JPH0333023B2 - - Google Patents

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to powders of various malodorous gases such as hydrogen sulfide, ammonia, and amines, and more specifically to powders of various malodorous gases such as hydrogen sulfide, ammonia, and amines, and more specifically, powders of titanium oxide (usually titanium dioxide), magnesium oxide, and The present invention relates to the provision of a completely new deodorizing agent in the form of white fine powder, which is mainly composed of a calcium oxide hybrid and 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 increasing public awareness of powders that have the ability to remove gases, and various types of deodorizers are in practice. 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, and it must be highly safe.
It must be easy to handle, inexpensive, and clean. However, no deodorizing agent that fully satisfies all of the above conditions has hitherto existed, and no deodorizing agent has yet been developed despite recent research. For example, activated carbon, which is most commonly used as a deodorizing agent, 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 ivy. In order to improve this point, a product called impregnated carbon, which is activated carbon loaded with acid, alkali, or some 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 handled as a type of hazardous material. In addition, an essential drawback of activated carbon is that it is black.
Because of this color tone, the uses of deodorizers based on activated carbon are becoming narrower. In addition, iron sulfate (FeSO ₄ ) combined with L-alcorbic acid has a good deodorizing effect on basic malodorous gases such as ammonia and amines, but has little deodorizing effect on hydrogen sulfide, mercaptans, aldehydes, etc. Moreover, since it dissolves in water, it has the disadvantage that it cannot be used to deodorize humid gases. There are deodorants 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 drawbacks of being 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, conventional deodorizers include
There was no one that satisfactorily met all of the conditions. [Purpose] The present invention was made in view of the above-mentioned circumstances, and its purpose is to have a good deodorizing effect on malodorous gases such as hydrogen sulfide, ammonia, mercaptans, amines and aldehydes generated in daily life. The object of the present invention is to provide a deodorizing agent having a completely new composition that is highly safe and 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, and has accomplished the invention based on this. Applied for a patent (patent application 1986)
-198396) conducted further research on water-soluble titanium compounds, water-soluble magnesium compounds and/or water-soluble magnesium compounds.
Or, the final combined solution of a mixed aqueous solution of a water-soluble calcium compound and an alkaline aqueous solution is
Titanium oxide (usually
A white precipitate consisting of TiO ₂ ), magnesium oxide (MgO) and/or calcium oxide (CaO), and bound water (H ₂ O) is formed, which is then separated from the combined liquid and dried. The present invention was achieved based on the discovery that the white fine powder obtained by this method has good deodorizing performance against malodorous gases such as hydrogen sulfide and ammonia. It was confirmed that CaO and MgO have almost the same effect in this deodorizer. In the production of the deodorizing agent of the present invention, titanium sulfate, titanyl sulfate, titanium chloride, titanium nitrate, etc. can be used as a water-soluble titanium compound as a raw material, and magnesium sulfate, magnesium chloride, nitric acid, etc. can be used as a water-soluble magnesium compound. Magnesium etc. 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. The mixing ratio of water-soluble titanium compound and water-soluble magnesium and/or calcium compound is
The molar ratio of TiO ₂ to MgO 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 MgO and/or CaO than 1:9 in the molar ratio of TiO ₂ to MgO and/or CaO, or a composition region with more TiO ₂ than 9:1, respectively. They exhibit adsorption properties similar to those of the end components magnesium oxide and/or calcium oxide or titanic acid, and their adsorption properties are substantially inferior to those of the fine powders obtained in the composition range of the present invention. Titanic acid begins to form a precipitate when the pH is around 1 or above, but magnesium hydroxide and calcium hydroxide do not form a precipitate unless the pH is above 9-10. However, in a mixed aqueous solution, TiO ₂ and MgO and/or
When the molar ratio of TiO ₂ to CaO is more than 1:1, almost 100% of the aqueous magnesium and/or calcium hydroxide will precipitate together with titanic acid if the pH of the mixed aqueous solution is set to 8 or higher. If the combined liquid has a pH of 12 or higher, alkali or alkaline earth metal ions will remain in the precipitate, and the pH of the final white deodorizer will become high, which is undesirable for use. In the method of gradually adding an alkaline aqueous solution to a mixed aqueous solution and ultimately 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. Mixing a mixed aqueous solution and an alkaline aqueous solution
The temperature at which the precipitate consisting of _TiO2 .(MgO and/or CaO) _.H2O is generated can be in the range of 20 to 80C, preferably 40 to 60C. Furthermore, the drying temperature after over-washing the precipitate is
Although a range of 100 to 300°C can be adopted, a range of 150 to 250°C is preferred. Note that TiO ₂ according to the present invention
For MgO and/or CaO-based deodorizers,
It maintains good adsorption properties when heated below 400℃. [Effect of the invention] TiO ₂ (MgO and/or
CaO)-based white deodorizer has good properties for deodorizing various malodorous gases such as hydrogen sulfide, ammonia, and amines generated in daily life, and is composed of non-toxic TiO ₂ , MgO, and CaO. It is highly safe, and since it is a fine powder, it can be easily supported on paper and sheets, it is thermally stable up to about 400℃, and it can be added to plastics, making it excellent in processability, making it industrially useful as a deodorizing agent. It is highly sexual,
In particular, since it is white, it can be used for various purposes, such as being suitable for cosmetics, sanitary products, and disposable diapers. [Example] Examples will be given below to explain in more detail,
This is provided for illustrative purposes only, and the scope of the invention is not limited thereby. Example 1 Pure water 1 was taken into 5 beakers and heated and maintained at a temperature of 60°C while stirring. I then prepared a separate
Titanium sulfate/magnesium sulfate mixed aqueous solution 2 containing 120 g of TiO ₂ and 20 g of MgO and an ammonia aqueous solution were simultaneously added to the pure water for 30 minutes while being careful to maintain the pH of the combined solution at 8. dripped. 200℃ after overwashing the product
The mixture was dried for 3 hours to produce a TiO ₂ .MgO.H ₂ O-based white deodorizer of the present invention. 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.
Put 100 mg of white powder into a glass vial with an internal volume of 120 ml, seal it with a rubber stopper, and then inject the specified amount of malodorous gas component into the vial using an icrosyringe. Two hours after injecting the gas, air is taken out from the vial using an icrosyringe, and the gas concentration is measured using a gas chromatograph. The results are shown in Table 1. Example 2 TiO _{2 ·}
A MgO·H ₂ O-based white deodorizer was obtained. Table 1 shows the adsorption properties for various malodorous gases. Example 3 TiO ₂ · _CaO ·
A H ₂ O-based white deodorizer was obtained. Table 1 shows the adsorption properties for various malodorous gases. Example 4 TiO ₂ ·CaO _·
A H ₂ O-based white deodorizer was obtained. Table 1 shows the adsorption properties for various malodorous gases. Example 5 Except for using a titanium chloride/magnesium chloride/calcium chloride mixed aqueous solution containing 80 g of TiO ₂ , 20 g of MgO, and 28 g of CaO,
A TiO ₂ .CaO .H ₂ O-based white deodorizer was obtained in exactly the same manner as in Example 1. Table 1 shows the adsorption properties for various malodorous gases. Comparative Example 1 Pure water 1 was taken into 5 beakers and heated and maintained at a temperature of 60°C while stirring. Next, titanium sulfate aqueous solution 2 containing 160 g of TiO ₂ was prepared separately.
and ammonia aqueous solution, the PH of these combined liquids
They were simultaneously dropped into the pure water over a period of 30 minutes while being careful to maintain a pH of 8. After over-cleaning the product
It was dried 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
Comparative Example 1 except that the magnesium sulfate aqueous solution containing 80 g of MgO was used and the pH of the combined liquid was changed to 9.
Magnesium oxide powder was obtained in exactly the same manner as above. Table 1 shows the adsorption properties of this magnesium oxide powder for various malodorous gases. Comparative Example 3 Calcium oxide powder was obtained in exactly the same manner as in Comparative Example 1, except that the titanium sulfate aqueous solution was changed to a calcium chloride aqueous solution containing 56 g of CaO, and the pH of the combined liquid 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. 【table】

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 A mixed aqueous solution containing a water-soluble titanium compound, a water-soluble magnesium compound, and/or a water-soluble calcium compound and an alkaline aqueous solution are mixed in portions so that the pH of the combined solution after combining both becomes a value in the range of 8 to 12. Alternatively, all of them can be combined at the same time to form a precipitate, and the precipitate can be separated from the combined liquid and then dried to form TiO ₂ (MgO and/or CaO).
A method for producing a white deodorizer, characterized by obtaining a white fine powder consisting of H ₂ O. 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 reaction temperature of the precipitation formation is 40 to 60°C,
The method according to any one of claims 4 to 6, wherein the drying temperature of the powder is 150 to 250°C.