JPS63183065A - White deodorant and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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, and amines, and more specifically to a deodorizing agent for various malodorous gases such as hydrogen sulfide, ammonia, and amines.
The present invention relates to a completely new deodorizing agent in the form of a fine white powder, which is mainly composed of a hybrid of titanium dioxide (usually titanium dioxide), magnesium oxide and/or calcium oxide, contains some water molecules, and has extremely 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 growing social interest in deodorizers that have the function of removing gas.
Various types of deodorizers are actually used.

Since these deodorants are used in daily life, they are required to satisfy at least the following conditions.

■ It must have good deodorizing performance against various malodorous gases such as hydrogen sulfide, ammonia, mercaptans, and amines that are generated in daily life, ■ It must be highly safe, and ■ It must be easy to handle. ■It must be inexpensive; ■It must be clean.

However, no deodorizing agent has hitherto existed that fully satisfies all of the above conditions, and no deodorizing agent has yet been developed through recent research. For example, activated carbon, which is most commonly used as a deodorizer, has an excellent deodorizing effect on malodorous gases such as mercaptans and amines, but it has poor deodorizing properties against hydrogen sulfide and ammonia, which are typical malodorous gases generated in daily life. It is something that In order to improve this point, a product called impregnated carbon, in which activated carbon is loaded with acid, alkali, or a certain type of halide, is also produced, but products that have undergone such treatment may not contain the acid or alkali itself. Similarly, it is not suitable for use in daily life as it needs to be handled as a type of hazardous material. In addition, an essential drawback of activated carbon is that it is black, and this color tone limits the applications of deodorizing agents based on activated carbon.

In addition, iron sulfate (FeSO4) combined with L-ascorbic acid has a good deodorizing effect on basic malodorous gases such as ammonia and amines, but has almost no deodorizing effect on hydrogen sulfide, mercaptans, aldehydes, etc. Also, since it dissolves in water, it has the disadvantage that it cannot be used to deodorize humid gases.

There are deodorizers that are classified as other chemical deodorants, but many have strong acidity or alkalinity, the types of gases that can be deodorized are limited, and they are easily affected by moisture absorption or dryness. There is.

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

As mentioned above, there is no conventional deodorizing agent that fully 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 completely 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.

[Structure] As a result of intensive research to achieve the above object, the present inventor discovered that a hybrid consisting of titanium dioxide and zinc oxide exhibits an excellent deodorizing effect. However, after further research, a combination of a mixed aqueous solution of a water-soluble titanium compound, a water-soluble magnesium compound and/or a water-soluble calcium compound, and an alkaline aqueous solution was finally obtained. They are simultaneously mixed so that the DH of the liquid is 8 or more, preferably 8 to 12, and as a result, titanium oxide (usually T + 02>, magnesium chloride (MgQ) and/or calcium oxide (CaO)) is added to the combined liquid. , and bound water (H2O)). Next, this precipitate is separated from the combined liquid and dried to produce a white fine powder that is highly resistant to foul-smelling gases such as hydrogen sulfide and ammonia. It was discovered that it has good deodorizing performance, and the present invention was achieved.

In this deodorizer, it was confirmed that CaO and M(l 2 O) have almost the same effect.

In the production of the deodorizing agent of the present invention, the water-soluble titanium compounds used as raw materials include titanium acid, titanyl sulfate, titanium chloride, titanium nitrate, etc., and the water-soluble magnesium compounds include magnesium sulfate, magnesium chloride, Magnesium nitrate or the like can be used. Further, as the water-soluble calcium compound, calcium chloride, calcium nitrate, etc. can be used. As the alkaline aqueous solution used for neutralization, aqueous solutions of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, etc. can be used. However, since calcium ions react with sulfate groups to form insoluble precipitates, a combination in which the two coexist is not preferred.

Water-soluble titanium compound and water-soluble magnesium and/or
Or the mixing ratio with calcium compound is TiO2 to Ma
The molar ratio of O and/or cao ranges from 1:9 to 9:1, preferably from 4:6 to 8:2.

That is, the fine powder obtained from the precipitate produced in a composition region with more M2O and/or CaO than 1:9 in the molar ratio of TiO3 to MgO and/or CaO, or a composition region with more TiO□ than 9:1, respectively. It exhibits adsorption properties similar to those of the components magnesium oxide and/or calcium oxide or titanic acid, and their adsorption properties are substantially inferior to those of fine powders obtained in the composition range of the present invention.

Titanic acid begins to form a precipitate at a pH of around 1, but magnesium hydroxide and calcium hydroxide start to form at a pH of 9 to 1.
If it is not more than 0, it will not be precipitated.

However, in the mixed aqueous solution, the molar ratio of T i O2 and MgO and/or CaO is less than 1:1 than T +
When there is a large amount of 02, if the pH of the mixed aqueous solution is set to 8 or higher, almost 100% of magnesium hydroxide and/or calcium hydroxide will precipitate together with titanic acid.

If the pH of the combined liquid is 12 or more, alkali or alkaline earth metal ions remain in the precipitate, and the pH of the final white deodorizer increases, which is undesirable for use.

In the method of gradually adding an alkaline aqueous solution to a mixed aqueous solution and finally adjusting the pH of the solution to 8 to 12, magnesium hydroxide and calcium did not precipitate together with titanic acid, and the composition of the product was different from the intended one. Become something. Further, there is no particular restriction on the concentration of the mixed aqueous solution of a water-soluble titanium compound and a water-soluble magnesium and/or calcium compound.

TiO'(
M! The temperature for forming the precipitate consisting of 10 and/or Ca0)-H2O can be in the range of 20 to 80C, but preferably 40 to 60C.

Furthermore, the drying temperature after filtering and washing the precipitate is 100~
Although a range of 300°C can be adopted, a range of 150 to 250'C is preferable.
400 for O and/or CaO based deodorizers
It maintains good adsorption properties when heated below ℃.

[Effect of the invention] TiO・(M(I O and/or C
The ab) type white deodorizer has good properties for deodorizing various malodorous gases such as hydrogen sulfide, ammonia, and amines that are generated in daily life.
Since it is composed of gO and CaO, 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℃, making it possible to add it to plastics and process it. It has excellent industrial properties as a deodorizer, and because it is particularly white, it can be used for a variety of purposes, such as being suitable for cosmetics, sanitary products, and disposable diapers.

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

Example 1 Take 1 j of water into a 5 ρ beaker and bring to a temperature of 6 with stirring.
The temperature was maintained at 0°C. Next, a separately prepared titanium sulfate/magnesium sulfate mixed aqueous solution 29 containing 120 tr as TiO2 and 20 sr as MgO and an ammonia aqueous solution were heated as described above for 30 minutes while being careful to maintain the PTL of the combined solution at 8. They were simultaneously dropped into pure water. After the product was filtered and washed, it was dried at 200°C for 3 hours,
A TiO2.MGO-H2O-based white deodorizer of the present invention was manufactured. When this white deodorizer was examined by X-ray diffraction, it was found to be amorphous.

The adsorption properties of this white deodorizer for malodorous gases such as hydrogen sulfide and ammonia were investigated as follows.

Contains 100cm of white powder! After placing it in a 120 ml glass vial and sealing it with a rubber stopper, a predetermined amount of the malodorous gas component is injected into the vial using a microsyringe. Two hours after injecting the gas, the air in the vial is taken out with a microsyringe and the gas concentration is measured using a gas chromatograph. The results are shown in Table 1.

Example 2 T i O2): , aot and M(IO and T4
Ti O2
Obtain a white deodorizer based on -Ma 0-H2O.

Table 1 shows the adsorption properties for various malodorous gases.

Example 3 TiO2, CaO, H2O was prepared in exactly the same manner as in Example 1, except that a titanium chloride/calcium chloride mixed aqueous solution containing 120 g of TiO2 and 28 g of CaO was used.
A white deodorizing agent was obtained.

Table 1 shows the adsorption properties for various malodorous gases.

Example 4 Except for using a titanium chloride/calcium chloride mixed aqueous solution containing 80 g of Ti02 and 56 g of CaO,
T i O2・CaO・H2 in exactly the same manner as in Example 1
A 0-series Hakubutsusen odorant was obtained. Table 1 shows the adsorption characteristics for each of the poor gases.

Example 5 80g as TiO2, 20g as MgO and CaO
Contains 28g of titanium chloride, magnesium chloride,
A TiO2/CaO/H20-based Hakubutsu odorant was obtained in exactly the same manner as in Example 1, except that a calcium chloride mixed aqueous solution was used. Table 1 shows the adsorption properties for various malodorous gases.

Comparative Example 1 1 jl of pure water was taken into a 51-beaker and heated and maintained at a temperature of 60° C. while stirring. Next, separately prepared T +
2 jl of an aqueous titanium sulfate solution containing 160 g of 02 and an ammonia aqueous solution were simultaneously dropped into the pure water over 30 minutes while being careful to maintain the pH of the combined solution at 8. After filtering and washing the product, dry it at 200°C for 3 hours to obtain titanic acid powder.

Table 1 shows the adsorption properties of titanic acid powder for various malodorous gases.

Comparative Example 2 In Comparative Example 1, titanium sulfate aqueous solution was added to magnesium sulfate aqueous solution containing 80 g of MgO, and p of the combined liquid was
Magnesium oxide powder was obtained in exactly the same manner as in Comparative Example 1 except that H was changed to 9.

Table 1 shows the adsorption properties of this magnesium oxide powder for various malodorous gases.

Comparative Example 3 In Comparative Example 1, a calcium chloride aqueous solution containing 56 g of vit titanium acid aqueous solution aO, and p of the combined liquid were added.
Calcium oxide powder was obtained in exactly the same manner as in Comparative Example 1 except that H was changed to 9.

Table 1 shows the adsorption properties of this calcium oxide powder for various malodorous gases.

Comparative Example 4 Table 1 shows the results of investigating the adsorption properties of commercially available activated carbon for various malodorous gases.

Claims (1)

[Scope of Claims] 1. A white deodorizing agent characterized in that it is a white fine powder consisting of tightly aggregated particles of titanium oxide, magnesium oxide and/or calcium oxide. 2. The white deodorizer according to claim 1, wherein the molar ratio of TiO_2 to MgO and/or CaO is in the range of 1:9 to 9:1. 3. The white deodorizer according to claim 2, wherein the molar ratio of TiO_2 to MgO and/or CaO is in the range of 4:6 to 8:2. 4. P of the combined liquid after combining the mixed aqueous solution containing the water-soluble titanium compound, the water-soluble magnesium compound and/or the water-soluble calcium compound, and the alkaline aqueous solution.
A precipitate is formed by coalescing in part or all at the same time so that H has a value in the range of 8 to 12, and the precipitate is separated from the coalescing liquid and dried to form TiO_2 (MgO and/or CaO). )・H_2O A method for producing a white deodorizer, characterized by obtaining a fine white powder. 5. The manufacturing method according to claim 4, wherein the molar ratio of TiO_2 to MgO and/or CaO is in the range of 1:9 to 9:1. 6. The manufacturing method according to claim 5, wherein the molar ratio of TiO_2 to MgO and/or CaO is in the range of 4:6 to 8:2. 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 150 to 250°C.