KR20130063747A - Offensive mixed odor treatment system of low concentration and mid concentration by using catalytic oxidizing water. - Google Patents

Abstract

PURPOSE: A complex bad smell processing system is provided to remove bad smells by spraying catalyst oxidizing water containing OH radicals which is able to react with all kinds of bad smells of basic, acidic and neutral components among complex bad smell components. CONSTITUTION: A complex bad smell processing system uses catalyst oxidizing water(2) produced by the following steps: putting three kinds of ceramic catalysts in a catalyst charging tower; introducing a solution including sodium hypochlorite, calcium hypochlorite, chlorine dioxide and chlorine gas in the lower part of the catalyst charging tower; and contacting with the catalysts, while mixing water to circulating water and make-up water of a catalyst oxidizing water cleaning tower. The catalyst oxidizing water is sprayed downward in a mist form to process the bad smell components at a low or medium concentration discharged upward. The three kinds of ceramic catalysts consist of a first particle of black color, a second particle of brown color, and a third particle of white color. The first particle is a magnetic material and a metal oxide of iron(3.2wt%), molybdenum(0.5wt%), cobalt(0.7wt%), titanium(0.2wt%), magnesium(1.4wt%), aluminum(4.8wt%), potassium(0.8wt%), zirconium(1.6wt%), silicon(0.9wt%), tungsten(0.05wt%), and chrome(2.6wt%) which are combined to a ferrite-based material and sintered. The second particle is at least one magnetic material and a metal oxide of iron(3.2wt%), manganese(2.6wt%), cobalt(0.7wt%), titanium(0.2wt%), magnesium(1.4wt%), aluminum(4.8wt%), potassium(0.8wt%), zirconium(1.6wt%), silicon(0.9wt%), calcium(0.4wt%), and germanium(4.4wt%) which are combined to a ferrite-based material, and sintered. The third particle is at least one metal oxide of aluminum oxide(18wt%), zirconium oxide(6.3wt%), diatomite(12.6wt%), barium titanate(0.8wt%) which is combined and sintered.

Description

Offensive mixed odor treatment system of Low concentration and Mid Concentration by using Catalytic Oxidizing Water. }

The technical field to which the present invention belongs is a PCB factory for manufacturing semiconductor or electronic circuit boards such as LCD and LED, a tire production factory for rubber vulcanization reaction, a factory for producing plastic, a factory for coating work, a food waste treatment plant, sewage It is a technical field for treating medium and low concentration complex odors composed of basic, acidic and neutral components generated from sludge dewatering cakes, sludge drying facilities, livestock wastewater and sludge treatment facilities, and acid odors such as methyl mercaptan and sulfur dioxide. Of deodorization equipment such as single or continuous washing towers or biofilm towers installed in factories that generate complex odors of medium and low concentrations containing some or all of basic odor components such as ammonia and amines and neutral odor components such as acetaldehyde. By installing a two-fluid nozzle in the exhaust gas duct or stack, the catalytic oxidation water is mixed with compressed air It is a field of environmental technology to further oxidatively decompose the untreated residual complex odor through the catalytic oxidation water by spraying in an aerosol state.

In the case of a washing tower, which is a general odor treatment facility that simply absorbs odor components by spraying water or causes chemical reactions with odor components such as sulfuric acid or caustic soda to neutralize odor components with chemicals to remove odors, It is effective when absorbed well in water, but the treatment effect is not satisfactory for the complex odor that is not absorbed well in water.

In addition, odors of basic components such as ammonia and amines are treated in an acid washing tower using sulfuric acid, and acid odors such as methyl mercaptan and hydrogen sulfide among residual odors are treated in an alkali washing tower using caustic soda, followed by acetaldehyde as a residual odor. Neutral odors have been attempted to be treated in biosystems such as biofilm towers using microorganisms. However, caustic soda scattered in alkaline scrubbers in the front often causes deterioration of microorganisms in biosystems. The satisfactory treatment of complex odors is unsuccessful due to the growth of specific microorganisms to react and the technical difficulties of maintaining microorganisms and maintaining the system within a certain range of temperature, pH and humidity.

Therefore, the present invention is made by contacting the aqueous sodium hypochlorite solution of about 100ppm concentration with a special functional catalyst to make the catalytic oxidation water, mixed with compressed air and a dilute nozzle, and untreated residual odor components and chemicals in the duct and stack of the existing exhaust gas equipment The reaction is easily induced to remove odor by complex decomposition.

The existing single washing tower or double washing tower, or biofilm tower or bio-system to treat low and medium concentrations of odors composed of basic, acidic and neutral components, or untreated due to the limitation of the treatment efficiency of the existing equipment. In case of workplaces that have to deal with residual odors emitted to the public, or workplaces that need to supplement existing odor facilities due to different legal regulations at the time of installation, or installation site of supplementary facilities that can handle odors generated in an expanded factory. It is a field of complementary equipment that can be applied to workplaces that cannot handle residual odors because it cannot install a separate supplementary facility due to the concerned workplace or other reasons, and is a conventional technology for treating complex odors of medium and low concentration. Odors of basic components such as ammonia and amines are added to the acid washing tower using hydrochloric acid or sulfuric acid. After treating acidic odors such as methyl mercaptan and hydrogen sulfide in the alkaline washing tower using caustic soda, neutral odors such as acetaldehyde, which is the final residual odors, are treated in a separate third process such as a biofilm tower or a biosystem. Although the odor has been removed from the plant, the treatment efficiency of treating the odor of the aldehyde component in the short treatment time in the third treatment plant is low, and the odor law at the time of the odor treatment plant was installed, but it was not regulated. Complementary equipment should be installed to comply with odor laws, but neutral odor components may be treated only partially when treating basic odors and acid odors in existing acid scrubbers, alkaline scrubbers, and biofilm towers. It's happening.

In addition, even in the case of installing and operating the washing towers according to each characteristic continuously, the efficiency of the individual washing towers is about 85%, which is almost untreated with the remaining 15% of acid and basic odors that are not treated in the existing washing towers. There has been an urgent need for a third washing tower that can simultaneously handle the neutral neutral odors, but it is economically and technically a complex odor of low and medium concentrations, such as the problem of lack of a site to install supplementary equipment by connecting to an existing washing tower. The installation of a facility that can handle is not easy, and there was no satisfactory facility for treating complex odors of medium and low concentration by applying or applying the prior art.

Complex odors of medium and low concentrations composed of basic, acidic, and neutral components that occur during the operation of facilities in factories that produce various products needed by people's daily lives are increasing and their treatment methods are difficult. As a result, environmental pollution and civil complaints are becoming more severe, and in order to prevent environmental pollution and civil complaints caused by odors, mandatory installation of odor treatment facilities is required at workplaces and facilities where odors occur. This is mandatory through various laws and regulations.

However, in the case of medium and low concentration of odor, it is not a odor or one or two kinds of odors but a complex constituent containing all 12 odors specified by the law. In the case of a washing tower, which is a general odor treatment facility that removes odors by reacting odor components with chemicals by causing chemical reactions with chemicals such as sodium hydroxide or caustic soda, odors that are well absorbed by water or odors of a single component Although somewhat effective in the odor treatment of the complex component is insufficient.

Therefore, odors of basic components such as ammonia and amine are treated in an acid washing tower using sulfuric acid, and acid odors such as methyl mercaptan and hydrogen sulfide among residual odors are treated in an alkali washing tower using caustic soda, followed by acetaldehyde as a residual odor. Neutral odors have been attempted to be treated in biosystems such as biofilm towers using microorganisms. However, caustic soda scattered in alkaline scrubbers in the front often causes deterioration of microorganisms in biosystems. It has been reported to be unsuccessful due to the difficulty of growing specific microorganisms that react, maintaining difficult temperature and humidity, and technical difficulties in culturing microorganisms and maintaining the system.

According to the present invention, the growth of specific microorganisms that frequently generate untreated residual malodor or microorganism growth and react only to specific malodorous ingredients due to the marginal efficiency in the conventional single or continuous washing tower, maintain temperature, pH and humidity within a certain range The present invention is to treat untreated residual odors in biofilm towers where difficult microbial cultivation and technical maintenance, etc. occur, and catalyzed oxidation by a device for producing catalytic oxidation water using a simple ceramic catalyst, which is a kind of functional ceramics. (2) to generate and spray down the mist (11) of the existing odor facility in the form of a mist downwards and process complex pressure through the chemical reaction with the residual odor component discharged upwards to supplement the existing equipment economically and efficiently. It would be.

In the present invention, a catalytic nozzle (2) made by contacting a ceramic catalyst sintered with a ferrite-based metal oxide and an aqueous solution containing chlorine in a discharge stack 11 of an existing deodorization system in the form of a mist, a double-fluid nozzle (1) It is intended to supplement existing equipment by removing downward odor through chemical reaction and residual odor discharged upward by untreated by spraying downward.

Catalytically oxidized water has many kinds and functions, but for the system configuration of the present invention, since oxygen and OH radical having strong oxidizing power are required, ferrite-based at least magnetic material, iron, manganese, cobalt, titanium, molybdenum, aluminum, zirconium, Catalytic filling of an aqueous solution containing chlorine (sodium hypochlorite, calcium hypochlorite, chlorine dioxide, chlorine gas) The catalytic oxidized water (2) produced by the catalytic action by passing through the tower is subjected to a chemical reaction with all residual odors of acidic, basic and neutral components among the remaining odorous components to purify the odor.

The present invention relates to a method for treating malodors through chemical reactions of oxygen OH and OH radicals of acidic, basic and neutral constituents of catalytically oxidized water (2) in a treatment system. 11) Its technical purpose is to develop and operate the process that can easily complement the facilities for treating complex odors of medium and low concentrations by constructing the whole system connected in series.

In the present invention, in the treatment of untreated residual odors in single or continuous chemical cleaning towers or biofilm towers, the odors of complex components composed of medium, low concentrations of acid, basic, and neutral are sintered with ferrite-based metal oxides. The catalytically oxidized water (2) containing OH radicals made by the contact between the catalyst and the aqueous solution containing chlorine is sprayed downwardly through the double-fluid nozzle (1) in the final discharge stack (11) of the existing deodorizing equipment to the mist state. The present invention relates to the theory of chemical reactions of the complementary device that treats complex odors through the continuous chemical reaction with all remaining odorous constituents, and to the configuration of the device and the operation of the entire facility.

In the present invention, in treating residual odors of complex components of medium and low concentrations, odors of basic components such as ammonia and amine, untreated and discharged from existing single or continuous washing towers or biofilm towers, and methyl mercaptan, hydrogen sulfide, etc. Neutralization of oxygen and OH radicals and the generation of catalytically oxidized water (2), which sprays odors of acidic components and residual odors of neutral components such as acetaldehyde in the form of mist through the nozzle (1) from the flue (11) as the final outlet. It consists of a continuous tandem device that complements the existing deodorization equipment that is reacted and treated.

As a binder for producing the catalytically oxidized water (2), the ceramic catalyst uses resin or glass, and at least ferrite-based magnetic material, iron (3.2 Wt%), molybdenum (0.5 Wt%), cobalt (0.7 Wt%), titanium (0.2) Wt%), magnesium (1.4Wt%), aluminum (4.8Wt%), potassium (0.8Wt%), zirconium (1.6Wt%), silicon (0.9Wt%), tungsten (0.05Wt%), chromium (2.6Wt % Black metal particles sintered with a combination of metal oxides, ferrite-based at least magnetic material and iron (3.2 Wt%), manganese (2.6 Wt%), cobalt (0.7 Wt%), titanium (0.2 Wt%) Of magnesium (1.4 Wt%), aluminum (4.8 Wt%), potassium (0.8 Wt%), zirconium (1.6 Wt%), silicon (0.9 Wt%), calcium (0.4 Wt%), germanium (4.4 Wt%) By sintering the second particles of brown color sintered with metal oxide, at least aluminum oxide (18 Wt%), zirconium oxide (6.3 Wt%), diatomaceous earth (12.6 Wt%), and barium titanate (0.8 Wt%) Three kinds of ceramic catalysts composed of sintered white particles (third particle: first particle: second particle: third particle ratio) 78Wt%: 19Wt%: the 3Wt%) of sodium hypochlorite, calcium hypochlorite, chlorine dioxide, chlorine gas, chlorine packed in a catalyst packed column in a catalyst packed column bottom was added and mixed for about 0.5 ~ 500ppm. The chlorine concentration can be changed depending on the type of purification target and the degree of purification, but the effect can be sufficiently obtained even if it is normally used at 1 to several ten ppm. By introducing the aqueous solution containing the above chlorine and contacting with the catalyst, the catalytic oxidation water (2) is contacted with the odor component by using the mixed water in the circulating water (1: 1.3 * 10 ³ ) and supplemental water of the catalytic oxidation water washing tower. Some or all of the basic odor and equivalent odors of the neutral component are reacted by using some or all of the generated oxygen and OH radicals in the water use solution. It can be simply increased to handle the equivalent to equivalent ratio.

In addition, the Z-shaped eliminator is installed in two stages in front of the outlet of the stack 11 so that the catalytically oxidized water 2 sprayed in the form of mist is discharged through the two-fluid nozzle 1 to deal with the residual odor discharged upward from the stack. Prevents air from flying out of the stack due to air pressure.

The main chemical reaction with the residual malodorous component in the stack 11, which is the final outlet constituting the present invention, is as follows.

 ■ Preparation of catalytic oxidation water is as follows.

NaOCl + H ₂ O → NaOH + HOCl

 NaOCl → Na + + OCl-

OCl- is stable because the NaOCl stock solution itself is alkaline, but NaOCl is mixed with water and diluted (4) before being introduced into the catalyst tower (5), so the pH is neutral and HOCl is stable.

When introduced into the catalyst tower 5 and then in contact with the catalyst, the following reaction occurs.

  HOCl → exists as HCl + [O]

                 (Under catalyst) (oxygen generator)

Cl ₂ + H ₂ O → HClO + HCl

HOCl → HCl + O (oxygen generator)

^{HOCl ← --- → H + + OCl} - or Cl - + OH (radical)

When sodium hypochlorite (or chlorine) is dissolved in water, sodium hypochlorite is made of sodium hydroxide (NaOH) and an aqueous solution of sodium hypochlorite decomposed into hypochlorite (HOCl) and becomes alkaline. This reaction is extremely slow and does not easily proceed in the right direction under normal conditions, but the ceramic catalyst acts as a catalyst which markedly promotes the reaction in the right direction. Hypochlorous acid decomposes and generates oxygen in the generator, and this oxygen shows a strong oxidation. Since the catalytically oxidized water (2) has up to 300 times more powerful oxidizing power than the general chlorine system, the generated oxygen and OH radical of the catalytically oxidized water (2) undergo a chemical reaction with the odor, and the oxidation reaction is extremely excellent.

Due to limitations in the efficiency of single or continuous cleaning towers in conventional systems, conventional biofilm towers have different treatment efficiencies due to untreated medium and low concentrations of odors and changes in biofilm towers or biosystems. OH radicals that can be chemically reacted with all of the basic, acidic, and neutral odors of the complex odor components by being connected in series to the final discharge stack 11 of the existing odor treatment system to completely treat the untreated odors in the By spraying the contained catalytic oxidation water (2) in the form of a mist with a two-fluid nozzle (1) has a remarkable effect in complementing the untreated odor in the existing odor treatment system.

1 is a schematic diagram for the practice of the present invention.

In the catalytic oxidation tower (2) spraying system in the washing tower or the conventional biofilm tower or the stack (11) that supplements the bio system, the ceramic catalyst, which is a kind of functional ceramic, is contained in the catalyst filling tower. In the aqueous solution containing chlorine in contact with the catalyst and the catalytic oxidation water (2) generated by spraying in the form of a spray downwardly through the two-fluid nozzle (1) from the stack 11, acid, basic, neutral discharged upward The residual odor of the component is treated by chemical reaction. The functional ceramic catalyst is a mixture of various kinds of metal oxides having different component concentrations. The first particles are ferrite-based at least magnetic material, iron (3.2 Wt%) and molybdenum (0.5 Wt%). ), Cobalt (0.7Wt%), titanium (0.2Wt%), magnesium (1.4Wt%), aluminum (4.8Wt%), potassium (0.8Wt%), zirconium (1.6Wt%), silicon (0.9Wt%) When combining a metal oxide of tungsten (0.05Wt%) and chromium (2.6Wt%) It is black color sintered, and the second particle is ferrite-based at least magnetic material, iron (3.2Wt%), manganese (2.6Wt%), cobalt (0.7Wt%), titanium (0.2Wt%), magnesium (1.4Wt%) ), Sintered with a combination of metal oxides of aluminum (4.8 Wt%), potassium (0.8 Wt%), zirconium (1.6 Wt%), silicon (0.9 Wt%), calcium (0.4 Wt%) and germanium (4.4 Wt%) It is a brown color, and the third particle is a white color sintered by combining a metal oxide of at least aluminum oxide (18 Wt%), zirconium oxide (6.3 Wt%), diatomaceous earth (12.6 Wt%), and barium titanate (0.8 Wt%). It is spherical with a diameter of about 15mm to 25mm. The ratio of first particles: second particles: third particles is 78Wt%: 19Wt%: 3Wt%.

In addition, the effective chlorine concentration of the chlorine-containing aqueous solution introduced into the catalyst packing tower is sodium hypochlorite (100 mg / l), calcium hypochlorite (100 mg / l), chlorine dioxide (100 mg / l), and chlorine gas (100 mg / l). .

According to the present invention as described above, after filling the ceramic catalyst inside the catalyst filling tower, the aqueous solution containing the appropriate concentration of chlorine is passed through the catalyst filling tower and brought into contact with the catalyst to form chlorine (NaOCl or Cl ₂ ) by the catalytic action of the ceramic catalyst. The aqueous solution contained is converted into catalytic oxidation water (2). When the catalytic oxidation water is sprayed in the form of mist through the double-fluid nozzle 1 from the stack 11, which is the final outlet of the existing deodorization equipment, the odor of acidic, basic, and neutral components is generated in the spray droplets of the catalytic oxidation water (2). Neutralizes by chemical reaction between oxygen and OH radicals.

■ The reaction formula of neutral odor and residual odor components using catalytic oxidation water is as follows.

1) Acetaldehyde: CH ₃ CHO

CH ₃ CHO + [O] → CH ₃ COOH (acetic acid); Soluble in water and no smell

2) Hydrogen Sulfide: H ₂ S

H ₂ S + 4 [O] → H ₂ SO4 (Sulfate: Soluble in water)

3) Methylmercaptan (CH ₃ SH)

CH ₃ SH + 3 [O] → CH ₃ SO ₃ H (methylsulfonic acid: soluble in water)

4) Methyl sulfide: CH ₃ SCH ₃

CH ₃ SCH ₃ + [O] → (CH ₃ ) ₂ SO (dimethylsulfooxide: continued reaction with oxygen)

(CH ₃ ) ₂ SO + 2 [O] → (CH ₃ ) ₂ SO ₃ (Dimethylsulfonic acid: soluble in water)

5) Methyl Disulfide: (CH ₃ ) ₂ S ₂

(CH ₃ ) ₂ S ₂ + H ₂ O → CH ₃ SH (Methylmercaptan) + CH ₃ SOH

                                                     (Metasulfenic acid: Soluble in water)

CH ₃ SH + 3 [O] → CH ₃ SO ₃ H (methylsulfonic acid: soluble in water)

■ Catalytic oxidized water sprayed downward from the stack is collected in the circulating water service tank and circulated to general rinse water or discharged to the sump of the wastewater treatment plant.

The catalytic oxidation water (2) supplied to the two-fluid nozzle (1) of the stack (11) is to be introduced in a quantitative manner using a metering pump.

■ Catalyst tower (5), chemical storage tank and chemical liquid supply pump (3) for making catalyst oxidation water (3) are materials that do not react with sodium hypochlorite, according to the special specifications.

One; Airflow nozzle 2; Catalytic oxidation water in 3; Chemical liquid supply pump 4; NaOCl Diluent
5; Catalyst tower 6; Compressed air in 7; Flue gas in 8; air blower
9; Regulator 10; Drain 11; Stack

Claims (5)

In the whole system connected in series with the stack 11 of the existing odor treatment deodorization equipment, at least ferrite-based magnetic material, iron (3.2 Wt%), molybdenum (0.5 Wt%), cobalt (0.7 Wt%), titanium ( 0.2 Wt%), Magnesium (1.4 Wt%), Aluminum (4.8 Wt%), Potassium (0.8 Wt%), Zirconium (1.6 Wt%), Silicon (0.9 Wt%), Tungsten (0.05 Wt%), Chromium (2.6 Black color particles sintered by combining a metal oxide of Wt%), ferrite-based at least magnetic material and iron (3.2Wt%), manganese (2.6Wt%), cobalt (0.7Wt%), titanium (0.2Wt% ), Magnesium (1.4 Wt%), aluminum (4.8 Wt%), potassium (0.8 Wt%), zirconium (1.6 Wt%), silicon (0.9 Wt%), calcium (0.4 Wt%), germanium (4.4 Wt%) A second color of brown color sintered by combining a metal oxide of at least aluminum oxide, at least aluminum oxide (18 Wt%), zirconium oxide (6.3 Wt%), diatomaceous earth (12.6 Wt%), and barium titanate (0.8 Wt%) 3 kinds of ceramic catalysts of 3rd particles of white color sintered by At the bottom, an aqueous solution containing sodium hypochlorite, calcium hypochlorite, chlorine dioxide, and chlorine gas chlorine was introduced, and the catalytic oxidation water (2) produced by contacting the catalyst was used as mixed water in the circulating water and the supplemental water of the catalytic oxidation water washing tower. By spraying the catalytic oxidation water (2) downward in the form of a mist through the two-fluid nozzle (1) in the final discharge stack (11) of the existing deodorizing equipment can be treated odor components of low to medium concentrations discharged upward Complex Odor Treatment System
The complex odor treatment system according to claim 1, wherein the ratio of the composition of the ceramic catalyst is 78Wt%: 19Wt%: 3Wt% of the first particles of black color: second particles of brown color: third particles of white color.
The complex odor treatment system according to claim 1, wherein as the chlorine-containing material, sodium hypochlorite, calcium hypochlorite, chlorine gas, and chlorine dioxide are used, and the concentration thereof is 0.5 _to 1000 ppm.
The complex odor treatment system according to claim 1, wherein the ratio of the catalytic oxidation water 2 to the circulating water of the catalytic oxidation water washing tower is 1: 1.3 * 10 ³ .
 The method of claim 1, characterized in that the Z-type Eliminator treatment system for preventing the droplets of catalytically oxidized water (2) sprayed downward in the mist form with the air pressure discharged upwards to be scattered into the air outside the stack (11). Complex odor treatment system

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