platinum, which is highly active even at low temperatures. Sulfur compounds are not preferable because they act as catalyst poisons on platinum catalysts. Therefore, the hydrophobic deodorant material of the present invention which does not release sulfur monoxide and sulfur dioxide produced by the heat regeneration treatment has an excellent effect of not lowering the catalytic activity of the platinum group catalyst even when used in combination with the platinum group catalyst. .

[0023]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

1. Preparation of adsorption layer (1) Silicalite adsorption layer 40.0 kg Snowtex (S
(containing 20% by weight of iO ₂ ) was added to 27.5 kg of ion-exchanged water to prepare a binder solution, and 46 kg of PURAS IV-420 manufactured by UOP Co. having a silica / alumina ratio of 400 or more was stirred with a propeller. The mixture was added with stirring with a machine to prepare 113.5 Kg of a slurry solution having a solid content of 47.5% by weight (SiO ₂ : 7.0% by weight, silicalite: 40.5% by weight). Nichias hanicle carrier (600 cells, dimensions 230 mm x 90 mm x 20 mm), which is an aggregate of ceramic fibers
The above-mentioned slurry solution was sprinkled on it, and the excess slurry was blown with air to remove it, and then dried at a temperature of 150 ° C. for 3 hours. The dried carrier was calcined at a temperature of 380 ° C. for 1 hour to prepare an adsorption carrier A coated with 130 g of solid content (containing 110 g / l of silicalite) per liter of the carrier.

(2) Mordenite zeolite adsorption layer 450 g of Snowtex (SiO
20% by weight as ₂ ) was added to 950 g of ion-exchanged water to prepare a binder solution, and 600 g of silica / alumina ratio of 11 LOP-LZM-5 mordenite zeolite having a silica / alumina ratio of 11 was added to the binder solution using a propeller stirrer. The mixture was charged with stirring to prepare 2000 g of a slurry solution having a solid content of 34.5% by weight (SiO ₂ : 4.5% by weight, mordenite zeolite: 30.0% by weight). Similarly, this slurry solution was used as a nicicle carrier (6
No. 00 cell, size 230 mm × 90 mm × 20 mm), and the excess slurry is blown off with air to remove, and then dried at a temperature of 150 ° C. for 3 hours.
Calcination at a temperature of 80 ° C. for 1 hour gives 9 per liter of carrier.
An adsorption carrier B coated with 0 g of solid content (containing 78 g / liter of mordenite zeolite) was prepared.

2. Preparation of Impregnation Solution (1) Manganese Nitrate Solution A manganese nitrate solution (containing 50% by weight as Mn (NO ₃ ) ₂ ) manufactured by Tanaka Chemical Co., containing 15.4% by weight in terms of Mn was used. (2) Copper nitrate solution 354 g of ion-exchanged water was added to 500 g of copper nitrate [Cu (NO ₃ ) ₂ .3H ₂ O] crystals to be dissolved and converted to Cu to be 1
A copper nitrate solution containing 5.4% by weight was prepared. (3) Manganese nitrate / copper nitrate solution A 600 g of the manganese nitrate solution (converted to Mn is 1
5.4% by weight) and 200 g of the copper nitrate solution (C
mixed with 15.4 wt% (converted to u) to obtain Mn
Solution of manganese nitrate / copper nitrate (Mn: Cu) containing 11.5% by weight in terms of Mn and 3.85% by weight in terms of Cu.
A weight ratio = 3: 1) was prepared. (4) Manganese nitrate / copper nitrate solution B To 600 g of the above 15.4% manganese nitrate solution, 11
Manganese nitrate containing 7 g of copper nitrate [Cu (NO ₃ ) ₂ .3H ₂ O] crystals dissolved therein and containing 12.9% by weight in terms of Mn and 4.29% by weight in terms of Cu. A copper nitrate solution (Mn: Cu weight ratio = 3: 1) was prepared.

3. Preparation of Catalyst Example 1 The adsorption carrier A was immersed in a manganese nitrate / copper nitrate solution A, taken out, and the excess impregnating solution was blown with air to remove it, followed by drying at a temperature of 150 ° C. for 3 hours. Baking for 1 hour at a temperature of 380 ° C while flowing air, and 60 g / l of MnO ₂ · CuO with respect to the hydrophobic deodorizing material
The deodorizing material A carrying was prepared. The composition of the deodorizing material A was such that silicalite was 29.7% by weight, manganese dioxide was 12.2% by weight in terms of MnO ₂ , and copper oxide was 4.0% by weight in terms of CuO with respect to the total amount. It was

Example 2 In the same manner as in Example 1 except that the manganese nitrate / copper nitrate solution B was used as the impregnation solution, 100 g / liter of MnO ₂ .CuO was added to the hydrophobic deodorizing material.
The deodorizing material B carrying was prepared. The composition of the deodorizing material B was such that silicalite was 26.8% by weight, manganese dioxide was 18.3% by weight in terms of MnO ₂ , and copper oxide was 6.1% by weight in terms of CuO with respect to the total amount. It was

Comparative Example 1 In the same manner as in Example 1 except that the manganese nitrate solution (containing 15.4% by weight in terms of Mn) was used as the impregnating solution, a hydrophobic deodorizing material was prepared. 60g
A deodorizing material M carrying 1 / liter of MnO ₂ was prepared.
The composition of the deodorizing material M is such that silicalite is 2
9.7% by weight, manganese dioxide is 1 in terms of MnO _2.
It was 6.2% by weight.

Comparative Example 2 The copper nitrate solution (C
A deodorizing material N supporting 60 g / liter of CuO was prepared with respect to the hydrophobic deodorizing material in the same manner as in Example 1 except that 15.4% by weight in terms of u was used). Deodorant material N
In the composition, the silicalite was 29.7 wt% and the copper oxide was 16.2 wt% in terms of CuO with respect to the total amount.

Comparative Example 3 In the same manner as in Example 1 except that the adsorbent B was used as the adsorbent, the hydrophobic deodorant was mixed with the deodorant 6%.
Deodorant O supporting 0 g / l of MnO ₂ · CuO
Was adjusted. The composition of the deodorizing material O is 23.6% by weight of mordenite zeolite, 13.7% by weight of manganese dioxide in terms of MnO ₂ and Cu of Cu oxide.
It was 4.4% by weight in terms of O.

4. Deodorization performance evaluation method A sample cut into a size of 57 mm x 70 mm x 20 mm (volume: about 80 ml) was left overnight in saturated water vapor in a desiccator filled with water to be sufficiently absorbed. It was confirmed that the sample, which had been left to absorb moisture overnight, stopped increasing in weight and showed a constant weight value, and saturated moisture absorption.

(1) Measurement of Amount of Adsorption of Ammonia The moisture-absorbed sample was placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C., and concentrated ammonia gas 9.6 while rotating a fan for atmospheric circulation. The initial concentration of ammonia in the reaction vessel is adjusted to 600 by injecting milliliter into the reaction vessel.
Adjusted to ppm / 16 liter. After leaving in this state for 30 minutes, the ammonia concentration was measured by a detector tube.
When no ammonia gas was detected, this operation was repeated many times to create an adsorption isotherm at an ammonia gas temperature of 25 ° C. The amount of adsorbed ammonia at the equilibrium concentration of 1 ppm was determined from the adsorption isotherm, and the amount of adsorbed ammonia (mg) per 80 ml of the sample at 1 ppm was calculated and shown in Table 1.

[0034]

[Table 1] Hanicle carrier Adsorption carrier A Deodorizing material M Deodorizing material O Deodorizing material A Deodorizing material B Ammonia adsorption amount 1.6 18 25 17 34 45 (mg)

As is clear from Table 1, sufficient adsorption of ammonia was not carried out only by the hanicle carrier having no adsorption layer, and the adsorption carrier A having an adsorption layer made of hydrophobic silicalite was It can be seen that the amount of adsorption of ammonia is increasing due to physical adsorption. The deodorizing material M, the deodorizing material A and the deodorizing material B which have a catalyst component in addition to the adsorption layer,
In addition to physical adsorption, an increase in the amount of ammonia adsorbed by chemical adsorption was observed, and the deodorizing material A and deodorizing material B of the present invention carrying both manganese dioxide and copper oxide were simply deodorizing materials carrying only manganese dioxide. It has been proved to have a better ammonia adsorption capacity than M. The deodorizing material O having an adsorption layer made of mordenite zeolite having no hydrophobicity is the deodorizing material A of the present invention having an adsorption layer made of silicalite having hydrophobicity, which is not subjected to the moisture absorption and adsorption treatment.
And has an ammonia adsorption capacity equivalent to that of the deodorizing material B. However, the one that has been subjected to moisture absorption shows only the amount of ammonia adsorbed by chemisorption by the catalyst component as is clear from Table 1, and the adsorption layer of mordenite zeolite has a significantly higher ammonia adsorption capacity by absorbing moisture. It turns out that it is almost non-functional.
That is, the deodorizing material A and the deodorizing material B of the present invention having the adsorption layer made of silicalite having hydrophobicity and the catalyst component made of manganese dioxide and copper oxide have excellent adsorption of ammonia even under severe conditions of high humidity. Proved to have performance.

(2) Measurement of Decomposition Rate of Methyl Mercaptan Although mercaptan is hardly physically adsorbed, it is converted to dimethyldisulfide by the catalyst component, and the converted dimethyldisulfide can be adsorbed and removed by physical adsorption. A 1 ppm methyl mercaptan sample gas was prepared by mixing 1000 ppm methyl mercaptan at a rate of 60 milliliters / minute with air having a flow rate of 60 liters / minute adjusted to a relative humidity of 90% through a humidifier. A sufficiently hygroscopic sample was placed in a flow reaction tube, and 1 ppm of methyl mercaptan sample gas prepared as described above and kept at a temperature of 25 ° C. was flowed at a flow rate of 60 ml / min (S
V value = 45000 Hr ^-1 ). The inlet concentration and the outlet concentration of methyl mercaptan in the flow reaction tube were measured by an FID gas chromatography-analyzer, and the decomposition rate (%) after 24 hours was determined, and the results are shown in Table 2.

[0037]

[Table 2] Hanicle carrier Adsorption carrier A Deodorizing material M Deodorizing material N Deodorizing material O Deodorizing material A 0 0 90 10 96 96 98.8 Degradation rate (%) of methyl mercaptan

As is clear from Table 2, the mercaptan in the hanicle carrier or the adsorption carrier A having no catalyst component is
Not converted to dimethyl disulfide. Further, even the deodorizing material N supporting copper oxide was hardly converted to dimethyldisulfide. However, the deodorizing material M supporting manganese dioxide easily converts mercaptan into dimethyldisulfide, and further, the deodorizing material O and the deodorizing material A of the present invention having a catalyst component composed of manganese dioxide and copper oxide are more remarkable. It has been proved that it has the resolution of various methyl mercaptans. However, as will be described later, the deodorizing material O cannot adsorb and remove the converted dimethyldisulfide, and thus produces a bad odor of dimethyldisulfide.

(3) Measurement of the amount of dimethyldisulfide adsorbed The moisture-absorbed sample was placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C., and the dimethyldisulfide solution was rotated while rotating a fan for atmospheric circulation. 6 microliters was injected into the reaction tank to adjust the initial concentration of dimethyldisulfide in the reaction tank to 90 ppm / 16 liter. After standing in this state for 30 minutes to reach adsorption equilibrium, the concentration of dimethyldisulfide was measured by an FID gas chromatography analyzer. This operation was repeated 4 times to prepare an adsorption isotherm of dimethyldisulfide at a temperature of 25 ° C. The adsorption amount of dimethyldisulfide at the equilibrium concentration of 0.1 ppm was determined from the adsorption isotherm,
The adsorbed amount (mg) of dimethyldisulfide per 80 ml of the sample at 0.1 ppm was calculated and shown in Table 3.

[0040]

[Table 3] Hanicle carrier Adsorption carrier A Deodorant M Deodorant O Deodorant A Dimethyldisulfide 0.3 23 22 1.3 24 Adsorption amount (mg) Table 3 clearly shows that silicalite having hydrophobicity is high. It has been proved that it has an adsorption capacity for dimethyldisulfide.

(4) Measurement of adsorbed amount of acetic acid The moisture-absorbed sample was placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C., and 5 microliters of acetic acid was reacted while rotating a fan for air circulation. The initial concentration of acetic acid in the reaction tank was adjusted to 100 ppm / 16 liter by dropping it on a heater installed in the tank and evaporating it.
After leaving it in this state for 30 minutes, the acetic acid concentration was measured with a detector tube. When acetic acid is not detected, this operation is repeated many times until the acetic acid concentration is detected by the detection tube (detection limit concentration of acetic acid detected by the detection tube: 0.1 ppm) until the concentration is below the detection limit concentration (0 ppm). The amount of acetic acid adsorbed (mg) was measured and the results are shown in Table 4.

[0042]

[Table 4] Adsorption carrier A Deodorant M Deodorant O Deodorant A Deodorant B Acetic acid adsorption amount 5 or less 10 15 5 20 25 (mg)

As is clear from Table 4, it is obvious that the hanicle carrier having no adsorption layer has no acetic acid odor even if it is the deodorizing material O having an adsorption layer made of adsorption-treated non-hydrophobic mordenite zeolite. Cannot be removed. As for the bad odor caused by organic acid such as acetic acid odor, it is clear from Table 4 that the deodorization by the chemical adsorption by the catalyst component is more effective than the deodorization by the physical adsorption by the partial pressure effect. It was proved from the fact that the deodorizing material M having it and the deodorizing materials A and B of the present invention have excellent acetic acid adsorption ability. Further, from the deodorizing material M supporting manganese dioxide, the deodorizing material A and the deodorizing material B of the present invention having a catalyst component composed of manganese dioxide and copper oxide.
However, it has an excellent ability to adsorb and remove acetic acid. That is, the deodorizing material A and the deodorizing material B of the present invention having the adsorption layer made of silicalite having hydrophobicity and the catalyst component made of manganese dioxide and copper oxide are excellent in the adsorption of acetic acid even under severe conditions of high humidity. Proved to have performance.

Example 3 Regeneration test of deodorizing material after adsorption of ammonia By the same method as the measurement method of the adsorption amount of monia, dimensions 57 mm ×
Using a sample cut into a size of 70 mm × 20 mm (volume: about 80 ml), concentrated ammonia gas 9.6
After injecting milliliter into the reaction tank and leaving it for 30 minutes to reach the adsorption equilibrium, the ammonia concentration was measured by a detector tube. This operation was repeated to inject 96 ml of ammonia in total to create an adsorption isotherm at a temperature of 25 ° C. of the ammonia gas to determine the adsorption amount (mg) of ammonia per 80 ml of the sample. The sample that reached the adsorption equilibrium was placed in an electric furnace and heated and regenerated by changing the regeneration temperature and regeneration time. Similarly, the amount of adsorbed ammonia of the sample subjected to the regeneration treatment is also obtained, and the regeneration rate (%) is obtained with the amount of adsorbed ammonia of the sample before regeneration being 100. The regeneration time at which the regeneration rate reaches 100% at each temperature is obtained. Table 5 shows the results.

[0045]

[Table 5] Regeneration temperature (° C) 200 250 300 Regeneration time (min) 60 20 10 As is clear from Table 5, even at a temperature of 200 ° C or higher, even a deodorizing material that has adsorbed ammonia and has a reduced adsorption capacity. It has been proved that it can be heated and regenerated. NOx was not detected in the gas discharged from the electric furnace.

Example 4 Regeneration of Deodorant Material after Adsorption of Acetaldehyde The sample was placed in a 16-liter glass reaction tank kept at a temperature of 25 ° C., and 4 microliters of acetaldehyde solution was reacted while rotating a fan for circulating air. After the mixture was poured into the tank and left for 15 minutes to reach adsorption equilibrium, the concentration of acetaldehyde was measured by a FID gas chromatography analyzer. By repeating this operation, a total of 56 microliters of acetaldehyde was injected to prepare an adsorption isotherm at a temperature of acetaldehyde of 25 ° C. The adsorbed amount of acetaldehyde at the equilibrium concentration of 0.1 ppm was obtained from the adsorption isotherm, and the adsorbed amount of acetaldehyde per 80 ml of the sample at 0.1 ppm (mg)
Was calculated. The sample that reached the adsorption equilibrium was placed in an electric furnace in the same manner as in Example 3 and was heated and regenerated by changing the regeneration temperature and regeneration time. Similarly, the amount of acetaldehyde adsorbed on the regenerated sample was calculated, and the regeneration rate (%) was calculated with the amount of acetaldehyde adsorbed on the sample before regeneration being 100. The regeneration time at which the regeneration rate reached 100% at each temperature was calculated. Table 6 shows the results.

[0047]

[Table 6] Regeneration temperature (° C) 150 200 250 Regeneration time (min) 60 20 10 As is clear from Table 6, even a deodorant material that has adsorbed acetaldehyde and has a reduced adsorption capacity is still at a temperature of 150 ° C or higher. It has been proved that it can be heated and regenerated.

Example 5 Regeneration of Deodorizing Material after Adsorption of Dimethyldisulfide In Example 4, dimethyldisulfide was used instead of acetaldehyde, left for 1 hour to reach adsorption equilibrium, and then the concentration of dimethyldisulfide was changed to FID. A total of 100 microliters of dimethyldisulfide was injected to prepare an adsorption isotherm at a temperature of 25 ° C. of dimethyldisulfide in the same manner as in Example 4 except that the measurement was performed with a gas chromatography analyzer. The adsorption amount of dimethyldisulfide at the equilibrium concentration of 0.1 ppm was obtained from the adsorption isotherm, and the sample 80 at the concentration of 0.1 ppm was obtained.
The amount of dimethyldisulfide adsorbed per milliliter (mg) was calculated.

The sample that reached the adsorption equilibrium was placed in an electric furnace in the same manner as in Example 3 and was heated and regenerated by changing the regeneration temperature and regeneration time. At a regeneration temperature of 150 ° C., even if the sample was heated and regenerated for 1 hour, a bad odor remained in the sample, and the regenerating treatment could not be performed sufficiently. When the regeneration temperature was 200 ° C., the regenerated sample was heated for 10 minutes, and no bad odor was sensed in the regenerated sample. Temperature rise desorption analysis of exhaust gas generated during heat regeneration treatment (TPD gas chromatography mass spectrometry)
However, the generation of SOx was not recognized at any regeneration treatment temperature up to 500 ° C. Further, it was confirmed that the weight of the sample increased due to the adsorption of the sulfur component by the heat regeneration treatment. The adsorption capacity of the heat-regenerated sample was slightly lower than that of the new deodorant material by the first heat-regeneration treatment, but even after repeated heat-regeneration treatments, the adsorption capacity decreased little and became almost constant, and the adsorption capacity was stable. . That is, it was proved that the poisoning by the stored sulfur compound was hardly affected.

Example 6 Regeneration of deodorizing material after adsorption of acetic acid After acetic acid was sufficiently adsorbed to reach an adsorption equilibrium, temperature-programmed oxidation analysis (TPO FID gas chromatography analysis) revealed that acetic acid was oxidized at 200 ° C to 250 ° C. It was confirmed that it was disassembled. As described above, by continuously performing the deodorizing treatment, the malodorous substance is occluded by the hydrophobic deodorizing material of the present invention by physical adsorption or chemical adsorption, and the deodorizing performance is reduced to a hydrophobic deodorizing material at a temperature of 150 to 500 ° C. The deodorizing performance can be recovered by heating and regenerating with
It was proved that it is possible to heat-regenerate the deodorant material having a reduced deodorizing performance.

Example 7 In the exhaust gas outlet of the electric furnace for regeneration heating treatment, 3
A platinum catalyst heated to a temperature of 00 ° C. was installed, and exhaust gas was post-treated. The malodorous substances emitted when the temperature rises below the activation temperature of the sample are completely treated by the platinum catalyst,
No odor was detected by the sense of smell. Even if the sample on which the sulfur-based malodorous substance, for example, dimethyldisulfide, was adsorbed was repeatedly subjected to the thermal regeneration treatment, the activity of the platinum catalyst was not lowered. This is because, of course, the sulfur-based compound, which is the largest catalyst poison, is not discharged out of the system by the heat regeneration treatment.

[0052]

【effect】

1. Even in a high-humidity environment, a high deodorizing treatment capacity can be maintained for a long time. 2. The deodorizing ability can be regenerated many times by the heat regeneration treatment. 3. In the decomposing ability of methyl mercaptan, each adsorption ability of ammonia, dimethyldisulfide, acetic acid, and each regeneration ability of the deodorizing material after adsorbing ammonia, dimethyldisulfide, acetic acid, and acetaldehyde, the hydrophobic deodorizing material of the present invention is , In each case, excellent results were paid. On the other hand, those lacking the specific requirements for the adsorption layer or those lacking any of the catalyst components showed some defects in any of the adsorption capacity or the regeneration capacity. 4. Since SOx and NOx are not emitted along with the heating and regeneration treatment, the surrounding environment is not polluted. 5. Since the sulfur compound which becomes a catalyst poison is not discharged during the heating regeneration treatment, the exhaust gas can be easily subjected to the secondary treatment by the oxidation catalyst to further enhance the deodorizing effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01J 23/89 B01J 29/035 29/035 29/90 29/90 B01D 53/36 ZABH

Claims (10)

[Claims] 1. A carrier, an adsorption layer made of hydrophobic zeolite having a silica / alumina ratio of at least 100 or more formed thereon, and a catalyst component made of manganese dioxide and copper oxide supported on the adsorption layer. A hydrophobic deodorizing material characterized in that 2. The honeycomb structure, wherein the carrier is formed by stacking sheet-shaped aggregates of ceramic fibers bonded to each other by silica gel in a honeycomb shape.
The hydrophobic deodorizing material described. 3. The hydrophobic deodorizing material according to claim 1, wherein the hydrophobic zeolite is silicalite. 4. The hydrophobic deodorizing material according to claim 1, 2 or 3, wherein the amount of the adsorption layer carried is 15 to 40% by weight based on the hydrophobic deodorizing material. 5. The hydrophobic deodorizing material according to claim 1, wherein the supported amount of manganese dioxide is 5 to 25% by weight in terms of MnO _{2 with} respect to the hydrophobic deodorizing material. 6. The amount of the copper oxide supported is 2 to 20% by weight in terms of CuO with respect to the hydrophobic deodorizing material.
The hydrophobic deodorizing material described in 2, 3, 4 or 5. 7. A method for regenerating a hydrophobic deodorant material, which comprises subjecting the hydrophobic deodorant material according to claim 1, 2, 3, 4, 5 or 6 to heat regeneration treatment at a regeneration temperature of 150 to 500 ° C. . 8. The method for regenerating a hydrophobic deodorizing material according to claim 7, wherein the regeneration temperature is 250 to 300 ° C. 9. The exhaust gas from the heating regeneration treatment is at 100 to 500 ° C.
The method for regenerating a hydrophobic deodorizing material according to claim 7 or 8, wherein the method is oxidative decomposition treatment with an oxidation catalyst heated to the activation temperature of. 10. The method for regenerating a hydrophobic deodorizing material according to claim 9, wherein the oxidation catalyst contains a platinum group metal.