JPS63185445A - White deodorant and its production - Google Patents

Abstract

PURPOSE:To enhance the capability of the deodorant in adsorbing a malodorous gas such as H2S by preparing the white deodorant from the fine powder of the tight agglomerate of titanium oxide, zinc oxide, and magnesium oxide and/or calcium oxide and water. CONSTITUTION:The aq. mixed soln. contg. a water-soluble titanium compd., a water-soluble zinc compd., and a water-soluble magnesium compd. and/or a water-soluble calcium compd. and an aq. alkaline soln. are partly or wholly mixed so that the pH of the obtained liq. mixture is controlled to 7-11, and a deposit is formed. The deposit is then separated from the liq. mixture, and then dried to obtain the white deodorant, the white powder, consisting of TiO2, ZnO, (MgO and/or CaO), and H2O. The deodorant has excellent capability in adsorbing hydrogen sulfide, mercaptans, amines, ammonia, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a deodorizing agent for various malodorous gases such as hydrogen sulfide, ammonia, mercaptans, amines and aldehydes, and more specifically to deodorizing agents for various malodorous gases such as hydrogen sulfide, ammonia, mercaptans, amines and aldehydes. Mainly composed of a mixture of magnesium and/or calcium oxide,
The present invention relates to the provision of a completely new deodorizing agent in the form of a white fine powder containing some water molecules and having very good adsorption properties.

[Prior art] In recent years, various foul-smelling gases such as hydrogen sulfide, ammonia, mercaptans, amines, and aldehydes generated in daily life have significantly worsened the living environment. There is increasing social interest in deodorizing agents having the function of removing gases, and various types of deodorizing agents are actually used.

These deodorizers are used in daily life, so
It is required that at least the following conditions be met.

■ Hydrogen sulfide, ammonia, and
It must have good deodorizing performance against various malodorous gases such as mercaptans, amines, and aldehydes.

■It must be highly safe.

■ It must be easy to handle.

■ It must be inexpensive.

■ Must have a sense of cleanliness.

However, until now there has been no deodorizing agent that fully satisfies all of the above conditions, and even recent research has not yet developed one.For example, the activated carbons most commonly used as deodorizing agents include mercaptans and amines. Although it has an excellent deodorizing effect on malodorous gases, its deodorizing performance against hydrogen sulfide and ammonia, which are typical malodorous gases generated in daily life, is poor. In order to improve this point, a product called impregnated carbon, which is made by loading activated carbon with acid, alkali, or a certain type of halide, has been made, but products that have been treated in this way do not contain the acid or alkali itself. Similarly, it is not suitable for use in daily life as it needs to be treated as a type of hazardous material.
An essential drawback of activated carbon is that it is black, and because of this color, the uses of deodorizing agents based on activated carbon are limited.

Also, fJ! Although acid iron (Fe5O4) combined with L-ascorbic acid has a good deodorizing effect on basic malodorous gases such as ammonia and amines, it has almost no deodorizing effect on hydrogen sulfide, mercaptans, aldehydes, etc. It also has the disadvantage that it cannot be used to deodorize wet gases because it dissolves when wet with water.

There are deodorizers that are classified as other chemical deodorants, but many of them are strongly acidic or alkaline, the types of gases that can be deodorized are limited, and they have the disadvantage of being easily affected by moisture absorption or dryness. .

There are also organic deodorizers, but they have poor heat resistance, making them difficult to process and expensive.

As described above, none of the conventional deodorizing agents satisfactorily satisfies all of the conditions (1) to (4) above.

[Purpose] The present invention was made in view of the above-mentioned circumstances, and its purpose is to eliminate hydrogen sulfide and hydrogen sulfide generated in daily life.
The object of the present invention is to provide a deodorizing agent having a new composition, which has a good deodorizing effect against malodorous gases such as ammonia, mercaptans, amines, and aldehydes, is highly safe, and is easy to handle.

[Nari Kozue] The present inventor has already reported (Japanese Patent Application No. 198396/1983) that white TiO-ZnO and H
It was shown that white fine powder consisting of 2O has excellent adsorption properties for various malodorous gases.

As a result of extensive research in order to further improve its adsorption properties, the inventor finally succeeded in combining a mixed aqueous solution of a water-soluble titanium compound, a water-soluble zinc compound, a water-soluble magnesium and/or calcium compound, and an alkaline gas or aqueous solution. The pH of the resulting combined liquid is 7 to 11, preferably 7 to 9.
This causes T to be mixed in the combined liquid.
iO2.

A white precipitate consisting of ZnO, MgO and/or CaO, H2O is produced, and then this precipitate is separated from the combined liquid and dried to produce a fine white powder containing hydrogen sulfide, ammonia, It was discovered that the present invention has extremely good deodorizing performance against malodorous gases such as mercaptans, amines, and aldehydes, and the present invention was completed based on this discovery.

In the production of the deodorizing agent of the present invention, water-soluble titanium compounds that are raw materials include titanium acid, titanyl sulfate, titanium chloride, titanium nitrate, etc., and water-soluble zinc compounds include zinc sulfate, zinc chloride, Zinc nitrate, #acidzinc, etc. can be used. In addition, water-soluble magnesium compounds include calcium sulfate, magnesium chloride,
Magnesium nitrate, magnesium acetate, etc. can be used, and as water-soluble calcium compounds, calcium chloride, calcium nitrate, etc. can be used, but in the case of producing a deodorizer containing calcium oxide, titanium, zinc or magnesium is added to the mixed aqueous solution. The use of sulfates is undesirable because it will form a precipitate of insoluble calcium sulfate in the mixed aqueous solution, and the alkaline aqueous solutions used for neutralization include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and water. Aqueous solutions such as barium oxide and ammonia can be used. However, if the mixed aqueous solution contains sulfate, using calcium hydroxide or barium hydroxide as the alkaline aqueous solution will result in the formation of water-insoluble salts, which is not preferable.

The mixing ratio of water-soluble titanium compound, water-soluble zinc compound, and water-soluble magnesium and/or calcium compound is 10 to 90 mol% and 10 to 90 mol%, respectively.
and in the range of 0.1 to 50 mol%, preferably 3
The ranges are 0-70 mol%, 30-70 mol% and 0.5-30 mol%. That is, at a mixing ratio smaller than this range, the effect of the mixing is not clear, and conversely, at a mixing ratio larger than this range, each T is a fraction.
+02, ZnO.

It is recognized that these adsorption properties are substantially similar to those of MgO and/or CaO, and these adsorption properties are substantially inferior to those of fine powders obtained in the composition range of the present invention.

Regarding the mixing method of a mixed aqueous solution consisting of a water-soluble titanium compound, a water-soluble zinc compound, a water-soluble magnesium compound and/or a water-soluble calcium compound, and an alkaline aqueous solution, the pH of the combined solution of these rainwater solutions is 7.
It is important to mix at the same time so that the number is 11 to 11.

Zinc hydroxide has a high solubility in an aqueous solution at a pH of 6 or below and a pH of 11 or above, resulting in a poor yield in the form of a precipitate. on the other hand,
Magnesium hydroxide, calcium hydroxide p119-1
If it is less than 0, the solubility in an aqueous solution is large and the yield in the form of a precipitate is poor. However, when using a mixed aqueous solution containing a water-soluble titanium compound as in the present invention, the pH is 7 to 1.
In the range 1, zinc hydroxide, magnesium hydroxide, and calcium hydroxide co-precipitate with titanic acid to form hydroxides, so
Good yield and little deviation from liquid composition.

Add an alkaline aqueous solution to the mixed aqueous solution to adjust the pH of the combined solution.
A method of adjusting tA to 7 to 11, or conversely, adding a mixed aqueous solution to an alkaline aqueous solution to adjust the 98 of the combined liquid to 7 to 11.
In the precipitate obtained by the method, titanic acid, zinc hydroxide, magnesium hydroxide, and calcium hydroxide each form separate particles due to their different precipitate formation regions, and the powder obtained by drying these particles. There are particular restrictions on the concentration of mixed aqueous solutions of water-soluble titanium compounds, water-soluble zinc compounds, water-soluble magnesium compounds, and/or water-soluble calcium compounds, where it is impossible to obtain products with excellent properties because they are a mixture of fractions. However, from an industrial point of view, a darker one is preferable.

Also, by combining the mixed aqueous solution and the alkaline aqueous solution, Ti
The temperature when generating a precipitate consisting of O2, ZnO, MUO and/or CaO and H2O is 20-8
Although a temperature range of 0°C can be adopted, a range of 40 to 60°C is preferable. Furthermore, as for the drying temperature after filtering and washing the precipitate, a wide range of 100 to 220°C can be used without any inconvenience, but a temperature of 150 to 220°C is preferable. A range is preferred.

Regarding the thermal stability of the TiO2.ZnO-(M(lO and/or CaO).H2O) deodorizer according to the present invention, heating to 220°C or higher causes a slight change in adsorption properties. , good characteristics are maintained up to around 400°C.

[Effects of the Invention] The TiO,...ZnO-(M!IO and/or CaO)-based white deodorizer according to the present invention eliminates hydrogen sulfide, mercaptans, amines, ammonia, aldehydes, etc. generated in daily life. Not only does it have extremely good properties when it comes to deodorizing various foul-smelling gases, but it also has excellent properties! r: Toxicity T i
Since it is composed of O2, Z n O1M (] O, Ca O, it is highly safe, and since it is a fine powder, it can be easily supported on paper and sheets, and it is thermally stable up to about 400℃. It has excellent processability, such as being able to be kneaded into plastics, so it has high industrial applicability as a deodorizer, and its white color makes it suitable for applications such as cosmetics, sanitary products, and disposable diapers. It can be used for various purposes such as.

[Examples] The following examples will be described in more detail, but these are merely for illustrative purposes, and the scope of the invention is not limited thereto.

Example 1 5j! Pour pure water 11 into a beaker and raise the temperature to 6 while stirring.
The temperature was maintained at 0°C. Next, separately prepared T + 0
79.1 g as ZnO, 65.9 g as ZnO and M
(10) A titanium sulfate/[zinc acid, magnesium sulfate mixed aqueous solution 2ρ containing 8.1 g and an ammonia aqueous solution were added to the pure water for 30 minutes while being careful to maintain the pH of the combined solution at 8. The product was filtered, washed, and dried at 200°C for 3 hours.
2.ZnO.M (10 series white deodorizer was produced.

This white deodorizer was examined by X-ray diffraction and was found to be amorphous.

The adsorption properties of this white deodorizer for malodorous gases such as hydrogen sulfide, mercaptans, ammonia, and amines were investigated as follows. After putting 100 ml of white deodorizing powder into a glass vial with an internal volume of 120 m and sealing it with a rubber stopper, a predetermined amount of malodorous gas component is injected into the vial using a microsyringe. Two hours after injecting the gas, the air in the vial is removed using a microsyringe, and the gas concentration is measured using a gas chromatograph.

The measurement results are shown in Table 1.

Example 2 il! The amounts of TiO2, ZnOl and MgO in 2g of the titanium acid-zinc sulfate-magnesium sulfate mixed aqueous solution were each 61.5g, 51.3. A white deodorizer was obtained in exactly the same manner as in Example 1, except that the amount was 33.6 g. The adsorption ability of this white deodorizer to various malodorous gases is
Shown in the table.

Example 3 'I'i 02. in a mixed aqueous solution 2j consisting of titanium chloride-zinc chloride-calcium chloride. The amounts of ZnO and CaO were 79.1g, 65.9g and 12.1g, respectively.
Ti was prepared in the same manner as in Example 1 except that
An O2-Zn0-CaO-based white deodorizing agent was obtained.

The adsorption properties of this white deodorizer for various malodorous gases were evaluated first.
Shown in the table.

Example 4 Titanium chloride-zinc chloride-calcium chloride mixed aqueous solution 21
[Medium] The amounts of T i O2, Z n O and CaO were each 61.5. , 51.3. TiO2・ZnO・
A CaO-based white deodorizing agent was obtained. Various types of this white deodorizer 7
1! Table 1 shows the adsorption characteristics for inner gas.

Example 5 Titanium chloride-zinc chloride-magnesium chloride-calcium chloride mixed aqueous solution 2! Tie in I...

The amounts of ZnO, MQO and CaO are each 61.5
T i O2 was prepared in exactly the same manner as in Example 1, except that the amounts were 51.3 g, 16.8 g, and 12.1 g.
- A ZnO.MgO-CaO-based white deodorizer was obtained. Table 1 shows the adsorption properties of this white deodorizer for each of the eight malodorous gases.

Comparative example 1 1 g of pure water was taken into a 5 g beaker, and the temperature was raised to 6 while stirring.
While heating and maintaining at 0° C., 1 g of a separately prepared titanium dodecate solution containing 79.9 f as TiO2 and an ammonia aqueous solution were added to the above solution while being careful to maintain the pH of the combined solution at 7.5. They were simultaneously dropped into pure water. The generated precipitate was filtered and washed, and then dried at 200° C. for 3 hours to obtain titanic acid powder. Table 1 shows the adsorption properties of this titanic acid to various malodorous gases.

Comparative Example 2 81.4 g of the titanium sulfate aqueous solution of Comparative Example 1 as ZnO
Zinc oxide powder was obtained in exactly the same manner except that the zinc oxide aqueous solution was used. Table 1 shows its adsorption properties for various malodorous gases.

Comparative Example 3 Oxidation was carried out in exactly the same manner as in Comparative Example 1, except that the titanium sulfate aqueous solution in Comparative Example 1 was changed to 1j! of a magnesium sulfate aqueous solution containing 80 g as M (10), and the neutralization pH was changed from 7.5 to 11. Magnesium powder was obtained.

Table 1 shows its adsorption characteristics for each of the eight malodorous gases.

Comparative Example 4 A titanium sulfate aqueous solution with a ratio of $1111 as CaO is 56
Calcium oxide powder was obtained in exactly the same manner as in Comparative Example 1, except that the pH of the neutralization was changed from 7.5 to 11.

Table 1 shows its adsorption properties for various malodorous gases.

Comparative Example 5 Regarding commercially available activated carbon (specific surface area 1200 m 2 / g), each Pf! Table 1 shows the adsorption properties for malodorous gases.

Claims (1)

[Scope of Claims] 1. A white deodorizer characterized by being a white fine powder consisting of an aggregate of closely bound particles of titanium oxide, zinc oxide, magnesium oxide and/or calcium oxide, and water (H_2O). . 2. The proportions of titanium oxide, zinc oxide, and magnesium oxide and/or calcium oxide in the composition are 10 to 90 mol%, 10 to 90 mol%, and 0.
The white deodorizer according to claim 1, in the range of 1 to 50 mol%. 3. The proportions of titanium oxide, zinc oxide, and magnesium oxide and/or calcium oxide in the composition are 30 to 70 mol%, 30 to 70 mol%, and 0.
The white deodorizer according to claim 2, in the range of 5 to 30 mol%. 4. A mixed aqueous solution containing a water-soluble titanium compound, a water-soluble zinc compound, a water-soluble magnesium compound and/or a water-soluble calcium compound, and an alkaline aqueous solution are combined, and the pH of the combined solution is in the range of 7 to 11. A precipitate is formed by coalescing one part at a time or all at the same time so that the precipitate is separated from the coalescing liquid and then dried to form a mixture consisting of TiO_2.ZnO.(MgO and/or CaO) and H_2O. A method for producing a white deodorizer, characterized by obtaining a white fine powder. 5. TiO_2, ZnO and (Mg
O and/or CaO) ratio is 10 to 90, respectively.
5. The method of claim 4, wherein the mole % ranges from 10 to 90 mole % and from 0.1 to 50 mole %. 6. TiO_2, ZnO and (Mg
O and/or CaO) ratio is 30 to 70, respectively.
The method for producing a white deodorizer according to claim 5, wherein the mol% is in the range of 30 to 70 mol% and 0.5 to 30 mol%. 7. The method according to any one of claims 4 to 6, wherein the reaction temperature for forming the precipitation is 40 to 60°C, and the drying temperature of the powder is 120 to 220°C.