JP2663230B2 - Air-purified product and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to CH ₃ CHO (acetaldehyde), HCHO (formaldehyde), (CH
₃₎ it relates to ₃ N (triethylamine) and air cleaning product and a manufacturing method thereof for removing NH ₃ and the like.

[0002]

2. Description of the Related Art Offensive odor gases in the air are removed by an adsorption method using activated carbon, a masking method using other fragrances, a chemical method of chemically reacting odors, etc., or the discomfort is reduced. I have. However, the adsorption method using activated carbon has a problem that the deodorizing performance deteriorates in a short period of time, and also has a disadvantage that it is likely to cause a fire due to its flammability. In the masking method using other fragrances, the fragrance may give a new discomfort and is not a fundamental solution. As a chemical method for causing a chemical reaction, for example, there is a method of oxidizing and decomposing a malodorous gas with ozone. However, since excess ozone is harmful to a human body, it causes new harm. That is, since it is difficult to control the amount of the chemical substance that just reacts with the odorous gas, an unnecessary chemical substance is generated, and it is hardly a fundamental solution.

In particular, CH ₃ C, which is a main component of the smell of tobacco
It is difficult to remove HO with activated carbon.
As described in JP-A-6-53744, aniline having high chemical reactivity is impregnated into activated carbon to improve the removal performance.
Various countermeasures have been taken, such as removal by chemical reaction with phenylhydrazine as in -95319. However, according to the knowledge of the present inventor, there is a problem that the odor of the chemically reactive substance itself becomes a problem, and there are weak points such as difficulty in maintaining the activity of the chemical substance and a short life, and it was hardly a fundamental solution. .

The present inventors have proposed NH ₃ , (CH ₃ ) ₃ N, H
A composition excellent in the removal rate and the life of the malodor represented by the four major malodors of ₂ S and CH ₃ SH (methyl mercaptan) was invented, and was proposed earlier in Japanese Patent Application Laid-Open No. 3-188939. In this method, a reaction product formed by bringing ascorbic acid or the like into contact with a metal such as iron or manganese coexists with unreacted iron or manganese. This composition can be manufactured at a low cost, the deterioration of the air cleaning power is extremely small, and the problem of the prior art is improved. However, the CH ₃ CHO performance is practically required to be further improved. there were.

[0005]

SUMMARY OF THE INVENTION The present invention relates to Japanese Patent Application Laid-Open
No. 88939, further improving and supplementing the deodorizing performance of the composition,
It is another object of the present invention to provide an air-purified product made of a new material by a simple process and a method for producing the same. Especially CH ₃ removal
CHO, de-HCHO, de- (CH ₃ ) ₃ N and de-NH ₃
There is a need for a deodorant that improves speed and exhibits its performance over a long period of time.

[0006]

The present invention solves the above-mentioned problems, and is characterized in that it is a double salt of hydrazine with one or more metal salts of Ni, Al, Zn and Ti. Air purifier.

[0007] Further, there is provided an air-purified product characterized in that a molded product of chain magnesium silicate is used as a support, and a double salt of the above metal salt and hydrazine is supported.

The chain magnesium silicate is Ni, A
1, immersed in a mixed aqueous solution of one or more metal salts of Zn and Ti and hydrazine and then dried, or immersed in an aqueous solution of one or more metal salts of Ni, Al, Zn and Ti And then immersing in a hydrazine aqueous solution, followed by drying to deposit and carry a metal salt hydrazine double salt.

[0009]

According to the present inventors, research, metal complex which is the reaction product of a polybasic acid and metal NH ₃ and (CH _{3) 3} adsorbed very basic gas such as N but CH ₃ The adsorption power of SH gas is weak. One solution is to provide a solid base as described in Japanese Patent Application No. 63-273195 by the present inventors.

[0010] However, in subsequent studies, it was found that substances having a strong adsorbing power for acidic gases such as H ₂ S were iron hydroxide and ferric oxide formed by dissolving metallic iron in an aqueous solution. In addition, they found that it was necessary to form a state in which metallic iron and iron hydroxide, ferric oxide, and magnetite coexist in order to effectively produce iron hydroxide and maintain the effect stably for a long period of time. . Further, it was found that when the H ₂ S removal performance was improved, the CH ₃ SH removal performance was also excellent.

[0011] It is considered that the reason why the improved de-H ₂ S performance is also improved is that the de-CH ₃ SH performance is improved because H of the -SH group has the same property as H ₂ S. Therefore, it can be inferred that it is effective to effectively generate iron hydroxide. However, studies by the present inventors have found that good H ₂ S removal performance is not a sufficient condition for good CH ₃ SH removal performance. For example, iron and an aqueous solution of L-ascorbic acid are brought into contact with each other in the air, and a co-existent product of the complex salt and iron is formed at 150 ° C for 2 hours.
The reaction product subjected to the heat treatment for 4 hours has very good H ₂ S removal performance, but slightly inferior CH ₃ SH performance.

[0012] de CH ₃ SH performance results of the study of various measures to improve, found that the de-CH ₃ SH performance by adsorbing hydrogen sulfide on iron oxide is greatly improved, especially in the earlier A patent application was filed in Japanese Patent Application No. 3-120473. However, de-CH ₃ CHO performance, de-HCHO performance,
Research on the development of a composition excellent in (CH ₃ ) ₃ N performance and NH ₃ removal performance requires research from a completely different viewpoint, and extensive research has been carried out on metals other than iron. Succeeded in developing an air purifier with excellent performance.

More specifically, the reaction products of various metal salts and hydrazine were tested for deodorizing performance. Among them, an aqueous solution of one or more metal salts of Ni, Al, Zn and Ti was reacted with hydrazine. For the composition obtained by drying the resulting double salt of metal salt hydrazine,
De-CH ₃ CHO performance, de-HCHO performance, de- (CH ₃ ) ₃
It was confirmed that N performance and NH ₃ removal performance were excellent.

Hydrazine is a highly reactive substance having a strong reducing power, and has a strong self-decomposition property and naturally reacts with NH ₃ , N ₂ ,
It is a substance that is decomposed or oxidized to H ₂ , H ₂ O, etc., but its chemical stability is increased by forming a double salt with a metal salt, and hydrazine is used until it reacts with gases having stronger activity. Can be stable. Gases having stronger activity include aldehydes such as CH ₃ CHO and the like, which have a strong chemical adsorption power to hydrazine and are taken into double salts to enable air purification.

The above-mentioned sulfates of Ni, Al, Zn and Ti;
The mixed concentration of hydrazine and a metal salt selected from one or more of hydrochloride and nitrate is the most deodorizing initial performance and sustainable air cleaning when the metal salt and hydrazine are almost equal in molar concentration in terms of metal ion. However, as the distance increases, the performance gradually decreases. The reason is considered that when the amount of hydrazine is small, the interaction between the metal salt and hydrazine becomes too strong, and when the amount of hydrazine is too large, the metal salt is partially reduced and exerts a catalytic action to decompose hydrazine. To promote or enhance the composition
It is considered that hydrazine is easily decomposed because H approaches the basic side.

The dried composition comprising the double salt of the metal salt hydrazine is obtained in the form of particles. This particulate composition,
For example, a powder pulverized to under 44 microns has a specific surface area of about 4 m ² / g, but can be used as it is as a deodorant in a bag, for example. Further, a molded product obtained by molding this powdery composition into pellets can be used as a deodorant.

The above-mentioned double salt of the metal salt hydrazine has a deodorizing property against a plurality of unpleasant odor sources which has not existed conventionally.
In order to maximize this deodorizing performance, it is necessary to increase the specific surface area to expand the reaction interface with malodor,
And the air permeability may be increased. These two conditions can be satisfied by utilizing a carrier.

In the present invention, a chain magnesium silicate which is relatively inexpensively available is used as a carrier. This chain magnesium silicate, for example, sepiolite, palygorskite and the like are known as natural minerals. Its structure is a fibrous structure in which small pieces of talc (talc) are bricked, and is a lump of magnesium silicate having a specific surface area of 230 to 260 m ² / g. This sepiolite is
For example, these chain magnesium silicates are used as adsorbents because they have many pores of 200 Å and palygorskite has many pores slightly smaller than sepiolite. However, for example, the removal of CH ₃ CHO from 1 to 5 mm sepiolite particles
The performance was as follows: CH ₃ CHO rate after one month was 50%, 6
After 3 months, the CH ₃ CHO removal rate is 30%, which is not sufficient as the deodorization performance targeted by the present inventors.

As described above, chain magnesium silicate has the property of sintering while maintaining its porosity, and has no catalytic action by itself and does not impair the chemical stability of the loaded material. It is. The present invention relates to a molded product of this chain magnesium silicate, for example,
mm, crushed into granules, sepiolite particles mixed with a binder, paste, and formed into a sheet, and further formed into a honeycomb-shaped formed body as a carrier, Ni, A double salt, which is a compound of hydrazine and a metal salt of Al, Zn and Ti alone or in combination,
An air-purified product dispersed and supported on the surface or in the pores of the molded product.

As a method for producing the above-mentioned air-purified product, a method for immersing a molded product of the chain-like magnesium silicate, which is the above-mentioned support, in a mixed aqueous solution of a metal salt and hydrazine, followed by drying, or a method for preparing the molded product in the aqueous metal salt solution, After immersion, a double salt of a metal salt hydrazine can be supported on the surface or in the pores of the linear magnesium silicate molded article by using a method of immersing in an aqueous solution of hydrazine and then drying.

[0021]

Next, an embodiment of the present invention will be described. Example 1 Sepiolite particles having a particle size of 1 to 5 mm were mixed with nickel sulfate,
An aqueous solution of a metal salt alone or a mixture of aluminum sulfate, aluminum chloride, ferrous sulfate, zinc sulfate, zinc chloride, titanium sulfate, iron ascorbic acid, cobalt sulfate, copper sulfate, manganese sulfate, etc. 1.0
It was immersed for 1 minute in an aqueous solution mixed with each mol / liter, drained, and then naturally dried in the air for one month to produce a deodorant. Table 1 shows typical examples and comparative examples of the mixing conditions of the aqueous solution.

[0022]

[Table 1]

[0023] As deodorizing characteristics of the conventional deodorization aldehydes which are said to be difficult to take a drug, each de-CH ₃
The CHO performance was evaluated, and those with good performance were also evaluated for durability. The deodorizing test apparatus has the structure shown in FIG. 1, and a circulation fan 2 having a blowing capacity of 400 liter / min is installed in a closed container 1 having a capacity of 40 liter. In the figure, 3 is a filter-shaped air-purified product as a sample,
4 is a gas inlet, 5 is a gas sampling port, and gas is circulated in the direction of arrow 6.

The evaluation amount of the deodorizer is 40 g each time,
Approximately 90mm × 80 with the side made of cardboard and the top and bottom made of nonwoven
Those packed in a box of 10 mm × 10 mm were set on the entrance side of the fan, and the deodorizing performance was evaluated. The initial concentration is 100 ppm. Table 1 also shows the evaluation results 1 month and 6 months after production.

The deodorization rate was determined by measuring how much the concentration decreased after 10, 20 and 30 minutes, and was determined by the concentration ratio of the removed gas components. In some cases, a deodorization rate of 100% was achieved in 10 minutes, but only the reached value in 30 minutes is shown in the table. As is clear from the table, the deodorant loaded with the target metal of the present invention showed a high deodorization rate, but the iron sulfate of Comparative Example,
With respect to iron chloride, iron L-ascorbate, cobalt sulfate, copper sulfate and manganese sulfate, the effect of improving the performance is extremely small, and the mixing with the metal salt targeted in the present invention removes CH _3.
Although CHO performance is observed, the performance is significantly degraded after 6 months, and there is a problem in practical use.

Example 2 Using the same deodorizing agent as in Example 1,
_{3) 3} N results of the properties was evaluated for confirmation shown in Table 2.

[0027]

[Table 2]

As is clear from the table, the deodorant supporting the target metal of the present invention exhibited a high deodorization rate against nitrogenous odor. Moreover, iron sulfate of the comparative example, iron chloride, L- ascorbic iron was seen cobalt sulfate, copper sulfate, high de (CH ₃₎ also manganese sulfate ₃ N performance.

[0029]

According to the present invention, CH ₃ CHO, HCH
An air-purified product having high O, (CH ₃ ) ₃ N, and NH ₃ performances can be produced inexpensively and easily, and the deodorized performance of the obtained air-purified product functions over a long period of time, and its practical value is high.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing the structure of a test device for evaluating a deodorizing device.

[Description of Signs] 1 Closed container 2 Circulation fan 3 Deodorizing material evaluation sample 4 Gas inlet 5 Gas sampling port 6 Gas circulation direction

Claims (4)

(57) [Claims] 1. An air-purified product which is a double salt of hydrazine with one or more metal salts of Ni, Al, Zn and Ti. 2. An air-purified product comprising a molded product of chain-like magnesium silicate as a support and carrying the double salt according to claim 1. 3. A chain magnesium silicate comprising Ni, Al, Z
A method for producing an air-purified product, comprising immersing in a mixed aqueous solution of one or two or more metal salts of n and Ti and hydrazine, followed by drying to deposit and carry a metal salt hydrazine double salt. 4. A linear magnesium silicate comprising Ni, Al, Z
Production of an air-purified product characterized by depositing and supporting a metal salt hydrazine double salt by immersion in an aqueous solution of one or more metal salts of n and Ti, followed by immersion in an aqueous solution of hydrazine, followed by drying. Method.