JPH0919489A - Deodorant, its manufacture, and deodorizing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently remove malodor components or toxic components (sulfur compound and nitrogen compound) with a single deodorant over a long period. SOLUTION: A gas to be treated is treated by use of a deodorant in which an acid such as manganese dioxide (1a) or phosphoric acid (2) is carried by a carrier such as activated charcoal honeycomb, whereby sulfur compounds and nitrogen compounds are effectively removed. Further, an oxide (1b) of a metal of the group 5A of the periodic table, a metal of the group 6A of the periodic table a metal of the group 8 of the periodic table, a metal of the group 1B of the periodic table, or a metal of the group 2B of the periodic table (e.g. oxide of copper, zinc, iron, or nickel) may be carried by the carrier. A ratio of the manganese dioxide (1a) to the metal oxide (1b) is set to about the former/the latter=100/1-0.2/1, converted to metallic atomic ratio. To the whose deodorant, carrying quantity of the metal oxide component (1) consisting of the manganese dioxide (1a) and the metal oxide (1b) is set to 3-80%, and the carrying quantity of the acid (2) to about 0.5-15wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant useful for removing acidic, basic and neutral odorous components and harmful components, a method for producing the same, and a deodorizing method using the deodorant.

[0002]

2. Description of the Related Art Various deodorizing agents have been proposed to remove odorous and harmful components such as hydrogen sulfide, sulfur-containing compounds such as methyl mercaptan, and nitrogen-containing compounds such as ammonia and amines. For example, Japanese Patent Publication No. 59-3340
No. 9 discloses that an activated carbon having activated manganese oxide and an alkali metal salt and / or an alkaline earth metal salt carried thereon after contacting a gas containing an odor component and ozone with activated carbon having high adsorption performance. A method of treating a gas by contacting and removing ozone and odorous components is disclosed. However, in this method, ozone is required, and it is necessary to treat the ozone-containing gas with two types of activated carbon having a high adsorption capacity and activated carbon carrying manganese oxide or the like.

Japanese Patent Publication No. 2-39297 discloses manganese compounds, V, Mo, W, Cr, Fe, Co, Ni,
It has been proposed that a coprecipitate with a compound selected from Cu and Ag is calcined, and the obtained composite oxide catalyst is contacted with ammonia and / or amines to decompose the ammonia and amines into nitrogen. There is. Japanese Unexamined Patent Publication No. 7-16465 discloses manganese dioxide 10 to 70% by weight, activated carbon and / or activated carbon fiber 25 to 85% by weight, and Cu, F.
A deodorizing member containing 3 to 20% by weight of an oxide of a metal selected from the group consisting of e, Ni, Co, V, Pt and Au has been proposed.

However, even if these metal oxides are used,
It is difficult to effectively remove the odorous component because the deodorizing performance for either one of the sulfur-containing compound and the basic compound, especially the removing ability for the nitrogen-containing compound and the basic compound is small.

Further, in Japanese Patent Laid-Open No. 63-258644, one kind selected from phosphoric acid, phosphorous acid and hypophosphorous acid and at least one kind of peroxide and / or metal oxide are used. A deodorant is disclosed, hydrogen peroxide as a peroxide,
Inorganic peroxides and organic peroxides are described, and examples of the metal oxides include Fe, Co, Ni, Ti, Zr, V and C.
r, Mo, W, Mn, Cu, Ag, Zn, Ge, Ca,
An oxide of a metal selected from the group consisting of Sr and Ba is described.

The deodorant described in this document has a relatively high deodorizing performance for sulfur-containing compounds and nitrogen compounds. However, the ability to remove both the sulfur-containing compound and the nitrogen-containing compound is still insufficient.

[0007]

Therefore, the object of the present invention is to effectively remove a wide range of odorous and harmful components such as sulfur-containing compounds and nitrogen-containing compounds despite being a single deodorant. A deodorant and a method for producing the same are provided. Another object of the present invention is to provide a deodorant capable of removing odorous components and harmful components with high efficiency for a long period of time even with a short contact time, and a method for producing the same. Still another object of the present invention is to provide a deodorizing method capable of removing a wide range of odorous components and harmful components with high efficiency even though it is a single deodorant.

[0008]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that when a carrier such as activated carbon is loaded with manganese dioxide and an acid, both the sulfur-containing compound and the sulfur-containing compound are formed. The inventors have found that odorous components and harmful components can be effectively removed, and completed the present invention. That is, the deodorant of the present invention has (1a) manganese dioxide and (2) acid supported on the carrier. The carrier may be activated carbon or may be honeycomb-shaped. The acid may be a non-volatile inorganic acid such as phosphoric acid or sulfuric acid. Further, the carrier includes (1b) Group 5A metal of the periodic table and 6A of the periodic table.
An oxide of at least one metal selected from the group consisting of Group 8 metals, Group 8 metals of the Periodic Table, Group 1B metals of the Periodic Table and Group 2B metals of the Periodic Table (eg, selected from the group consisting of copper, zinc, iron and nickel). At least one metal oxide)
May be carried. Such deodorants include (1a) manganese dioxide (3 to 80% by weight) and (2) acid (0.5 to 15% by weight) based on the total amount of the deodorant. Among the deodorants used, (1
(1a) Manganese dioxide and (1) Manganese dioxide and (1b) The ratio of metal oxide to metal atom ratio is the former / the latter = 100/1 to 0.2 / 1 1b) copper,
(1) Metal oxide whose ratio with the oxide of at least one metal selected from the group consisting of iron, zinc and nickel is 50/1 to 0.3 / 1 in terms of metal atomic ratio. A deodorant and the like in which 5 to 70% by weight of the component and (2) 1 to 12% by weight of phosphoric acid are supported are included. In the production method of the present invention, the deodorant is produced by supporting (1a) manganese dioxide and (2) acid on the carrier. Further, in the deodorizing method of the present invention, deodorizing is performed by bringing a gas to be treated containing an odor component into contact with the deodorizing agent. Incidentally, the preparation conditions of the manganese dioxide (e.g., heating temperature and the like heating atmosphere) by, in addition to _{MnO 2, MnO, Mn 3 O} 4, Mn 2
It is known that O ₃ , Mn ₂ O _7, etc. are generated. Therefore, in the present specification, “manganese dioxide” means manganese oxide containing MnO ₂ as a main component.
In addition, in the present specification, manganese dioxide and oxides of metals in the periodic table may be simply referred to as “metal oxide components”.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The type of the carrier is not particularly limited, and examples thereof include activated carbon, alumina, silica, silica-alumina, magnesia, silica-magnesia, natural or synthetic zeolite, kaolin, bentonite, and diatomaceous earth.
These carriers are often porous and have a specific surface area of
Depending on the type of carrier, for example, it can be selected from the range of about ^{2 to} 4000 m ² / g.

The form of the carrier may be any of powder, granule, macaroni, fiber, honeycomb and the like.
The carrier is often in the form of powder, granules, or honeycomb. The honeycomb-shaped carrier has an advantage that pressure loss can be reduced while maintaining a high contact area with the gas to be treated. The carrier may contain a binder such as a resin binder.

The preferred carrier includes activated carbon in the form of powder, granules, honeycombs, etc., particularly honeycomb-shaped activated carbon. The BET specific surface area of activated carbon is, for example, 200 to 4
^{000m 2 / g, 400~3500m 2 /} g, preferably 500~3000m ² / g approximately, 700-25
It is often about 00 m ² / g. When activated carbon having such a specific surface area is used, the catalytic activity of manganese dioxide or the like can be enhanced, and the deodorizing or deodorizing ability can be enhanced. In addition, the activated carbon itself has a bad odor adsorption performance.

The carrier carries (1) a metal oxide component containing at least (1a) manganese dioxide and (2) an acid. (1) The metal oxide component may be composed of the (1a) manganese dioxide alone, but in order to maintain a high deodorizing ability for a long period of time, in addition to the (1a) manganese dioxide, (1)
b) Periodic table group 5A metal (for example, vanadium V), periodic table group 6A metal (for example, chromium Cr, molybdenum Mo, tungsten W), periodic table group 8 metal or transition metal (for example, iron Fe, cobalt Co, nickel) Ni, palladium Pd, platinum Pt), metal of Group 1B of the periodic table (for example, copper C)
u, silver Ag, gold Au) and at least one metal oxide selected from the group consisting of metals of Group 2B of the Periodic Table (eg zinc Zn). These periodic metal oxides can be used alone or in combination of two or more.

Preferred (1b) metal oxides include Periodic Table 1B.
Group metals (eg, copper), Periodic Table 2B group metals (eg, zinc), Periodic Table Group 8 metals or transition metals (eg,
Metal oxides selected from the group consisting of iron, cobalt, nickel, etc.), in particular oxides of copper, zinc, iron, nickel. (1a) Manganese dioxide and (1b) in the case of supporting a metal oxide in combination, (1a) manganese dioxide and
(1b) the ratio with the metal oxide is a range that does not impair the deodorizing ability and can suppress the reduction of the deodorizing ability, for example, in terms of metal atom ratio,
Former / latter = 100/1 to 0.2 / 1, preferably 50
/ 1 to 0.3 / 1, more preferably 20/1 to 0.5
It is about / 1.

(1) The amount of the metal oxide component supported can be selected within a range that does not impair the deodorizing performance, and is, for example, 3 to 80% by weight, preferably 5 to 70% by weight, based on the total amount of the deodorant.
More preferably, it is 10 to 60% by weight.

In general, the acid-supporting deodorant in which only the acid (2) is supported on the carrier can effectively remove the nitrogen-containing compound and the basic compound and enhance the deodorizing effect. But,
With the acid-supported deodorant, the deodorizing performance for sulfur-containing compounds and acidic compounds is significantly reduced. In contrast, the above (1)
By combining the (1) metal oxide component containing manganese dioxide with the (2) acid, while maintaining the high deodorizing effect of manganese dioxide (especially high deodorizing effect for sulfur-containing compounds), nitrogen-containing compounds and basic compounds The deodorizing effect of can be significantly improved.

(2) The acid may be either an organic acid and / or an inorganic acid. Organic acids include, for example, fumaric acid,
Polyvalent carboxylic acids such as maleic acid, oxalic acid, malonic acid, tartaric acid, succinic acid, citric acid, malic acid, glutaric acid and hydroxycarboxylic acid are included, and inorganic acids include
For example, phosphoric acid, sulfuric acid, nitric acid, etc. are included. These acids can be used alone or in combination of two or more.

Preferred acids include non-volatile acids having a boiling point of 100 ° C. or higher, for example, fumaric acid, maleic acid, oxalic acid, tartaric acid, citric acid, malic acid and other organic acids (particularly hydroxycarboxylic acids), phosphorus. Inorganic acids such as acids and sulfuric acids are included. Particularly preferred acids are non-volatile inorganic acids, especially phosphoric acid. The use of phosphoric acid has the advantage that the ignition temperature can be increased and flame retardancy can be imparted even when activated carbon is used as a carrier. The phosphoric acid may be orthophosphoric acid, which is a tribasic acid, and a condensate thereof, such as orthophosphoric acid, metaphosphoric acid, or polyphosphoric acid, and usually orthophosphoric acid is often used.

(2) The amount of the acid supported can be selected within a range capable of maintaining the ability to remove odorous components and harmful components. For example, 0.5 to 15% by weight, 1 to 12% by weight, relative to the total amount of the deodorant, More preferably, it is about 2 to 10% by weight. When the amount of acid supported increases, the activity of the metal oxide component containing manganese dioxide may be reduced, and the removal efficiency for odorous components and harmful components such as sulfur-containing compounds and nitrogen-containing compounds may be reduced.

The deodorant of the present invention can be obtained, for example, by supporting a carrier with (1) a metal oxide component containing at least (1a) manganese dioxide and (2) an acid.
As described above, as the (1) metal oxide component,
The metal oxide of (1b) periodic table may be supported together with (1a) manganese dioxide.

The loading of (1a) manganese dioxide and (1b) metal oxide is required by a conventional method, for example, by holding a solution of a water-soluble manganese salt or a metal salt in a carrier by spraying, impregnating, immersing, etc. After drying, it is baked according to (1a)
A method for producing manganese dioxide or a metal oxide (1b),
A method in which a sparingly soluble manganese salt and a sparingly soluble metal salt are mixed with a carrier together with a binder as required, and after molding if necessary, (1a) manganese dioxide or (1b) a metal oxide is produced, It can be carried out by a method in which manganese dioxide or a metal oxide is mixed with a binder together with a binder, and the mixture is molded if necessary and then dried or calcined. In addition, (1a) manganese dioxide and (1b) metal oxide may be supported by combining the above-mentioned methods.

Examples of the water-soluble manganese salt include chloride,
Inorganic acid salts such as sulfates and nitrates, and organic acid salts such as acetates and thiocyanates are included. Examples of the sparingly soluble manganese salt include phosphates and carbonates. (1b) the metal salt corresponding to the metal oxide, the solubility in water changes depending on the type of metal, for example, chloride,
It can be appropriately selected from inorganic acid salts such as sulfates, nitrates, carbonates and phosphates, and organic acid salts such as acetates and oxalates.

The (2) acid such as phosphoric acid can be carried as it is or by holding its aqueous solution or organic solvent solution in a carrier by spraying, impregnating, dipping or the like, and drying it if necessary. Alternatively, it may be supported by mixing an acid and a carrier before molding. In the loading, the order of loading (1a) manganese dioxide, (1b) metal oxide and (2) acid is not particularly limited, and includes (1a) manganese dioxide loading, (1b) metal oxide loading, ( 2) Any of the acid loading may be carried out first, and two or three components may be loaded simultaneously by a method such as spraying, impregnation, dipping, and mixing.

The deodorant of the present invention is a sulfur-containing compound, a nitrogen-containing compound or a basic compound alone, a lower fatty acid (eg, formic acid, acetic acid, propionic acid, dairy acid, valeric acid, etc.), an aldehyde (eg, It has high ability to remove and deodorize various odorous components such as formaldehyde and acetaldehyde, etc. and harmful components. Especially, high deodorizing ability is maintained for a long time with respect to hydrogen-sulfide, mercaptans such as methyl mercaptan, sulfur-containing compounds such as sulfides; nitrogen-containing compounds such as ammonia, amines such as monomethylamine, dimethylamine and trimethylamine. it can. Therefore, the deodorizing method (gas treatment method) of the present invention
Then, even a single deodorant can efficiently remove odorous components and harmful components. In particular, when a honeycomb-shaped deodorant is used, it is possible to smoothly and efficiently remove odorous components and harmful components with a small air flow resistance, and also to reduce the accommodation space in a gas treatment device such as a deodorizing device and to make the device compact. .

In the deodorizing method of the present invention, deodorizing treatment is carried out by bringing a gas to be treated containing an odorous component or a harmful component into contact with the deodorizing agent. As the gas to be treated, gases containing various odorous components and harmful components can be used, but usually at least one component selected from the sulfur-containing compounds, nitrogen-containing compounds, lower fatty acids, aldehydes and hydrocarbons is used. Often, a gas containing is used. In particular, the deodorant is
It has a high ability to remove various components including the sulfur-containing compound and the nitrogen-containing compound. Therefore, the deodorizing method of the present invention is useful for treating a gas to be treated containing at least the above-mentioned sulfur-containing compound, nitrogen-containing compound and other multi-component odorous components.

In processing the gas to be processed, the temperature of the gas to be processed is not particularly limited and can be selected from the range of, for example, -50 ° C to 100 ° C. The gas to be processed has, for example, a linear velocity of 1 to 500 cm / sec. The deodorant may be contacted to some extent.
The space velocity of the gas to be processed is, for example, 100 to 500,0.
It can be selected from the range of about 00 hr ^-1 .

In the method of the present invention, even with a single deodorant, various odorous components and harmful components can be removed only by bringing the gas to be treated into contact therewith. Therefore, in the method of the present invention, the gas to be treated may be treated with the deodorant alone, but if necessary, another deodorant or adsorbent (second deodorant), for example, chemical-free activated carbon. In combination with chemical-supporting activated carbon (for example, acid-supporting activated carbon, alkali-supporting activated carbon, bromine or bromine compound-supporting activated carbon, iodine or alkali metal iodide-supporting activated carbon (JP-A-6-126166), platinum group element-supporting activated carbon, etc.) Then, the gas to be treated may be treated. When treating the gas to be treated in combination with the second deodorant, the deodorant of the present invention is
The deodorant may be located upstream or downstream. The form of the second deodorant may be powder, granules, macaroni, fibrous, etc.,
It may have a honeycomb shape.

The deodorant of the present invention is used for a wide range of deodorization or deodorization, for example, a deodorizing gas treatment device or an exhaust gas treatment device in a chemical factory, a gas treatment device in an industrial waste elimination facility, a hospital, a karaoke box, indoors. It can be used for gas treatment equipment such as toilets, animal breeding rooms, refrigerators, shoe boxes, and deodorants.

[0028]

EFFECTS OF THE INVENTION Since the deodorant of the present invention has (1a) manganese dioxide and (2) acid supported on the carrier, it is a single deodorant, but it does not contain sulfur-containing compounds or nitrogen-containing compounds. A wide range of odorous and harmful components such as compounds can be efficiently removed. Further, even if the contact time is short, the odorous components and harmful components can be removed with high efficiency for a long period of time. Furthermore, (1b)
By further supporting the metal oxide, high deodorizing ability can be maintained for a long period of time. In the production method of the present invention, a deodorant having the above-mentioned excellent properties can be obtained by a simple operation of supporting the above components on a carrier. According to the deodorizing method of the present invention, a wide range of odorous components and harmful components can be removed with high efficiency simply by bringing the gas to be treated into contact with the deodorant, even though it is a single deodorant.

[0029]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 100 parts by weight of powdered activated carbon (manufactured by Takeda Pharmaceutical Co., Ltd., Shirasagi, BET specific surface area 1300 m ² / g) was mixed with 10% by weight aqueous solution of manganese nitrate as manganese dioxide MnO _2.
By weight, a 10 wt% copper nitrate aqueous solution was added as copper oxide CuO in an amount of 5 parts by weight, and the mixture was baked at 180 ° C for 8 hours. After firing, 5 parts by weight of a 20 wt% phosphoric acid aqueous solution was added as phosphoric acid, and the deodorant was prepared by drying at 115 ° C. for 2 hours.

Example 2 A deodorant (support amount as manganese dioxide MnO ₂ of 10 parts by weight, support amount as iron oxide Fe ₂ O ₃₎ was carried out in the same manner as in Example 1 except that iron nitrate was used instead of copper nitrate. 5 parts by weight)
I got

Example 3 A deodorizing agent (10 parts by weight of manganese dioxide MnO _{2 and} 5 parts by weight of zinc oxide ZnO) was prepared in the same manner as in Example 1 except that zinc nitrate was used instead of copper nitrate.
I got

Example 4 100 parts by weight of powdered activated carbon (manufactured by Takeda Yakuhin Kogyo Co., Ltd., Shirasagi, BET specific surface area 1300 m ² / g) was mixed with 10% by weight aqueous solution of manganese nitrate as manganese dioxide MnO _2.
It was attached so that it would be part by weight and baked at 180 ° C. for 8 hours. After firing, 5 parts by weight of phosphoric acid was attached and dried at 115 ° C. for 2 hours to prepare a deodorant.

Comparative Example 1 A deodorant having manganese dioxide supported on activated carbon was prepared in the same manner as in Example 1 without adding phosphoric acid.

Comparative Example 2 A deodorant in which activated carbon was loaded with manganese dioxide and copper oxide was prepared in the same manner as in Example 4 without adding phosphoric acid.

[Deodorizing Test] 100 mg of the deodorizing agents obtained in the above Examples and Comparative Examples were weighed in a Petri dish and sealed in a Tedlar bag (volume: 1 L). Then, 1 L of gas containing 1000 ppm of hydrogen sulfide was injected as an odor component, and the hydrogen sulfide concentration in the Tedlar bag after 2 hours was measured by gas chromatography. Further, a gas containing 1000 ppm of ammonia was similarly tested.
The residual concentration of ammonia was measured with a detector tube. The results are shown in Table 1.

[0036]

[Table 1] As is clear from the comparison between Examples and Comparative Examples in Table 1, the combination of manganese dioxide and phosphoric acid, the combination of manganese dioxide and other metal oxides and phosphoric acid produced both hydrogen sulfide and ammonia. Can be removed. In particular, the deodorants of the examples have high ammonia removal efficiency.

Example 5 Activated carbon honeycomb (manufactured by Takeda Pharmaceutical Co., Ltd., BET specific surface area 850 m ² / g, 300 cells / inch ² , size 30 m)
m × 30 mm × thickness 20 mm) 100 parts by weight of a 10% by weight aqueous solution of manganese nitrate was added as manganese dioxide MnO _{2 in an amount} of 10 parts by weight, and the mixture was baked at 180 ° C. for 8 hours. After firing, impregnate 8 parts by weight of phosphoric acid to 115
A honeycomb deodorant was prepared by drying at 0 ° C for 2 hours.

Examples 6 and 7 Two activated carbon honeycombs (BET manufactured by Takeda Pharmaceutical Co., Ltd.)
Specific surface area 850 m ² / g, 300 cells / inch ² , size 30 mm × 30 mm × thickness 20 mm) 100 parts by weight,
A 10 wt% aqueous solution of manganese nitrate was added to manganese dioxide MnO.
10 parts by weight of ₂ and 10 parts by weight of a 10% by weight copper nitrate aqueous solution were added as 5 parts by weight of copper oxide CuO, and the mixture was baked at 180 ° C. for 8 hours. After firing, one activated carbon honeycomb was impregnated with 5 parts by weight of phosphoric acid (Example 6) and the other activated carbon honeycomb was impregnated with 8 parts by weight of phosphoric acid (Example 7), and dried at 115 ° C. for 2 hours to obtain a honeycomb shape. Was prepared.

Hydrogen sulfide 300 ppb, methyl mercaptan 300 ppb and trimethylamine 300
A gas containing ppb was passed through the activated carbon honeycomb at a linear velocity of 95 cm / sec. After 1 hour, the concentration of each component at the inlet and outlet of the gas passing through the activated carbon honeycomb was measured by gas chromatography and the removal rate was calculated. The results shown in Table 2 were obtained. The removal rate is represented by the following formula. Removal rate = [(inlet concentration-outlet concentration) / inlet concentration] x 100

[0040]

[Table 2] As is clear from Table 2, the deodorants of Examples 5 to 7 have high removal ability for sulfur-containing compounds and nitrogen-containing compounds.

Claims (12)

[Claims] 1. A deodorant in which (1a) manganese dioxide and (2) acid are carried on a carrier. 2. The deodorant according to claim 1, wherein the carrier is activated carbon. 3. The deodorant according to claim 1, wherein the carrier has a honeycomb shape. 4. The deodorant according to claim 1, wherein the acid is a non-volatile inorganic acid. 5. The deodorant according to claim 1, wherein the acid is phosphoric acid. 6. Further, (1b) periodic table group 5A metal, periodic table 6
The deodorant according to claim 1, which carries an oxide of at least one metal selected from the group consisting of a Group A metal, a Group 8 metal of the periodic table, a Group 1B metal of the Periodic Table, and a Group 2B metal of the Periodic Table. 7. The deodorant according to claim 6, wherein the metal oxide (1b) is at least one metal oxide selected from the group consisting of copper, zinc, iron and nickel. 8. The total amount of (1a) manganese dioxide 3 to 8
The deodorant according to claim 1, which carries 0% by weight and 0.5 to 15% by weight of (2) acid. 9. The ratio of (1a) manganese dioxide and (1b) metal oxide in terms of metal atom ratio, former / latter = 100/1.
The deodorant according to claim 6, which is about 0.2 / 1. 10. Activated carbon containing (1a) manganese dioxide and (1b)
The ratio of the oxide of at least one metal selected from the group consisting of copper, iron, zinc and nickel is 50/1 to 0.3 / 1 in terms of metal atom ratio (1) metal Oxide component 5 to 70% by weight, and (2) phosphoric acid 1 to 12% by weight
Deodorant carrying and. 11. A carrier comprising (1a) manganese dioxide and (2)
A method for producing an acid deodorant. 12. A gas to be treated containing an odorous component.
A deodorizing method of contacting with the deodorant described.