JPH01148340A - Deodorant composition - Google Patents

Abstract

PURPOSE:To increase the deodorizing speed of a deodorant compsn. and to improve the durability by preparing the compsn. with aluminosilicate having a specified compsn. consisting of SiO2, Al2O3 and other metal oxide and a porous material having >=500m<2>/g specific surface area. CONSTITUTION:Aluminosilicate consisting of 5-80mol% SiO2, 5-65mol% MOn/2 (M is Zn, Cu, Ag, Co, Ni, Fe, Ti, Ba, Sn or Zr and n is the valence of the metal M) and 1-60mol% Al2O3 is produced. The aluminosilicate is blended with a porous material having >=500m<2>/g specific surface area to prepare a deodorant compsn. The porous material may be activated carbon, silica gel or synthetic zeolite. The pref. amt. of the alumlnosilicate used is 30-95wt.% and that of the porous material is 5-70wt.%.

Description

[Detailed description of the invention] The present invention has excellent deodorizing power, and is effective against daily life odors generated by human waste, wastewater, garbage, etc., and industrial odors generated at bulk factories, chemical factories, etc. This invention relates to a deodorizing base that can be used in a wide range of applications.

As people's daily lives become more urbanized and diversified, people become more concerned about the smells around them, and in particular, bad odors are being criticized more harshly. The following methods are generally known as methods for treating bad odors.

■Sensory deodorization...masking with perfume ■Physical deodorization...adsorption with activated carbon, etc. Absorption and inclusion by cyclodextrin.

■Chemical deodorization...neutralization with acids and alkalis.

Oxidation, oxidation and reduction with reducing agents. Addition with lauryl methacrylates, etc.

■Biological deodorization: Deodorization due to the bactericidal action of disinfectants and the effect of microorganisms or enzymes.

However, in the sensory deodorization method (2), the quality of the bad odor is changed by the fragrance, and the bad odor itself exists, and if it loses its balance with the fragrance, it may even create a feeling of disgust.

The physical deodorizing method (2) adsorbs or absorbs and includes malodors, but there is a problem in that the adsorption capacity for various malodorous gases is insufficient.

■Chemical deodorization has some safety issues, and although it is effective against a single type of bad odor, it cannot be a panacea against the complex odors of today's daily life. .

Biological deodorization (2) has shortcomings in terms of speed and sustainability, and a single deodorization method alone is not sufficient.

Activated carbon is the most commonly used deodorant and is known to adsorb various malodorous components. However, it has poor deodorizing power against hydrogen sulfide and ammonia among malodorous components.

In order to improve this point, activated carbon is made to support a halide (Japanese Unexamined Patent Publication No. 55-51421).

Research has been carried out on supporting metals (Japanese Patent Laid-Open No. 137089/1989) and impregnating acids and alkalis, but these have not yet been satisfactory. In addition, these activated carbons exhibit acidic/alkali properties due to adhesion of moisture, etc., causing corrosion and requiring handling as hazardous materials, so they are not suitable for use in daily life.

It is also known to use divalent iron salts or divalent iron salts as deodorants (Japanese Patent Laid-open Nos. 58-156539 and 59-146578). In particular, it has been reported that divalent iron salts have a deodorizing effect on basic malodors such as ammonia, but their deodorizing power against hydrogen sulfide, mercaptans, etc. is not sufficient.

Furthermore, the above-mentioned publications generally describe deodorizing performance against various types of bad odors, but when considering the uses of deodorants,
Deodorization speed and amount of deodorization are also important factors.

The present inventors previously proposed the use of an aluminosilicate having a composition containing SiO, MOY and AM, O□ in specific amounts as a deodorant, as a three-component ratio expressed as an oxide. (Patent Application No. 62-54860). This deodorizer exhibits excellent deodorizing effects against various types of bad odors.

INDUSTRIAL APPLICABILITY The present invention provides a deodorant composition that exhibits an excellent deodorizing effect against various types of bad odors, has a high deodorizing speed, and has excellent durability.

The deodorant composition of the present invention is characterized by containing the following components (a) and (b).

(a) An aluminosilicate having a three-component composition ratio expressed as an oxide corresponding to the following.

SiO,: 5 to 80 mol% MO: 5 to 65 mol% Kinuta Q, O,: 1 to 60 mo/L1% (M is zinc,
Copper, silver, cobalt, nickel.

(b) A porous material containing at least one metal selected from iron, titanium, barium, tin, and zirconium, where n represents the valence of the metal. (b) A porous material having a specific surface area of 500 r&/g or more.

The present invention will be explained in more detail below.

The alumino metal silicate of component (a) has a three-component composition ratio expressed as an oxide within the above range, and is preferably as follows.

S i O,: 25-75 MO/L/% MO,: 15-
60Mo) L1% A nil, O,: 1 to 45-T-/L/% The aluminosilicate of component (a) is obtained as a white or light-colored powder, and the amount corresponding to the above composition ratio Manufactured by reacting a water-soluble silicate, a water-soluble metal salt, a water-soluble aluminum salt and/or a water-soluble aluminate, etc. in the presence of water, and heating the resulting precipitate in the presence of water if necessary. be done.

This reaction easily proceeds by the so-called double decomposition method.

That is, an alkali silicate such as sodium silicate is used as the silica component, a water-soluble metal such as chloride, nitrate, or sulfate is used as the metal oxide component, and sodium aluminate and/or aluminum chloride is used as the alumina component. A water-soluble aluminum salt such as aluminum sulfate is used, and these are mixed in the presence of water to cause a reaction to occur by metathesis.

In order to carry out this metathesis reaction homogeneously, it is preferable to carry out the reaction while simultaneously pouring an aqueous silicate solution, an aqueous metal salt solution, and an aqueous solution containing an alumina component into water in which silica has been previously dispersed.

The reaction by metathesis is sufficient at room temperature, but it can also be carried out under heating (for example, reaction under heating up to about 95°C is of course possible).

The pH of the reaction system during simultaneous injection is 5-10, especially 6-10.
It is best to keep it within the range of 9. For this purpose, if necessary, an acid or alkali is added to the reaction system to maintain the pH of the solution within the above range.

The simultaneous addition produces an aluminosilicate precipitate whose composition approximately corresponds to the aqueous solution composition.

By separating this precipitate or, if necessary, heating it in the presence of moisture, it is obtained as a white to light-colored powdery substance.

As the component (b), a porous material having a BET specific surface area of 500 i/g or more, preferably 700 or more is used. Activated carbon, silica gel, and synthetic zeolite are typical examples of such porous materials. Activated carbon is obtained by treating coal, petroleum residue, charcoal, fruit shells, etc. with water vapor, carbon dioxide, etc. by a gas activation method, or by a chemical activation method such as zinc chloride, and has a BET specific surface area of 50.
0-2000 go/g, preferably 700-2000 go/g
The aluminosilicate of component (,) is preferably used in the deodorant composition in an amount of 30 to 95% by weight, preferably 50 to 90% by weight.

The porous material of component (b) has a content of 5 to 70% in the deodorant composition.
It is suitable to use it in an amount of 10 to 50% by weight, preferably 10 to 50% by weight.

If the amount of activated carbon in component (b) is less than 5% by weight, the deodorizing rate will not necessarily be sufficiently high, while if it exceeds 70% by weight, no increase in the amount of deodorizing will be observed.

Foul-smelling gases generated in daily life generally consist of many components.1 Typical malodorous components include nitrogen-based gases such as ammonia and amines, and sulfur-based gases such as hydrogen sulfide and mercaptans, which are generated in large amounts. Are known. However, since these nitrogen-based malodorous components and sulfur-based malodorous components behave differently, there has been no deodorizing base material that is effective against both malodorous components.

In the present invention, by using a specific aluminosilicate as component (a), it is possible to deodorize both malodorous components. In addition to being effective against various types of bad odors, the performance required for a deodorant is that it has a high deodorizing speed and a large amount of deodorizing, that is, it has excellent sustainability.

In the present invention, by using the aluminosilicate as the component (a), the product exhibits deodorizing power against various bad odors.

Furthermore, by combining a specific porous material as component (b), the deodorizing speed and amount were improved.

Aluminosilicate is said to have the characteristics of a solid acid and a solid acid group, and in silica-alumina catalysts, the acidity changes depending on the alumina content, and the acidity changes depending on the content ratio of alumina and silica. It is said that the aluminosilicate of component (a) is different from the acidic Si
Because it has a structure in which O, and a basic metal oxide are combined, it has basic and acidic polarity.1 It exhibits deodorizing effects mainly based on chemisorption and chemical reactions against both types of malodorous components. I think that the.

On the other hand, porous materials with a specific surface area of 500 rrr/g or more, such as activated carbon, are excellent in physical adsorption.

Although the deodorizing mechanism of the deodorant composition of the present invention is not clear, it is thought that physical adsorption proceeds at a very rapid rate until reaching equilibrium adsorption, followed by chemical adsorption and chemical reaction. That is, by combining the porous material of component (b) and the aluminosilicate of component (a), the speed of physical adsorption of the porous material with a large specific surface area and the chemical adsorption of the physically adsorbed bad odor by aluminosilicate・It is thought that the chemical reaction effect works synergistically to deodorize even more effectively.

In addition, odors captured through chemisorption and chemical reactions are no longer released as odors.
It is thought that the desorption of odors, which is a disadvantage of physical adsorption, was suppressed and the sustainability of the deodorizing effect was improved.

According to the deodorant composition of the present invention, the specific aluminosilicate as the component (a) and the specific surface area of the component (b) are 50 On-
By using a porous material of r/g or more in combination, it shows superior deodorizing power than when each is used alone, and shows excellent deodorizing power against various malodorous components, and has a large deodorizing effect. It is possible to express the deodorizing effect quickly and maintain the deodorizing effect for a long period of time.

Bad odors emitted from the human body, indoors, living environments, industrial facilities, etc. contain various malodorous components, but the deodorizer of the present invention quickly and over a long period of time deodorizes these components, so it can be used widely. can do.

The following is an example of the synthesis of aluminosilicate as component (a).

Examples of deodorant compositions using this and the evaluation results will be explained in order.

Synthesis example 1 No. 3 sodium silicate (S i O,: 22.0%.

109g of Na2O (0%) and 94g of sodium hydroxide
Dissolve g (NaOH content: 2.35 mol) in water, add the entire amount to IQ, and add this to liquid A (Si02 min: 0.4-
1-jLz).

On the other hand, 95 g of zinc chloride (anhydrous salt) and aluminum chloride (
Dissolve 97 g of hexahydrate salt in water to make the total amount 1a, and add this to Solution B (ZnO content = 0.7 mol, Afi, O.

minute: 0.2 mol).

Water IQ was placed in a 5Q beaker, and while stirring, liquids A and B were simultaneously added at a rate of about 25 cc/min. After the addition was completed, the pH of the reaction solution was 6.9.

After further stirring and aging for 30 minutes, 85~
Heated at 90°C for 2 hours. The reaction solution was suction filtered, washed with water, and dried at 110°C. The resulting cake was sorted through a sieve to obtain white granules of zinc aluminosilicate as granules of 8 to 16 meshes.

The three-component composition ratio and BET specific surface area of the obtained granules are shown after Synthesis Example 12 together with the subsequent Synthesis Examples.

Synthesis Example 2 As in Synthesis Example 1, No. 3 sodium silicate (S i O□: 2
Dissolve 139 g of sodium hydroxide (2%, Na, Onia, 0%) and 88 g of sodium hydroxide (NaOH content: 2.2 mol) in water, make the total amount IQ, and add this to liquid A (Sin 2 min: 0.51 mol). do.

On the other hand, 65 g of zinc chloride (anhydrous salt) and aluminum chloride (
126g of hexahydrate salt was taken as IQ, and this was used as solution B (Zn0 min:
0.48 mol, AQ, O, min: 0.26 mol).

Water IQ was placed in a 5Q beaker, and while stirring, liquids A and B were simultaneously added at a rate of about 25 cc/min. After the addition was completed, the pH of the reaction solution was 8.6.

Thereafter, the same treatment as in Example 1 was carried out to obtain zinc aluminosilicate as granules of 8 to 16 meshes.

Synthesis example 3 No. 3 sodium silicate (SiO,: 22.0%).

273g of Na, Onia, 0%) and 60g of sodium hydroxide
Dissolve g (NaOH content = 1.5 mol) in water and add the entire amount to I
This will be referred to as Q and this will be referred to as Solution A (Sin 2 min: 1.0 mol).

On the other hand, 34 g of silver nitrate and aluminum nitrate (9 hydrate)
Dissolve 225 g in water to make the total amount IQ, and use this as Solution B (AgzO content: 0.1 mol, AQ, O, content: 0.3 mol).

Water IQ was placed in a 5Q beaker, and while stirring, solutions A and B were simultaneously added at a rate of about 25 oc/min. After the addition was completed, the pH of the reaction solution was 8.9.

Stirring was continued and the mixture was aged for 1 hour. The resulting cake was sorted through a sieve to obtain silver aluminosilicate as granules of 8 to 16 meshes. Examples 9 to 11 Synthesis Examples 4 to 11 Cobalt, nickel, iron, copper, titanium, barium, tin, and zirconium were prepared in the same manner as in Synthesis Example 3 (silver salt) using Liquids A and B in Table 1 below, respectively. created an aluminosilicate containing

(Left below) Synthesis Example 12 No. 3 Sodium Silicate (SiO,: 22%, Na, Onia,
0%) and 94 g of sodium hydroxide (NaOH
2.35 mol) in water and take the total amount as IQ,
This is called liquid A (SiO□ min=0.4 mol).

On the other hand, 47 g of copper chloride (anhydrous salt), 48 g of zinc chloride (anhydrous salt), and 97 g of aluminum chloride (hexahydrate) were dissolved in water to make a total volume of 1 n, and this was dissolved in solution B (Cu 0 min: 0
．． 35 mol, Zn0 min: 0.35 mol.

AQ, O, min: 0.2 mol).

Water 12 was placed in a 5Q beaker, and while stirring, liquid A and liquid B were each simultaneously injected at a rate of about 25 cc/min. After the oil filling was completed, the pH of this reaction solution was 6.8. Stirring was continued, and the reaction solution 1, which had been aged for 1 hour, was suction-filtered, washed with water, and dried at 110°C. The resulting cake is sorted through a sieve and aluminosilicate (zinc) is removed as a blue-white granulate of 8 to 16 meshes.

Copper) was obtained.

Table 2 shows the measurement results of the three-component composition ratio and specific surface area of the powdery products obtained in Synthesis Examples 1 to 12.

Example 1 800 g of zinc aluminosilicate obtained by the method of Synthesis Example 1
and activated carbon manufactured by Mitsubishi Kasei (Diasorb G・6~1O
) (specific surface area: 900 i/g) to prepare a deodorant composition.

The evaluation results of this composition will be described later together with Examples 2 to 11.

Examples 2 to 10 Same as Example 1 except that the aluminosilicates obtained in Synthesis Examples 3 to 12 were used, respectively.

A deodorant composition was prepared.

Evaluation of deodorizing effect 1 Meat, vegetables, fish, etc. were placed in a 6Q desiccator and left for two weeks to create an artificial garbage odor.

5 g of the above deodorant composition was wrapped in a nonwoven fabric and placed in a 1.8Q wide mouth bottle to prepare a sample.

Furthermore, from a 6Q desiccator, put 10 mQ of headspace gas with an artificial raw garbage odor into a wide-mouthed bottle.

The odor intensity over time was sensory evaluated using the following criteria.

The evaluation was done by a panel of 5 people, and the top and bottom two people were cut out.
The average of the names was rounded off.

The results are shown in Table 3.

(Left below) Example 12 750 g of the aluminosilicate obtained by the method of Synthesis Example 2 and 250 g of powdered activated carbon (Diasorb F-100 manufactured by Mitsubishi Kasei ■, specific surface area 1050 m2/g) were mixed, and 500 g of water was added. 110℃ after addition and kneading using a mortar
and dried to obtain a cake. This cake was sieved through a sieve to obtain a deodorant composition as gray granules of 4 to 8 meshes.

The evaluation results of this composition will be described later together with Example 13.

Example 13 250 g of zinc aluminosilicate obtained by the method of Synthesis Example 2
A deodorant composition was prepared in the same manner as in Example 12, except that 750 g of the same activated carbon as in Example 1 were mixed.

Confirmation of deodorizing effect 2 Using the compositions obtained in Examples 12 and 13,
Exhaust gas treatment was carried out in a pigpen housing 100 pigs. For exhaust gas treatment, an air inlet was installed in the ceiling of the pigsty, and the air was forcibly exhausted from the lower side wall of the pigsty using an exhaust fan. The air in the pigpen was forcibly exhausted by passing through the deodorant composition layer at the front and rear stages of the exhaust fan. The exhaust gas passing through the latter deodorant composition layer was collected in a 3Q odor bag, and the odor intensity was determined by sensory evaluation.

The evaluation criteria and calculation method for sensory evaluation are as follows: Confirmation of deodorizing effect 1
Compliant with. The above results are shown in Table 4.

(Left below) Example 14 The zinc aluminosilicate salt obtained in Synthesis Example 1 was pulverized using a small impact pulverizer (sample mill).

It was made into a white fine powder.

Mix 800 g of this white fine powder with 200 g of powdered activated carbon (Diasorb F-100 manufactured by Mitsubishi Kasei ■), and add 3 ml of water.
00g was added and kneaded using a mortar, followed by drying at 110°C to obtain a cake. Sieve this cake through a sieve,
The deodorant composition was obtained as gray granules of 8 to 16 meshes.

When the obtained composition was spread on the floor bottom of a bird cage and two canaries were raised, no bird excrement odor was generated even after 7 days.

Claims (1)

[Claims] 1. (a) SiO in a three-component composition ratio expressed as an oxide
_2: 5 to 80 mol% MO_n: 5 to 65 mol% Al_2O_3: 1 to 60 mol% (M is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium) , n represents the valence of the metal); and (b) a porous substance having a specific surface area of 500 m^2/g or more. Composition. 2. Claim 1, wherein the porous material is activated carbon.
The deodorant composition described in section.