JPH0634810B2 - Air purifier - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to harmful gases such as NO _X , SO _X and O ₃ gas, and nitrogen compound gas such as NH ₃ and H ₂ S. Cleans polluted air containing sulfur compound-based gas, carboxyl group-based gas such as acetaldecht, carboxylic acid-based gas such as acetic acid, as an air cleaner, or for cleaning combustion exhaust gas and harmful gas The present invention relates to a composition that can be used as a material. The composition of the present invention can also be used as a food freshness-retaining agent.

[Prior Art] NO _X gas, SO _X gas, and O ₃ gas in the air should be reduced to cause respiratory diseases, and various combustion devices and gas scrubbing to prevent or reduce their generation Equipment and chemical processing equipment are used. However, air purification products that efficiently remove these harmful gases from polluted air using simple equipment have not been generalized.

Nitrogen compound gas and sulfur compound gas in the air are accompanied by a bad odor, so adsorption method using activated carbon, masking method using other fragrances, or chemical method of chemically reacting odor gas,
The odor is being processed. However, conventional deodorants are
There is a problem that the deodorizing power deteriorates in a short time.

Textile Society of Japan (Fiber and Industry) Vol.42, NO.12 (1986), P18-P2
6 describes that a complex compound obtained by reacting an Fe (II) compound and ascorbic acid in a solution state has a deodorizing power for a nitrogen compound-based odorous gas. However, according to the findings of the present inventors, this complex compound has a weak deodorizing power to a sulfur compound type odor gas, and a nitrogen compound type odor gas is adsorbed on the complex compound to be deodorized, but the adsorption amount is limited. However, there is a problem that the deodorizing power deteriorates in a short time.

The present inventors invented a composition in which ascorbic acid or the like is brought into contact with a metal such as iron or manganese, and a reaction product is allowed to coexist with unreacted iron or manganese. Filed a patent. This composition can be easily manufactured at low cost, and even if it is used for a long period of time, its air cleaning power is unlikely to deteriorate.

[Problems to be Solved by the Invention] The present inventors have further extensively studied the composition of Japanese Patent Application No. 1-280776 to arrive at the present invention. That is, the present invention
It is an object of the present invention to provide an air-purified product which is a new composition having an air purifying effect equivalent to or better than the composition of 1-280776 and which can be produced by a simpler method.

[Means for Solving the Problems] In the present invention, one or more metals of Fe, Mn, Al, Zn, Cr, and Cu and oxypolybasic acids having a molar ratio of 0.5 to 1.0 with respect to the metal are mixed with water. The reaction is carried out in the presence to form a reaction solution of metal and oxypolybasic acid at 7.5>pH> 5.0. Next, a base is added to this reaction solution to prepare an air cleaning composition solution adjusted to 14>pH> 6.0.

When oxypolybasic acids with a molar ratio of 0.5 to 1.0 are reacted in the presence of water for a sufficiently long time in the air, the pH of the metal and the oxypolybasic acids and oxygen are almost neutral. A colloidal reaction solution, which is the reaction product of, is obtained. When the amount of metal is excessive, unreacted metal precipitates on the bottom.

In the present invention, a colloidal reaction solution is used, but the effect does not change even if some unreacted precipitated metal is mixed.

When the molar ratio is 0.5 or less, the amount of unreacted metal increases and the amount of colloidal reaction solution produced is insufficient. If the molar ratio is 1.0 or more, it is difficult for the pH to become neutral even after a long time reaction,
Not preferable. The colloidal reaction solution nitrogen compound-based gas, O _3, SO _2, although the NO ₂ gas such as some ability to clean, sulfur compound-based gas, the ability to clean the gas such as acetaldehyde weak. In the present invention, the addition of a base is carried out in order to enhance the cleaning ability of gases such as sulfur compound type gas and acetaldehyde. That is, by adding a base to this reaction solution,
If adjusted to <6.0, the reaction site becomes alkaline and the ability to clean sulfur compound gas, acetaldehyde, etc. is strengthened. If the pH before the addition of the base is less than 5, the reaction product of the metal, the oxypolybasic acid and oxygen is not sufficiently formed, and the cleaning power is small. In the present invention, the reaction solution at the time of adding the base is 7.5>pH> 5.0, which is close to neutral, so the reaction product in the reaction solution does not undergo a large chemical change due to the added base, and the original nitrogen compound, O An air cleaning composition solution having sufficient cleaning ability to remove ₃ , SO ₂ , NO _2, etc. can be obtained.

As a base to be added, a general base such as Ca (OH) ₂ , NaOH, Mg (OH) ₂ , KOH or the like is added to the colloidal reaction solution as it is or as a solution. An addition amount of 0.2 to 2% by weight of the metal is sufficient.

In the present invention, the air cleaning composition solution is Fe, Mn, Al, Zn, C
An air-purified product is prepared by supporting one or more of r and Cu on a metallic carrier.

Although the metallic carrier will be described later, the purpose of supporting the metallic carrier is to improve the life of air cleaning of the air cleaning composition solution, and by coexisting with a reducing metal, The reducing power of the metal can be utilized to prevent oxidation of the air cleaning composition and improve the life of the air cleaning power.

As a method for supporting the air cleaning composition solution on the metal, the metallic carrier can be dipped in the air cleaning composition solution and dried, or the air cleaning composition solution can be supported on the metallic carrier. It can also be obtained by spraying and drying.

The metal used as the carrier in the present invention is preferably powdery in terms of reaction, but may be linear, plate-like or the like. Further, there is no particular need for the metal composition to have a high degree of purity, for example, pure iron powder may be used, or pig iron powder, Dalai powder, recovered iron powder, etc. may be used in place of pure iron powder to obtain the same effect. .

Compared to Japanese Patent Application No. 1-280776, the air purification product of the present invention,
Since an air-cleaning composition solution in which a base is directly added to and mixed with a colloidal reaction solution is used, a troublesome manufacturing process of arranging the base on the molded product later can be omitted, and the base is evenly distributed throughout the air-purified product. As it is distributed, it exhibits stable and good air purification performance.

Claim (2) of the present invention is an air-purified product obtained by further impregnating or mixing iron hydroxide and / or a base with the air-purified product.

Since iron hydroxide acts as a sulfur compound-based gas decomposition catalyst,
It is particularly preferable when it is desired to enhance the deodorizing power of sulfide-based gas.
Further to base impregnated or mixed when ^{_{H 2 S → H + + HS}} - → 2H + + S -
The decomposition reaction of (3) easily proceeds, and more preferable results are obtained.

As iron hydroxide, commercially available Fe (OH) ₂ , Fe (OH) ₃ may be used, or an alkaline solution such as NaOH, Ca (OH) ₂ , Mg (OH) ₂ or the like and FeSO ₄ , FeCl ₂ or the like. For example, let them react at an equimolar ratio,
The generated iron hydroxide may be used.

The coexistence of the metal of the present invention and the air cleaning composition, or further the coexistence of iron hydroxide and a base, that the air cleaning effect is large, is due to the chemical reaction between these coexisting materials and gas, Moisture in the air, because it comes from the regeneration effect by oxygen, when carrying the air cleaning composition solution on the metal, or when further impregnating iron hydroxide-base,
For example, it is an effective method to add a small amount of a wetting agent such as CaCl ₂ , polyphosphoric acid and propylene glycol to give the composition wettability.

In the present invention, the oxypolybasic acids refer to ascorbic acid, an acid similar to ascorbic acid having an OH group and a COOH group, or a mixed acid of two or more thereof. OH
Examples of the acid similar to ascorbic acid having a group and a COOH group include gluconic acid, citric acid, tartaric acid, tannic acid, gallic acid and phthalocyanine.

In claim (4) of the present invention, as the metallic carrier, Fe, Mn, A
A compact or sintered body of one or more metal powders of l, Zn, Cr, Cu is used as a carrier. The carrier formed by molding the metal powder, the metal powder is kneaded together with a binder, and the kneaded product is honeycomb-shaped by, for example, extrusion molding or pressure molding,
It can be obtained by forming a columnar tip or a hollow article.

As a sintered body, when metal powder is applied to urethane foam, foam beads, etc. and sintered in a non-oxidizing atmosphere, the urethane foam and foam beads are thermally decomposed and burned off, and a porous sintered metal is supported. Become a body.

In claim (5) of the present invention, a metallic carrier obtained by plating or spraying one or more of Fe, Mn, Al, Zn, Cr and Cu on an inorganic or organic substrate as a metallic carrier. use. Organic base materials include organic polymer-based three-dimensional porous materials, foam beads, non-woven fabrics, cloths and films, and inorganic base materials include shirasu balloons, zeolites, glass fibers, cloths, non-woven fabrics, papers, filters, etc. There is. The production of a metallic carrier by a plating method using these base materials can be easily carried out by electroless plating or a combination of electroless and electrolytic plating. In the case of thermal spraying, for example, the low temperature thermal spraying method of Panmetal Engineering Co., Ltd. can be carried out. For example, using a low temperature sprayer on acrylic non-woven fabric (100 mm × 100 mm × 10 mm)
When 2 mmφ Zn wire was melt-sprayed, 20 g of Zn could be deposited on the acrylic fibers constituting the nonwoven fabric almost evenly in the thickness direction of the nonwoven fabric.

In claim (6) of the present invention, Fe, Mn, Al, as a metallic carrier
A carrier in which one or more metal powders of Zn, Cr, Cu are arranged on an organic or inorganic substrate with an adhesive is used.

The metal powder may be a metal powder of Fe, Mn, Al, Zn, Cr, Cu or an alloy powder of these metals. Further, since it is not necessary to have high purity, dusts containing these metals generated during metal refining can be sufficiently used.

It is convenient to use water glass, ceramizole, CMC, PVA, methyl cellulose or the like as the adhesive.

As the base material, various organic or inorganic shapes such as the above-mentioned three-dimensional porous body and foamed beads are used. A cloth-like material or a fibrous material can be used.

[Operation] As described in Japanese Patent Application No. 1-280776, reaction products of metals such as Fe, Mn, Al, Zn, and oxypolybasic acids with Fe, Mn, A
Create a solid molded product that coexists with metals such as l and Zn.
After the solid molded product is produced, when a base is further impregnated on the solid molded product, nitrogen compounds, O ₃ , SO ₂ , N
It is possible to obtain an air purification material that has a strong ability to remove O ₂ as well as sulfur compound-based gas and the like.

However, Japanese Patent Application No. 1-280776, in which a solid molded article in which a reaction product and a metal are allowed to coexist is once produced, and then a base is attached to this molded article, is complicated in the production method, and a base is added. It is difficult to coexist sufficiently uniformly.

It is conceivable that a reaction product is produced by directly reacting a metal with a solution of oxypolybasic acids and a base, and then forming the reaction product into a solid. However, even if the solution of the metal and the oxypolybasic acid and the base are simultaneously mixed and stirred without special measures, a reaction product having a deodorizing power cannot be obtained.

The inventors of the present invention have extensively studied the addition timing and the mixing ratio of a solution of oxypolybasic acids and a base, and as a result, have achieved the present invention.

That is, the air-cleaning composition solution of the present invention is prepared by first adding oxypolybasic acids in an amount of 0.5 to 1.0 to the metal together with water in a molar ratio to the metal and allowing the reaction to proceed for a long time. This reaction is in solution
Repeat until pH reaches 5.0-7.5. After that, a basic solution is added to adjust the pH to 6.0-14. The air cleaning composition of the present invention is produced by supporting the air cleaning composition solution having a pH of 6.0 to 14 on a metal carrier.

When the metal and the oxypolybasic acids are reacted until the pH reaches 5.0 to 7.5, the oxypolybasic acids are used up for the reaction. There is no active reaction with the solution. Further, the reaction product already formed by the reaction between the metal and the oxypolybasic acid is kept in a state where the strong deodorizing performance for ammonia etc. is maintained.

In the composition having the air cleaning ability of Japanese Patent Application No. 1-280776 impregnated with a base, the removal performance of sulfur compounds also fluctuated due to the fluctuation of the work when the base was later impregnated, but the air cleaning of the present invention The compound has a uniform distribution of the base for adding the base to the reaction solution, and can always remove the sulfur compound with stable performance. Further, the air-purified product of the present invention,
It can be produced by a simpler process than the composition having an air cleaning power of Japanese Patent Application No. 1-280776.

[Examples] The present inventors mixed the metal powders shown in Table 1 with the oxypolybasic acid shown in with water of 1 and mixed and stirred for a time shown by the molar ratio of the oxypolybasic acid and the metal shown in Then
Where the metal, oxypolybasic acid and oxygen have been sufficiently reacted,
A reaction solution having the pH shown in was obtained. When the base shown in the reaction solution was added to the reaction solution in the amount shown in, and the mixture was stirred, a colloidal air-cleaning composition solution having a pH shown in was obtained. This colloidal air cleaning composition solution was coated with pig iron powder on a urethane foam having three-dimensional communication holes with an adhesive. The attached carrier was dipped, and after 1 minute, it was pulled up and dried, and a filter-like air-purified product of A _{1 to} G ₁ shown below was manufactured.

The A ₂ filter is the A ₁ filter, FeCl ₃ (0.5M), Ca
An aqueous solution containing (OH) ₂ (1M) / iron hydroxide was sprayed. Filter G1 is the pH of the reaction solution
Is a comparative example of less than 5.

Each air-purified product was tested for air-purifying power by the following method, and the results are shown in Table 1.

FIG. 1 shows an air cleaning power test device used in this example.
NH ₃ gas, H ₂ S gas, or SO ₂ gas is filled in the closed container 1 of 40, the circulation fan 2 is rotated, and the gas is passed through the filter-like air purification product 3.
After 30 minutes, the removal rate of each gas in the container 1 was calculated by the following formula.

Removal rate = {(initial gas concentration-30 minutes later gas concentration) / (initial gas concentration)} × 100 This removal rate is shown in the removal rate column (after 30 minutes) in Table 1.
Also, in Table 1, the removal rate of each gas (after 40 times) is as follows:
After leaving it in the air for 40 hours, refilling the closed container 1 with gas again, and using the filter-like air-purified product again for 30 minutes to remove gas, repeat 40 times, and then leave the filter in the atmosphere for 2 hours. It is the removal rate when the deodorization test is performed again for 30 minutes after air-drying.

The A ₂ filter has an enhanced H ₂ S removal capacity because iron hydroxide is attached to the A ₁ filter.

The B _{1 to} F ₁ filters have different types of metal powders and oxypolybasic acids, but all have good air cleaning power and have sufficient air cleaning power regeneration capability. It was

Since the base was added to the filter G1 at the stage of the composition whose pH of the reaction solution was close to 3.5, the air cleaning power was smaller than that of the other. It is assumed that the deodorant composition has been decomposed by the base.

[Example 2] The air-purified product of the present invention was obtained by immersing a carrier containing a metal represented by ~ in Table 2 for 1 minute in the colloidal air-cleaning composition solution of A ₁ in Table 1 and then drying. It was created. When this air-purified product was subjected to an air-purifying power test in the same manner as in Example 1, all of the air-purified products showed good deodorizing performance and regeneration effect as shown in Table 2.

[Advantages of the Invention] The air-purified product of the present invention is obtained by once producing a solid molded product in which a reaction product and a metal are allowed to coexist, and then allowing a base to coexist in the solid molded product. Compared to the composition having air cleaning power described in No. 280776, the production method is simple and the removal power of sulfur compounds, acetaldehyde and the like is stable and good.

[Brief description of drawings]

FIG. 1 is an explanatory view of the air cleaning power test device used in the examples. 1: Closed container, 2: Circulation fan, 3: Filter-like air purification product, 4: Gas introduction port, 5: Gas sample collection port, 6: Gas circulation direction.

Claims (6)

[Claims] 1. A metal or metals selected from the group consisting of Fe, Mn, Al, Zn, Cr and Cu, and a molar ratio of 0.5 to 1.0 with respect to the metals.
React with the oxypolybasic acids of 7. in the presence of water, and 7.
A reaction solution of a metal of 5>PH> 5.0 and an oxypolybasic acid is produced, and a base is added to the reaction solution to prepare an air cleaning composition solution of 14>PH> 6.0. , F
An air-purified product, which is supported on one or more metal-containing carriers selected from e, Mn, Al, Zn, Cr and Cu. 2. One or more metals selected from Fe, Mn, Al, Zn, Cr and Cu and a molar ratio of 0.5 to 1.0 with respect to the metals.
React with the oxypolybasic acids of 7. in the presence of water, and 7.
A reaction solution of a metal of 5>PH> 5.0 and an oxypolybasic acid is produced, and a base is added to the reaction solution to prepare an air cleaning composition solution of 14>PH> 6.0. , F
An air-purified product characterized by being supported on one or more metal-containing carriers selected from e, Mn, Al, Zn, Cr and Cu, and further impregnated with iron hydroxide and / or a base. . 3. Oxypolybasic acids include ascorbic acid, citric acid, gluconic acid, tartaric acid, tannic acid, gallic acid,
The air-purified product according to claim (1) or (2), which is a mixture of one or more selected from phthalocyanines. 4. The carrier according to claim 1, wherein the metallic carrier is a carrier formed by molding a metal powder or a sintered metal carrier. Air purifier. 5. A metal carrier is a carrier obtained by plating an organic or inorganic substrate with one or more metals selected from Fe, Mn, Al, Zn, Cr and Cu. Or, a carrier obtained by spraying one or more selected from Fe, Mn, Al, Zn, Cr and Cu onto an organic or inorganic substrate,
The air-purified product according to claim (1) or (2) or (3). 6. A metallic carrier comprising an organic base material or an inorganic base material coated with an adhesive with a powder of one or more kinds of metal selected from Fe, Mn, Al, Zn, Cr and Cu. The air-purified product according to claim (1), (2), or (3), which is a loaded carrier.