JPH05228339A - Deodorant and deodorization method - Google Patents

Abstract

PURPOSE:To provide a deodorant capable of being repeatedly used. CONSTITUTION:This deodorant consists of the fine particles of copper(I) chloride or copper(II) chloride, and the redox reaction between the copper(II) chloride and copper(I) chloride is utilized. A malodorous material is brought into contact with the copper(II) or copper(I) chloride in a gaseous phase, hence the copper(I) chloride is converted into copper(II) chloride or vice versa to deodorize the material, then the copper(II) chloride is converted into copper (I) chloride or vice versa by an oxidizing or reducing material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant and a deodorizing method.

[0002]

[Prior Art and Problems to be Solved by the Invention] Methyl mercaptan (CH ₃ SH), hydrogen sulfide (H ₂ S)
Ammonia (NH _3), trimethylamine ((CH _{3) 3} N) sulfur-containing, such as, include nitrogen-containing compounds. In recent years, with the improvement of living standards, it has been desired to develop a method for removing these odorous substances generated in the living environment.

Conventionally, there are various methods for removing a malodor, one of which is a method of bringing an odorous substance into contact with a metal oxide catalyst to decompose it into an odorless substance. The metal oxide catalyst used in this method is used by supporting one or more transition metal oxides on a carrier having a large specific surface area. The transition metal elements include iron, copper, manganese,
Cobalt, zinc, chromium, etc. are used, and their water-soluble salts are mainly used. That is, a halide,
Sulfates, nitrates, oxalates and the like are used. As the carrier having a large specific surface area, alumina, silica, titania, zirconia, zeolite, activated carbon or the like is used.

Although the deodorizing mechanism by these catalysts has not been clarified, the odorant is adsorbed on the surface of the catalyst and converted into a substance having a high threshold concentration by an oxidation-reduction reaction or a decomposition polymerization reaction to deodorize. Is. However, there are cases in which desorption of adsorbed substances does not go well, the surface is poisoned and the life ends, and there are cases in which the catalyst itself is oxidized or reduced and converted to a substance having no catalytic ability, In some cases, the ability as a deodorizing catalyst that is stable for a long period of time cannot be maintained.

In view of the above problems, it is an object of the present invention to provide a deodorant and a deodorizing method that can repeatedly use a deodorizing substance.

[0006]

In order to achieve this object, the deodorant according to the present invention comprises fine particles of copper (II or I) chloride, and a redox reaction between copper (II) chloride and copper (I) chloride. It is characterized by being used.

Further, in the deodorizing method according to the present invention, an odorous substance is brought into contact with copper chloride (II or I) in a vapor phase to cause the copper chloride (II or I) to have a different valence.
Or II) to deodorize an odorous substance by oxidation or reduction, and the copper chloride (I or II) after the change is converted to copper chloride (II or I) having an original valence by an oxidizing or reducing substance. It is characterized by regenerating into redox reaction.

In a more specific embodiment of the redox reaction of the present invention, an odor substance is brought into contact with copper (II) chloride in a gas phase to change the copper (II) chloride to copper (I) chloride to give an odor. There is a method in which a substance is oxidized to deodorize and copper (I) chloride is regenerated into copper (II) chloride by ozone.

The copper chloride (II or I) according to the present invention may be alumina, silica, zirconia, titania, etc., which are commonly used as carriers, as a simple substance or as a complex oxide. As a supporting method, the carrier is immersed in an aqueous solution of copper chloride and then dried, or copper chloride is dissolved in an aqueous solution containing fine particles of a compound constituting the carrier,
It may be prepared by spray pyrolysis at 0 ° C to 1200 ° C.

When these compounds are used as a catalyst, it is more preferable that the specific surface area thereof is large. However, in the case of the deodorant of the present invention, not only the reaction but also the deodorant itself contributes, and therefore the deodorant itself usually contributes. even the specific surface area of about sintering ceramics ^{(0.1m 2 / g~1m 2 / g} ) to exert a sufficiently deodorizing ability.

[0011]

In the present invention, copper (II) chloride adsorbs and decomposes a typical odorous substance that can be deodorized by the oxidation reaction of methylmercaptan, trimethylamine, etc., and at the same time, it is reduced to copper (I) chloride. To do. When copper (I) chloride is allowed to act on ozone, copper (I) chloride is oxidized to ozone and returns to copper (II) chloride. This deodorant repeats the valence of 1 to 2 in the cycle of contact with odorous substance-ozone to form a so-called redox reaction.

In the above case, NO _X and S are used as odor substances.
When adsorbing an odorous substance that can be deodorized by a reduction reaction of O _X , aldehyde, carboxylic acid, etc., contrary to the above, the odorous substance is adsorbed on copper (I) chloride, and then copper (II) chloride is oxidized by oxidation. The redox reaction can be formed by returning the copper chloride (I) converted to copper chloride (I) with a reducing substance such as hydrogen gas. Furthermore, for an odor in which an odorous substance that is deodorized by the oxidation reaction and an odorous substance that is deodorized by the reduction reaction are mixed, both odorous substances are oxidized and reduced without using ozone or hydrogen. A redox reaction can also be formed by oxidizing and reducing copper chloride (I or II) as a substance.

[0013]

EXAMPLES [Samples and Experimental Equipment] In producing a deodorant by the spray reaction method, the following salts were used as the salts dissolved in the raw material aqueous solution. Copper (II) chloride: CuCl ₂ Titanium tetrachloride: TiCl ₄ It was prepared to be 1. This is shown in FIG.
(Aqueous solution atomizer using ultrasonic transducer) The above aqueous solution was put in, and the atomized fog with an atomization rate of 50 cc / min was sucked by a suction device (not shown) provided downstream of the furnace 3. While
The ultrafine particles produced were introduced from the quartz tube 2 into the furnace 3 kept at 1000 ° C. for firing, and the generated ultrafine particles were collected by the glass filter 5 provided at the exit of the quartz tube 4 on the exit side of the furnace 3. as a result,
1 g of a spherical deodorant having a particle diameter of 0.4 μm to 1.0 μm was obtained.
The specific surface area of this product was 2.92 m ² / g. The surface area of the layer prepared by the coprecipitation method was 8.90 m ² / g.

[Measurement of Deodorizing Ability] Using the catalyst obtained in the above Example, a decomposition reaction of methyl mercaptan, which is a typical odor substance, was carried out using the apparatus shown in FIG. 1 (A). Figure 1
Device (A) includes a mass flow controller -7 methyl mercaptan CH ₃ SH, a float flow meter 8 of the nitrogen gas N ₂ to be mixed into methyl mercaptan CH ₃ SH, a float flow meter 9 for preprocessing helium He, It has four-way cocks 11 for switching the flow paths of the deodorant and methyl mercaptan reaction tubes 10A and 10B, filters 12A and 12B provided downstream of the reaction tubes 10A and 10B, and sample gas sampling chambers 13A and 13B. ..

Using this apparatus, first, one reaction tube 1
0.3 g of copper (II) chloride was put in 0 A, pretreated with helium gas at a temperature of 300 ° C. for 1 hour, and the other reaction tube 1
In the reaction tube 10B containing only glass wool, the methyl mercaptan was added to the glass tube 0B.
The mass flow controller 7 and the float flow meter 8 were adjusted so that a nitrogen gas containing 00 ppm could flow at 50 cc / min at 200 ° C., 0.5 ml of the gas was sampled from the sampling chamber 13B, and the methyl mercaptan concentration was measured by an FPD gas chromatograph. ..

Next, the four-way cock 11 was turned to introduce the gas containing methyl mercaptan into the reaction tube 10A kept at 200 ° C., and sampling was carried out in the same manner as described above, and measurement was carried out by a gas chromatograph. Then, the decomposition rate was calculated from the area of the peak of the gas chromatograph, and the change with time was taken. Then, the conversion rate to the product was obtained from the ratio of the peak area of the raw material gas and the peak area of the product.

As a result, both copper (II) chloride prepared by the spray reaction method and the coprecipitation method had a methyl mercaptan decomposition rate of 3%.
The value was close to 100% even after the lapse of time. Compared with other catalysts, the Ti-Cu-based deodorant was superior in its deodorizing ability.

[Measurement of Ozone Decomposition] As shown in FIG. 1 (B), a dryer 14, an ozone generator 15, and a reaction tube 16 are provided in an air passage sucked by a suction pump 18.
And an ozone concentration meter 17 are provided, the reaction tube 16 is inserted in the flow path so as to be separable, and 0.1 g of copper chloride (II or I) is placed in the reaction tube 16. First, do not install the reaction tube 16 in the flow path. Air was flowed and the ozone concentration was measured with an ozone concentration meter. Next, the reaction tube 16 is set in the flow path and the reaction tube 1
Ozone-containing air was flown through the sample No. 6, and the value of the ozone concentration meter 17 was read at the determined time.

FIG. 3 shows changes with time in the ozone decomposition reaction of copper (II) chloride supported on the Ti-Cu oxide produced by the spray reaction method and by the coprecipitation method. Ti-Cu
-Sp (by the spray reaction method) is 10 from the initial stage of the reaction.
The decomposition rate is close to 0%, and there is almost no decrease even after about 30 minutes. On the other hand, Ti-Cu-co (by the coprecipitation method) has a decomposition rate of about 40% at the initial stage of the reaction,
It has become inactive after 0 minutes. That is, Ti-Cu-s
p has excellent activity as compared with Ti-Cu-co, but from the X-ray diffraction pattern, Ti-Cu-sp is a chloride and Ti-Cu-co is an oxide. , It seems that this difference led to a difference in activity.

[X-ray diffraction pattern] FIG. 4 shows Ti-Cu-
The X-ray-diffraction pattern before and after reaction of sp is shown. Here, the measurement is performed before the reaction (a), after the methyl mercaptan oxidative decomposition reaction (b), after the ozone decomposition reaction (c), and after ozone decomposition and then methyl mercaptan oxidative decomposition reaction (d). I went about.

Before the reaction, peaks of TiO ₂ (Rutile), CuCl and CuCl ₂ are seen. After the oxidative decomposition reaction of methyl mercaptan (b), there was no change in the peak of TiO ₂ , but Cu
The Cl ₂ peak disappeared and the CuCl peak intensity increased. On the other hand, after the ozone decomposition reaction, the TiO ₂ peak did not change, but the CuCl peak disappeared.
₂ has some fluctuations but remains. Also, after the ozone decomposition-methyl mercaptan oxidative decomposition reaction (d), there is no change in TiO ₂ . However, the CuCl peak, which disappeared after ozone decomposition, appeared. From these, it can be seen that the valence of Cu varies before and after the reaction. In other words, it can be said that Cu was reduced by the oxidative decomposition reaction of methyl mercaptan and that it was oxidized by the ozone decomposition reaction.

[Measurement of Methyl Mercaptan Oxidation Decomposition] Then, the binding energy of Cu (2p) after the reaction with the collected product, methyl mercaptan and ozone was measured by X-ray photoelectron spectroscopy (XPS). , The oxidation state of Cu was confirmed. The result is shown in FIG. 5 (a) is the product, (b) is the reaction with methyl mercaptan,
(C) shows a spectrum after reacting with ozone, and (d) shows a spectrum after reacting with methyl mercaptan after reacting with ozone. The binding energy of Cu ⁰ 2p (3/2) is 932.4 (e
V), only the shoulder before the reaction can be seen, but the peaks are not seen in the rest. In addition, the peaks are shifted to the high energy side, and the energies of I valence and II valence are 935.0 (eV) and 937.
It is found near 0 (eV). In the spectrum before the reaction (a), it can be seen that Cu having an I valence and Cu having a II valence are mixed and the I valence is larger. Even after the oxidative decomposition reaction of methyl mercaptan,
Although II-valent Cu is mixed, the amount of I-valent Cu is decreasing. Further, the peaks of I valence and II valence are shifted to the low energy side as compared with those before the reaction, and it can be said that they are not completely I valence and II valence, and that they are in a low oxidation state. On the other hand, after the ozonolysis reaction, the I value peak decreased, and after the ozone decomposition-methylmercaptan oxidative decomposition reaction, the I value peak almost disappeared. From the above, changes in the oxidation state were confirmed, and Ti-
When Cu-sp performs a methyl mercaptan oxidative decomposition reaction in which ozone is also used, deodorization and regeneration can be performed by a redox reaction.

[Activation energy] Ti-Cu-sp, Ti-
The Cu-co Arrhenius plot is shown in FIG. The reciprocal number (K ⁻¹ ) of the reaction temperature was plotted on the horizontal axis of FIG. 6, and the decomposition reaction rate constant of methyl mercaptan was plotted on the vertical axis, and the activation energy k was determined from the gradient of the obtained straight line. Here, the decomposition reaction rate of methyl mercaptan was calculated by the following equation by approximating the reaction order as first order. k = (F _V / V) ln
(1-X _A ) where F _{A is the} raw material supply rate (ml / min),
V: Deodorant volume (ml) X _A : Substrate change rate As shown in FIG. 6, the value prepared by the spray reaction method was lower than that prepared by the coprecipitation method, and the deodorization was performed. Excellent performance as an agent is shown.

[0024]

EFFECTS OF THE INVENTION According to the deodorizing method and deodorant of the present invention, since deodorization and regeneration are carried out between copper (II) chloride and copper (I) chloride, the deodorizing action can be carried out for a long time.

[Brief description of drawings]

FIG. 1A is a configuration diagram of an apparatus used for measuring a decomposition function of methyl mercaptan by the deodorant of the present invention, and FIG. 1B is a configuration diagram of an apparatus used for measuring an ozone decomposition function.

FIG. 2 is a configuration diagram of an apparatus used for producing the deodorant of the present invention.

FIG. 3 is a diagram showing a result of ozone decomposing measurement of a deodorant obtained by the present invention in a relation of decomposition rate with respect to time.

FIG. 4 is a view showing an X-ray diffraction pattern by the reaction of the deodorant obtained by the present invention with methyl mercaptan and ozone.

FIG. 5 is an X-ray photoelectron spectroscopy spectrum diagram of the deodorant obtained by the present invention.

FIG. 6 is an Arrhenius plot of the deodorant obtained according to the present invention.

[Explanation of symbols]

1 Atomizer 2, 4 Quartz Tube 3 Furnace 5 Glass Filter 7 Mass Float Controller 8, 9 Float Flowmeter 10A, 10B Reaction Tube 11 Four-way Cock 12A, 1
2B Filters 13A, 13B Sampling chamber 14 Dryer 15 Ozone generator 16 Reaction tube 17
Ozone concentration meter 18 Suction pump

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[Procedure amendment]

[Submission date] December 30, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Deodorant and deodorizing method

Claims (3)

[Claims] 1. A deodorant comprising fine particles of copper (II or I) chloride and utilizing a redox reaction between copper (II) chloride and copper (I) chloride. 2. An odorant is obtained by bringing an odorant into contact with copper chloride (II or I) in a vapor phase to change the copper chloride (II or I) into copper chloride (I or II) having a different valence. Is deodorized by oxidation or reduction, and copper chloride (I or II) after the change is regenerated to copper chloride (II or I) having the original valence by an oxidizing substance or a reducing substance to cause a redox reaction. A deodorizing method characterized in that 3. A copper (II) chloride is brought into contact with copper chloride (II) in a gas phase to change the copper (II) chloride to copper (I) chloride to oxidize and deodorize the odorous substance. A deodorizing method characterized in that (I) is regenerated into copper (II) chloride to cause a redox reaction.