KR20030083831A - Deodorizing agent for removing odious smell using catalyst and hydrogen peroxide - Google Patents

Abstract

PURPOSE: Provided is a deodorizer which oxidizes the malodorous material in the air by TiO2 producing OH radical under UV radiation to enhance the oxidizing and deodorizing power and has the antifungal and antibacterial effect. CONSTITUTION: The deodorizing composition is characterized by containing the photocatalyst, TiO2/Cu and H2O2. TiO2 reacts with the dissolved oxygen and hydrogen peroxide under UV radiation to produce OH radical and oxidizes the causal materials of the malodor in the air to deodorize, and H2O2 accelerates the production of OH radical to enhance the oxidizing power of a deodorizer with the composition. TiO2/Cu is contained in a level of 10,000 to 100,000 mg/l, and H2O2 is contained in a level of 100 to 1000 mg/l. Additionally, the deodorizing composition contains an aroma in a level of 1,000 to 20,000 mg/l.

Description

Deodorizing agent for removing odious smell using catalyst and hydrogen peroxide

The present invention relates to a deodorant for removing odor using a photocatalyst / H ₂ O _2. More specifically, since TiO ₂ generates OH radicals under UV light, it can oxidize odorous substances in the air, thereby further improving oxidation and deodorizing power. The present invention also relates to a deodorant for removing odors, which can be doubled and anticipate antibacterial and bactericidal effects.

The modern society of Korea has been trying to improve national welfare and increase income with rapid development since 1980, but has emitted environmental pollutants such as harmful gases and odors from various wastes which are by-products of the industrial economy. Among them, odor is a complex and ambiguous property that can be detected even at low temperatures, causing discomfort and causing diseases such as loss of appetite, vomiting, insomnia, and allergies. Sources of such odors include garbage, dirty cleanup tanks, public toilets, sewers and polluted rivers, sewage treatment plants, manure treatment plants, chemical plants, animal husbandry facilities, rubber plants, synthetic resin manufacturing plants, and plating plants. Odor from leachate and leachate is a big problem

Conventionally, in order to remove such odors, a method by physical and chemical treatment, a method of treating by camouflage using a masking agent, or the like has been used. However, the method according to the prior art has problems such as low removal rate, high processing cost and secondary pollution, and thus complements the problems of the prior art, is excellent in efficacy and comfortable without generating secondary environmental pollution. There is a need for a competitive deodorant with a high treatment efficiency that can maintain a living environment.

On the other hand, the deodorization system can be classified into physical, chemical, biological, and other methods. The classification system is shown in FIG. The various methods of deodorization that have been classified so far have their own features and disadvantages and cannot be said to be perfect. In fact, the gas containing the odor component to be treated is often a low concentration complex component, and the properties of the contained component are usually different. In other words, it is the most economical by comprehensively reviewing technical data on the source of odor such as composition and concentration of odor components, temperature, air volume, humidity, working time, process change, working route, installation area, secondary pollution treatment measures, and fuel used. Phosphorus deodorization method will be selected.

However, even though the odor generated in everyday life is more directly unpleasant to people, it is difficult to install treatment facilities such as industrial sites, and a deodorization method without human body and secondary side effects should be devised. Looking at the odor generated in everyday life mainly sweat, body odor, toilet odor, foot odor, such as the smell that occurs in pets, these odors are causing odors that form discomfort in many places. In addition, the main causes of such odors are basic odors of nitrogen compounds such as ammonia and amines, and acidic odors such as hydrogen sulfide and methyl mercaptan. These odors may cause severe discomfort. .

Therefore, in order to solve this problem, spray deodorant, air freshener, bacteria and mold remover, and fragrance products for removing odorous substances and maintaining comfort and cleanliness of indoor and outdoor environments have been used for a long time. . However, if you look at these products, the deodorization efficiency is still low, masking products as the majority of the odor components do not fundamentally eliminate the odor components in the incense odor component is emitted once all the odor is emitted again begins to occur.

In addition, looking at the domestic prior patents related to deodorant, Korean Patent No. 3251 1 is blended with rice bran for yeast, kneaded by adding zeolite, fermented, and then mixed and dried iron sulfate to disclose a malodor treatment agent, Korea Patent No. 182845 discloses a deodorant using tartaric acid, sodium acetate, ascorbic acid and essential oils. In addition, Korean Patent No. 30353 discloses a composition for deodorizing and removing heavy metals consisting of NaOCl, sodium carbonate, sodium phosphate, alumina, ferrous sulfate, zeolite, acidic clay, sodium sulfite, aron floc and chlorine dioxide, have.

In addition, Korean Patent Laid-Open Publication No. 92-2170 discloses a deodorant using a microbial enzyme that removes various odors generated from organic waste using the microbial enzyme as an active ingredient. In addition, Korean Patent No. 139559 discloses activated carbon fibers and nonwoven fabrics and a method of manufacturing the same. As such, the conventional deodorant used in the biochemical oxidation method is mainly composed of chlorine (including chlorine dioxide) and bio-based.

However, the above patents are mainly made of NaOCl, which is classified as a toxic substance, or made of petroleum essential oil (Pine oil & Caster oil), and in the case of NaOCl, it reacts with an organic compound containing nitrogen to produce chloroamines. The compound is produced and reacts with a compound containing sulfur (S) to produce a sulfenyl chloride compound (Gmelin Handbook vol 6. 410-410). These amine chlorides and sulfenyl chlorides not only diffuse easily in the air, but also irritate mucous membranes in the eyes, skin, and oral cavity, causing problems of secondary pollution as substances harmful to the human body. Bio-systems, which are composed of pine oil & caster oil and natural plant essential oils (essential oils), contain fruit or acacia scents, but have no lasting effects as aromatic plants, and may have side effects such as headaches after prolonged exposure. On the other hand, it is economically disadvantageous or difficult to process conditions such as deodorizing ability is not even and foam is generated a lot.

As described above, the existing deodorizing method has a deodorizing performance, and when an incompletely processed odor spreads to the surroundings, it causes discomfort to the human body, and also generates a secondary problem such as generating a harmful substance to the human body or causing a headache.

Accordingly, an object of the present invention includes TiO ₂ , a photocatalyst which is a harmless component to the human body, in order to solve the problems of the prior art as described above. In addition, since the addition of H ₂ O ₂ can further promote the production of OH radicals, it has a high deodorization efficiency and can completely oxidize the odor causing substance, and thus no secondary pollutants are generated and odor is caused. It is to provide a deodorant composition that is excellent in deodorizing power, high safety, and long-lasting effect that can change all the causative substances into CO ₂ , H ₂ O and the like harmless gas.

1 is a diagram schematically illustrating the deodorization methods commonly used.

2 is a schematic diagram of the reaction for the photocatalytic oxidation method.

In order to achieve the above object, the present invention provides a deodorant composition for removing odor, characterized in that comprises a photocatalyst TiO ₂ / Cu and H ₂ O ₂ .

According to the present invention, the TiO ₂ constituting the deodorant composition according to the present invention reacts with dissolved oxygen and hydrogen peroxide under UV, thereby generating OH radicals to oxidize odor causing substances in the atmosphere to remove odors, and hydrogen peroxide. As described above, it is possible to further promote the production of OH radicals, thereby further enhancing the oxidizing power of the deodorant prepared from such a composition. That is, TiO ₂ / Cu used in the present invention is a photocatalyst oxide that is harmless to the human body, and can deoxidize not only ammonia, which is a basic odor, but also all odor causing substances such as hydrogen sulfide and methyl mercaptan, which are acidic odors. When the deodorant is prepared from the composition, it is possible to provide a deodorant having excellent deodorizing efficiency. Furthermore, since the deodorant can change the odor component into a harmless gas such as CO ₂ , H ₂ O and the like by photooxidation, secondary decontamination The generation of substances can also be prevented.

In the deodorant composition according to the present invention, the TiO ₂ / Cu is preferably included in a concentration of 10,000 ~ 100,000mg / l, the H ₂ O ₂ is preferably included in a concentration of 100 ~ 1,000mg / l. In particular, when the hydrogen peroxide is included at a concentration of 1000 mg / l or more, since it can generate other radicals in addition to the OH radical, it is preferably included below the concentration, if included in a concentration of 100 mg / l or less Since the oxidizing power of the deodorant cannot be properly improved, it is preferably contained at the concentration or higher.

In addition, it is preferred that the deodorant composition of the present invention additionally comprises fragrance. Such a scent can be generally used a scent that has been mainly used in the conventional deodorant, but is preferably included in a concentration of 1,000 ~ 20,000mg / l.

On the other hand, the present invention provides a spray deodorant for removing odor, foot odor and body odor generated in a dog, made of the deodorant composition according to the present invention.

Hereinafter, the configuration and operation of the present invention will be described in detail.

In the photocatalytic oxidation method used in the deodorant according to the present invention, as shown in the following reaction scheme, when the TiO ₂ , which is a catalyst having semiconductor properties, is suspended in water and irradiated with UV light, electrons excited and emitted are energized. Reacts with dissolved oxygen or hydrogen peroxide in water to form OH radicals, and OH radicals are formed by holes on the surface of the TiO ₂ photocatalyst, which means a method of oxidizing odor causing substances and the like.

TiO ₂ + hv → e ^- (Release) + h ⁺ (TiO ₂ surface)

The electrons emitted at this time

^{_{e - + O 2 → O 2}} - (Super Oxide Radical)

^{_{2O 2 - + 2H 2 O →}} 2 · OH + 2OH - generates · OH via a reaction of O ₂ +. _{On the} surface of TiO ₂ , · OH is formed by the reaction of h ⁺ + OH ⁻ → 2 .OH .

That is, the dissolved oxygen is changed to Super Oxide Radical by TiO ₂ , which decomposes H ₂ O to generate OH radicals. In order to promote this reaction, H ₂ O ₂ was added in the present invention, which played a role in promoting the following reaction in the photocatalytic oxidation. Principle of the production of such OH radicals is shown in FIG.

In addition, hydrogen peroxide undergoes a reaction as shown in the following reaction formula in titanium dioxide

TiO ₂ + hv → e ^- (Release) + h ⁺ (TiO ₂ surface)

By reacting with the released electrons to produce OH radicals, and also by reacting with superoxide radicals generated by reacting with dissolved oxygen to produce OH radicals, it is possible to generate more OH radicals generated in the existing dissolved oxygen. However, too much hydrogen peroxide injection can be counterproductive. This is because OH radicals form · OH ₂ and H ₂ O ⁻ by hydrogen peroxide when excess hydrogen peroxide is injected. The principle of OH radical formation of hydrogen peroxide is as follows.

H ₂ O ₂ + e ^- → OH + OH ^-

H ₂ O ₂ + O ₂ ^- → OH + OH ^- + O ₂

H ₂ O ₂ + · OH → · OH ₂ + H ₂ O ^-

Therefore, as main components of the deodorant (odor treatment agent) composition according to the present invention, TiO ₂ / Cu 10,000 to 100,000 mg / l and H ₂ O ₂ 100 to 1,000 mg / l are added, and an additional flavor is added thereto. This is preferable.

Specifically, it is preferable that TiO ₂ / Cu, which can generate OH radicals exhibiting strong oxidizing power, is contained at a concentration of 10,000-100,000 mg / l. If the concentration is less than 10,000 mg / l, the production of OH radicals is lowered. In addition, exceeding 100,000 mg / l may produce too much OH radicals, which may cause secondary damage by oxidation to the surrounding environment as well as odorous substances. In addition, hydrogen peroxide, which is another component that promotes the formation of OH radicals of the photocatalyst, is suitably 0.01 to 0.1% based on the amount of TiO ₂ / Cu added. Therefore, in the present invention, by adding 100 to 1,000 mg / l, May promote the formation of OH radicals. If it is less than 100mg / l, the promotion of the photocatalyst formation of TiO ₂ / Cu is very small, if it exceeds 1,000mg / l may promote the formation of OH radicals and adversely affected by the oxidation of the remaining hydrogen peroxide.

Depending on the use of the deodorant, the fragrance can be added. The fragrance is based on the use of natural fragrance. By adding the fragrance, the small amount of odor that has been oxidized and left can be masked into the fragrance to completely solve the odor. The amount is preferably 1,000 ~ 20,000mg / l, less than 1,000mg / l fragrance is too weak to see the effect of use, and more than 20,000mg / l is inferior in economic efficiency and too strong fragrance may cause headaches and discomfort.

In addition, when looking at the deodorant composition according to the present invention and the manufacturing process of the deodorant using the same, ① the quality and specification inspection of the raw material received, ② dry weight of the raw material, ③ after the precise weighing of the raw material at the compounding ratio suitable for the treatment odor, ④ chemical Adjust the pH (hydrogen ion concentration) according to the use through activity control work, and then measure and package the sealed product.

When the deodorant of the present invention is used, ㉠ deodorizing effect is fast and excellent in sustaining effect (reaction time: 5 seconds-30 minutes, duration 3 days), ㉡ harmless, odorless secondary generation of pollutants (CO ₂ + H ₂ O), 를 shows antibacterial and bactericidal effect. ㉣ Hypoallergenic to skin, no acute toxicity (PII: 0.05, LD ₅₀ : 5,000mg / kg or more).

Table 1 below describes the properties of the deodorant according to the present invention.

Properties of Deodorant According to the Present Invention Item standard Remarks main ingredient TiO ₂ / Cu + H ₂ O ₂ Color Light green color smell Odorless pH 6.0-8.0 Statue Liquid phase Acute Toxicity Test (LD ₅₀ ) 5,000 mg / l or less KFDA Notification No. 98-116 Skin irritation test (P.I.I) 0.05 -

On the other hand, the performance of the deodorant according to the invention and the performance of the existing product is described in Table 2 below.

Comparison of Deodorant of the Invention with Competitive Products in Korea Performance Category Invention Deodorant according to the prior art pH 6.5-8.0 4.12 Deodorizing ability Ammonia Removal rate: 93.3% Removal rate: 86.7% Trimethylamine : 86.7% : 81.7% Hydrogen sulfide : 91.7% : 74.0% Methyl mercaptan 92.0% : 85.0% Antimicrobial effect 99.0% 99% LD ₅₀ (mouse) 5,000 mg / l or more 5,000 mg / l or more P.I.I 0.05 0.35

As shown in Table 2, the deodorizing ability of the deodorant according to the present invention appears evenly it can be seen that the deodorizing effect is very excellent.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited thereto, but is presented as an example.

Example 1

The deodorant of the present invention consisting of TiO ₂ / Cu 20,000 mg / l and H ₂ O ₂ 500 mg / l was added to a standard gas at a concentration of 1,000 mg / l. It was.

division Measurement item Test Items unit ammonia Hydrogen sulfide Methyl mercaptan Trimethylamine Deodorization test Initial concentration ppm 60 60 50 60 30 minutes later ppm 10 15 17 16 1 hour later ppm 8 13 13 14 2 hours later ppm 6 10 9 11 4 hours later ppm 5 7 5 9 6 hours later ppm 4 5 4 8 Removal rate (%) 93.3% 91.7% 92.0% 86.7%

Example 2

To compare the test results for the deodorizing performance of the target standard gas composed of only TiO ₂ / Cu 20,000㎎ / l and deodorants with TiO ₂ / Cu 20,000㎎ / l of the present invention consisting of H ₂ O ₂ 500㎎ / l deodorants It is shown in Table 4.

Heavy metal detection test by deodorant of the present invention Classification Measurement Items TiO ₂ / Cu + H ₂ O ₂ TiO ₂ / Cu Remarks Before input After input % Removal Before input After input % Removal NH ₃ 60 ppm 8 ppm 86.67 60 ppm 12 ppm 80.00 H ₂ S 60 ppm 13 ppm 78.33 60 ppm 16 ppm 73.33 CH ₃ SH 50 ppm 13 ppm 74.00 50 ppm 18 ppm 64.00 (CH ₃ ) ₃ N 60 ppm 14 ppm 76.67 60 ppm 18 ppm 70.00 The above sample was collected in Tedla bag, and the analysis method was: GC-FID analysis. Result after 1 hour of drug (deodorant) administration.

Example 3

The same deodorant (deodorant using only the present invention and TiO ₂ / Cu) as in Example 2 was used, except that the concentration of the deodorant was changed to 2,000 mg / l. The results are shown in Table 5 below.

Odor elimination efficiency according to duration Classification Duration unit TiO ₂ / Cu + H ₂ O ₂ TiO ₂ / Cu Remarks H ₂ S NH ₃ H ₂ S NH ₃ Early ppm 60 60 60 60 0.5 hours ppm 10 8 15 12 1 hours ppm 8 6 11 9 4 hours ppm 5 5 8 7 24 hours ppm 2 4 5 6 48 hours ppm One 3 3 5 60 hours ppm 0.5 3 2 5 Average removal rate (%) 92.6% 91.9% 87.8% 87.8%

As described above, the deodorant of the present invention improves the oxidizing ability of the malodorous substance by TiO ₂ / Cu as a photocatalyst to H ₂ O ₂ , thereby further improving the deodorizing ability, and is excellent in safety due to the harmlessness of the photocatalyst. Since the effect is excellent, it can show the effect of removing odor in many fields.

Claims (4)

Deodorant composition for removing odor, comprising a photocatalyst TiO ₂ / Cu and H ₂ O ₂ The deodorant composition according to claim 1, wherein the TiO ₂ / Cu is included at a concentration of 10,000 to 100,000 mg / l, and the H ₂ O ₂ is included at a concentration of 100 to 1,000 mg / l. 2. The deodorant composition according to claim 1, further comprising fragrance at a concentration of 1,000 to 20,000 mg / l. A spray deodorant for removing odors, odors and body odor generated in a pet dog prepared from the deodorant composition according to any one of claims 1 to 3.