JPH0622673B2 - Porous deodorant filter - Google Patents

Description

TECHNICAL FIELD The present invention relates to a porous deodorizing filter. In detail, factory exhaust gas such as ammonia, hydrogen sulfide, acetaldehyde, tobacco acid generated in the living environment, body odor, human odor,
The present invention relates to a porous deodorizing filter used for deodorizing and purifying food odors in a refrigerator or exhaust gas from automobiles.

[Prior Art] Conventionally, a filter made of activated carbon has been used to deodorize and purify air.

On the other hand, a method of neutralizing and deodorizing malodorous components by a chemical reaction is known.For example, a porous substance is loaded with an extracted component extracted from a plant, and a substance that is difficult to be adsorbed by physical adsorption alone is adsorbed by a chemical reaction. A deodorizing filter according to Japanese Patent Laid-Open No. 62-360 has been proposed.

[Problems to be Solved by the Invention] However, activated carbon alone may not provide a sufficient effect depending on the type of malodorous component. For example, ammonia, which is the main component of malodorous substances generated in the living environment,
It is difficult to adsorb odorous substances with low molecular weight and polarity, such as acetaldehyde. In addition, since activated carbon is adsorbed by physical adsorption, it adsorbs substances other than malodorous components to be adsorbed and removed, such as water vapor and a good scent, resulting in a significant decrease in the adsorption ability of malodorous components to be originally removed. There was a problem. Further, in the physical adsorption, the capacity of the adsorbent is limited, and when the saturated adsorption state is reached, the malodorous component cannot be further adsorbed, and conversely, there is a problem that the malodorous component once adsorbed is re-released.

On the other hand, the above conventional deodorant filter utilizing a chemical reaction,
Adsorption and removal performance of ammonia is high, but removal performance for sulfur-based odors such as methyl mercaptan and hydrogen sulfide is not sufficient, and lower aldehydes such as formaldehyde and acetaldehyde can hardly be adsorbed. It was the current situation.

In addition, the manufacturing process is complicated and the cost is high, the workability is low, and the exhaust treatment after use is difficult.

Among the main malodorous components, salts of phenylhydrazine and 2,4-dinitrophenylhydrazine are known as effective chemicals for the adsorption and removal of lower aldehydes and are widely used for collecting and quantifying lower aldehydes. Especially 2,
The hydrochloride of 4-dinitrophenylhydrazine is used for the measurement of acetaldehyde specified in the Odor Control Law, and it seems to be effective in chemically removing acetaldehyde in the air.

However, since these chemicals are considered to be cancer-inducing factor substances, their effects on the human body are feared, and when used in a living space, the odors of their own may cause aversion to humans. It is not possible to apply these chemicals to deodorant filters, and deodorant filters that show a remarkable effect of removing lower aldehydes have not yet been realized.

Therefore, the object of the present invention is to provide ammonia, which is a main component of malodor generated in the living environment, nitrogen-based odors such as trimethylamine, sulfur-based odors such as hydrogen sulfide and methyl mercaptan, and lower aldehydes such as formaldehyde and acetaldehyde. An object of the present invention is to provide a deodorant filter which is excellent in removing odors from the system, is safe, inexpensive, has high workability, and is easily disposed of.

[Means for Solving the Problems] The present inventors have overcome such conventional drawbacks and have a quick and excellent effect of removing nitrogen-based odors, sulfur-based odors, and lower aldehyde-based odors. As a result of intensive studies to develop a deodorizing filter that exhibits the effect, paper containing sepiolite was used as an adsorption carrier, and o-, m-, or p-aminobenzoic acid or its salts, p-aminosalicylic acid or By supporting at least one selected from the salts, cupric chloride, or ferrous chloride,
It has been found that an extremely high effect can be obtained.

In the present invention, the paper on which the above-mentioned various compounds are carried is a paper containing sepiolite in the paper (hereinafter referred to as an adsorption carrier), and the usual production method such as a cylinder type, a short-net type and a Fourdrinth type is used. Paper manufactured by any method may be used. Further, it is also possible to carry out papermaking by a method in which fine powder of sepiolite is placed in a solution state and impregnated into paper.

Sepiolite well adsorbs malodorous gases such as ammonia, isovaleric acid, butyric acid, trimethylamine, and pyridine, and by fixing 50% by weight or more in paper, it is possible to impart an odorous component adsorption function to paper.

The shape of the adsorption carrier is not particularly limited, and may be, for example, a honeycomb shape, a sheet shape, a section shape, or a strip shape, but by making it a honeycomb shape, the pressure loss as a deodorant film is small, and A large contact area with the offensive odor gas makes it possible to improve deodorization efficiency.

The components supported on the adsorption carrier include o-, m-, or p-aminobenzoic acid, p-aminosalicylic acid (hereinafter referred to as aromatic amino acid), or salts of these aromatic amino acids, and further cupric chloride or chloride. Ferrous iron is preferably used. Specific examples of the salts of aromatic amino acids include metal salts such as sodium salts and potassium salts of the aromatic amino acids described above, inorganic salts such as sulfates, sulfates and hydrochlorides.

The deodorizing filter of the present invention is one in which at least one of an aromatic amino acid, a salt of an aromatic amino acid, cupric chloride, or ferrous chloride is supported on the adsorption carrier, and thereby excellent malodor removing performance is obtained. Is also expressed. Further, it is of course possible to use two or more kinds of the above-mentioned supported components in combination, and a higher effect can be obtained by their synergistic effect. At this time, for example, an aromatic amino acid or a salt of an aromatic amino acid has an extremely high effect on a malodorous gas of lower aldehydes, and cupric chloride and ferrous chloride have an extremely high effect on a malodorous gas of sulfur type and nitrogen type. It is more effective to use a combination of at least one kind of aromatic amino acid or salts of aromatic amino acid and at least one kind of cupric chloride or ferrous chloride.

The method for supporting these aromatic amino acids or salts thereof, cupric chloride, or ferrous chloride on the adsorption carrier is not particularly limited, but is dissolved in a soluble solvent such as water or ethyl alcohol, and the solution is sprayed, brushed, Impregnate with a pipette or soak up the adsorption carrier directly into the solution and pull up.
Then, a method of evaporating the solvent and supporting the solvent is used.

The amount of the aromatic amino acid or its salt, cupric chloride, or ferrous chloride loaded on the adsorption carrier is not particularly limited, but is usually 0.5 to 90% by weight relative to the adsorption carrier.
The range of is desirable. If the supported amount is less than 0.5% by weight, the effect of adsorbing and removing the malodorous component is small, and if it exceeds 90% by weight, the dispersibility in the carrier is poor and the effect of removing the malodorous component is reduced, which is not economical. Above all, it is more preferable to support 1 to 80% by weight.

[Operation] The porous deodorant filter of the present invention contains aromatic amino acids or salts thereof, cupric chloride, or ferrous chloride as its active ingredient, and is a main component of malodorous gas generated in the living environment. Adsorbs and removes nitrogen-based odors, sulfur-based odors, and lower aldehyde-based odors.

Of these, aromatic amino acids or salts thereof have a remarkable effect on the removal of malodorous gases of lower aldehydes,
The effect is further improved by supporting it on the adsorption carrier. This is because by supporting it on the adsorption carrier, the contact area between the aromatic amino acid or its salt and the malodorous gas based on the lower aldehydes is broadened, and the adsorption ability is enhanced, and in addition, the binding with the adsorption carrier is lower aldehyde. It is considered that this is because it has an action of promoting the adsorption of the compounds.

The mechanism of this action is not clearly known, but when the adsorption carrier carries an aromatic amino acid or its salt, the conjugation system at the molecular level changes, and the electrons of the carboxyl group and amino group are localized, and It is considered that the reaction with the aldehyde group is promoted when aldehydes come.

Cupric chloride or ferrous chloride is methyl mercaptan,
It is particularly effective for removing sulfur malodorous gases such as hydrogen sulfide and nitrogen malodorous gases such as ammonia and trimethylamine.

The ability to remove malodorous gas with cupric chloride or ferrous chloride is that these compounds produce copper sulfide or iron sulfide for sulfur malodorous gas, and complex for nitrogen malodorous gas. It is thought to be to generate. Then, by supporting the malodorous gas on the adsorption carrier, the contact area with the malodorous gas is expanded to further improve the malodorous gas adsorption ability.

The adsorption carrier retains these supported components in the pores in its structure to promote its action, and further improves the malodor removing performance of the deodorant filter due to the adsorption ability of the adsorption carrier itself.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples without departing from the gist thereof.

Example 1 One each of o-, m-, and p-aminobenzoic acid, p-aminosalicylic acid, and sodium o-aminobenzoate was used.
A 0 g beaker was weighed and 90 g of ethyl alcohol was added to prepare an ethyl alcohol solution of an aromatic amino acid or its salt.

Next, paper containing sepiolite (21.8 cm × 21.
8 cm × 0.13 cm, hereinafter referred to as an adsorption carrier), a solution of the aromatic amino acid or a salt thereof in ethyl alcohol was carefully dropped by a pipette so as to uniformly impregnate the solution. Then, this adsorbent carrier was heated and dried in a dryer at 100 ° C. for 16 hours to evaporate ethyl alcohol to obtain a porous deodorizing filter of the present invention (invention products 1 to 4).

A removal performance test of each of the obtained deodorizing filters for ammonia, hydrogen sulfide, and acetaldehyde was conducted as follows.

First, cut out the deodorant filter into 5 mm squares, and cut this piece 5 g.
Was weighed and put in the deodorizing column 1 of the deodorizing test device shown in FIG. The measurement conditions are shown in Table 1.

Next, while the malodorous gas was vaporized using the odorous substance vaporizer 3, it was introduced into the container 2 at 25. The initial concentrations of the malodorous gas were such that ammonia was 60 ppm, hydrogen sulfide was 9 ppm, and acetaldehyde was 50 ppm.

Under the conditions shown in Table 1, the air in the system was circulated using the circulation pump 4, and a small amount of the gas in the device after a predetermined time was sampled from the gas collection hole 5 using a microsyringe to change the gas concentration. Examined. The measurement was performed using a Kitagawa gas detector tube for ammonia and hydrogen sulfide, and a gas chromatograph for acetaldehyde. Table 2 shows the measurement conditions of the gas chromatograph. The results are shown in Tables 3-5. In the figure, 6 is a constant temperature and humidity chamber, 7 is a flow meter, and 8 is a manometer.

Example 2 10 g of cupric chloride was weighed in a beaker, 90 g of water was added to prepare an aqueous solution of cupric chloride, and the aqueous solution of cupric chloride was loaded on an adsorption carrier in the same manner as in Example 1 to remove the porosity of the present invention. An odor filter was obtained (invention product 6).

With respect to the obtained deodorizing filter, a removal performance test for ammonia, hydrogen sulfide and acetaldehyde was conducted in the same manner as in Example 1, and the results are shown in Table 6.

Example 3 10 g of ferrous chloride was weighed in a beaker, 90 g of water was added to prepare an aqueous solution of ferrous chloride, and the aqueous solution of ferrous chloride was loaded on an adsorption carrier in the same manner as in Example 1 to remove the porosity of the present invention. An odor filter was obtained (invention product 7).

With respect to the obtained deodorizing filter, a removal performance test for ammonia, hydrogen sulfide and acetaldehyde was conducted in the same manner as in Example 1, and the results are shown in Table 7.

Example 4 A single-sided E corrugated cardboard (number of steps: 95/30 cm, height of steps: 1.
2mm) and stacked and bonded to each other to form the corrugated honeycomb shown in Fig. 2 (dimensions per unit: width 30mm x height 20)
mm × thickness 14 mm, weight 2 g) were produced.

Next, 10 g of cupric chloride and 10 g of o-aminobenzoic acid were weighed in beakers, and 90 g of water and 90 g of ethyl alcohol were added to each, and a 10 wt% cupric chloride aqueous solution,
An ethyl alcohol solution of 10 wt% o-aminobenzoic acid was prepared.

Cupric chloride aqueous solution on one side of the corrugated honeycomb,
On the other hand, a solution of o-aminobenzoic acid in ethyl alcohol,
It was sprayed with a sprayer to ensure uniform impregnation. Next, this corrugated honeycomb is dried at 100 ° C. for 16 hours.
After heating and drying for a while, water and ethyl alcohol were evaporated to obtain a porous deodorant filter of the present invention (Invention product 8). The loadings of cupric chloride and o-aminobenzoic acid were each 10% by weight.

With respect to the obtained deodorizing filter, the internal dimensions of the deodorizing column 1 of the deodorizing test device used in Example 1 were 30 × 20 × 240 mm.
Example 1 except that the capacity of the container 2 was changed to 30
A odor gas removal performance test was conducted in the same manner as in. The initial concentration of malodorous gas is 40 ppm for ammonia and 9 for hydrogen sulfide.
ppm, methyl mercaptan was 9 ppm, and acetaldehyde was 30 ppm, and the results are shown in Table 8. Two deodorant filters were used in combination, and the deodorant filters were arranged in series in the deodorizing column 1 as shown in FIG.

For ammonia and acetaldehyde, see Table 9
The same test was performed by changing the initial concentration as shown in, and the relationship between the residual concentration of the gas in the container 2 after 30 minutes of circulating the gas in the device and the adsorption amount per unit volume of the sample was examined. It was

The adsorption amount w (mg / cm ³ ) was calculated according to the following formula, and the results are shown in Table 9.

Here, Mw: molecular weight of ammonia or acetaldehyde V: volume of container () C0: initial concentration (ppm) C30: residual concentration after 30 minutes (ppm) v: sample volume (cm ³ ).

Comparative Example 1 Using a commercially available deodorant filter obtained by processing a paper sheet made of pulp into one-sided E corrugated board, winding it into a roll, and impregnating this with an extract substance extracted from plants, A removal performance test for ammonia, hydrogen sulfide, and acetaldehyde was conducted in the same manner as in Example 1. The results are shown in Table 10.

Comparative Example 2 The same commercially available deodorant filter as that used in Comparative Example 1 was used.
A piece having a width of 30 mm, a height of 20 mm, and a thickness of 28 mm was cut out, and the same removal performance test as in Example 4 was conducted by using this. Table 11 shows the concentration changes of ammonia, hydrogen sulfide, methyl mercaptan, and acetaldehyde over time, and Table 1 shows the relationship between the residual concentration of ammonia and acetaldehyde and the adsorption amount.
Shown in 2.

From the above results, the porous deodorant filter of the present invention exerts a rapid and excellent removal effect on nitrogen-based odors, sulfur-based odors and lower aldehyde-based odors, and is a conventional deodorant filter. It can be seen that the adsorption and removal performance is remarkably excellent in comparison.

[Advantages of the Invention] The porous deodorant filter of the present invention comprises a nitrogen-based odor such as ammonia, trimethylamine and the like, which is a main component of malodor generated in a living environment, a sulfur-based odor such as methyl mercaptan and hydrogen sulfide, and formaldehyde. Excellent removal performance against odors of lower aldehydes such as acetaldehyde.

In addition, it has almost no odor itself and is excellent in safety for the human body. Moreover, since paper is used as the base material of the adsorption carrier, it can be manufactured at low cost, has extremely high workability, and is easily disposed of. Further, if the adsorption carrier is formed in a honeycomb shape, the deodorizing filter has a small pressure loss and a large contact area with the malodorous gas, so that the deodorizing efficiency can be further improved.

[Brief description of drawings]

FIG. 1 is an overall configuration diagram of a deodorizing test device used in an embodiment of the present invention, and FIG. 2 is an overall perspective view of a porous deodorizing filter of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 61-136438 (JP, A) JP-A 50-160186 (JP, A) JP-A 63-84618 (JP, A) JP-A 53- 50068 (JP, A) Japanese Patent Publication Sho 53-20954 (JP, B2)

Claims (1)

[Claims] 1. A paper containing sepiolite is used as an adsorption carrier, and o-, m-, or p-aminobenzoic acid or a salt thereof, p-aminosalicylic acid or a salt thereof, cupric chloride, or cuprous chloride is used. A porous deodorant filter carrying at least one selected from iron.