KR100713615B1 - Offensive odor treatment apparatus using chlorine dioxide - Google Patents

Abstract

The present invention chemically reacts sodium chlorite (NaClO ₂ ) or sodium hypochlorite (NaClO) with hydrochloric acid (HCl) to generate activated chlorine dioxide (ClO ₂ ), which is quickly contacted with the odor source without side reactions to cause odor. It has a technical configuration for removing the generating material.

Chlorine dioxide generated by the chemical reaction is a gas of a radical form having a high volatility, so the storage is inferior, and chlorine dioxide generator using a chemical reaction to facilitate storage because it is easy to deteriorate into by-products such as chloride during long-term accumulation and storage. In order to concentrate the chlorine dioxide (ClO ₂ ) generated through water using an ejector block, a chlorine dioxide (ClO ₂ ) concentrate is obtained, and a circular screw type or step type that induces a rapid flow so that the chlorine dioxide produced first is discharged first. It includes a means for rapidly transferring to the facility of the odor source reaction tank through the storage tank having a flow and injection into the odor source, wherein the generated chlorine dioxide is used locally, not limited to only partial effects, To increase the odor removal effect The present invention relates to an apparatus for removing odor generating substances using activated chlorine dioxide (ClO ₂ ), which has been started with technical problems and technical thoughts to maximize the use effect of chlorine dioxide administered by devising a method.

Odor generating substance, chlorine dioxide, chlorine dioxide generator,

Description

Offensive odor treatment apparatus using chlorine dioxide

1: Process odor removal process of the present application using chlorine dioxide (ClO ₂ )

2a: Illustrated storage tank having a skewed rotary pipe

2b: Illustrated storage tank having a zigzag flow guide plate

3: Example of grafting chlorine dioxide to an air supply line

Due to the rapid industrialization and the improvement of living standard, the quality of life of mankind is getting better and getting better and well being, but the natural environment of the earth is desolate day by day.

The amount of wastewater, household waste and household waste flowing out from each household and industry is increasing day by day, and the degree of pollution is intensified. Household wastes such as treatment facilities are flooded, and the treatment facilities for treating them are recognized as hate facilities due to odors and harmful gas generation, and these hate facilities cause many complaints and establish the treatment centers due to local complaints or group self-interest. Today's reality is that you can't find a place to do it.

Odor-generating facilities are generated at home and industrial sites such as sewage treatment plant, manure treatment plant, livestock manure treatment plant, restaurant, waste treatment plant, slaughterhouse, and other chemical manufacturing plant. , Methyl mercaptan, methyl sulfide, methyl disulfide, amines, acetaldehyde, etc. have been found, but the actual odor causing agents are much higher and there are hundreds of odorous substances.

Therefore, in order to remove odorous substances generated from various pollutants as described above, various removal technologies are required according to various factors by causes of occurrence and place of occurrence. Therefore, research has been conducted in a wide range of parts. Looking at the representative technologies that are disclosed or studied as a technology,

1) the technical field to use the Bio-Filter to remove odor gas by microorganisms nourishing odor component,

2) the technical field of the soil deodorization method to remove odorous substances by natural decomposition by microorganisms and adsorption of soil particles by passing malodorous gas through the soil layer;

3) the technical field of water washing to neutralize the malodor generating substance with acid or basic substance to remove the malodorous substance,

4) the technical field of the adsorption method for adsorption and removal of odor-causing substances using an adsorbent such as activated carbon,

5) the technical field of the masking method to remove odorous substances using the fragrance of aromatic substances,

6) The ozone oxidation method for oxidizing and decomposing odorous substances by using the oxidation of ozone is known.

The present application is a method for solving the odor occurrence problems occurring in various aversive facilities as described above by activating chlorine dioxide (NaClO ₂ ) or sodium hypochlorite (NaClO) by chemical reaction with hydrochloric acid (HCl) The present invention relates to a technique for generating ClO ₂ ) and rapidly removing the malodorous substances by contacting the malodorous sources.

Chlorine dioxide is a non-chlorine disinfectant and disinfectant. It has the strongest sterilizing power and bleaching power after ozone, and is used in the form of water-soluble oxidizing agent in which chlorine dioxide gas is dissolved in the solution.

In addition, chlorine dioxide has a strong oxidizing power over a wide range of pH, and in particular, the deodorizing effect is excellent in the oxidative removal of phenols, amines, hydrogen sulfide, etc. that cause odors in sewage treatment plants.

Chlorine dioxide (ClO ₂ ) exists in the form of a radical in the gas phase at room temperature. Chlorine dioxide has two types of stabilized chlorine dioxide and activated chlorine dioxide. Stabilized chlorine dioxide is a buffer solution in the form of carbonate and phosphate. The effect is shown as chlorine, and chlorine dioxide (ClO ₂ ) causes side reactions during long-term storage, and by-products such as carcinogens are generated and contained. In the case of using oxidizing power or deodorizing power of chlorine, stabilizing chlorine dioxide was used to perform the activation process again at the site of use.

Activated chlorine dioxide has low water solubility and severe change over time, which makes it difficult to store and has a problem of being easily decomposed by light, so its use is extremely limited.

The present invention obtains chlorine dioxide (ClO ₂ ) concentrate by using an ejector block in order to concentrate the chlorine dioxide (ClO ₂ ) generated through the chlorine dioxide generator using a chemical reaction, so that the chlorine dioxide produced first is discharged first It has a technical idea to remove odors by contacting odor generating sources by transferring them to the odor generating source reactor through a storage tank having a circular screw type or a stepped flow which induces a rapid flow.

Accordingly, in the present application, as an odor removing apparatus for reducing odor using chlorine dioxide (ClO ₂ ) in an industrial site having various odor generating sources, sodium chlorite (NaClO ₂ ) or sodium hypochlorite (NaClO) or the like may be used as hydrochloric acid ( HCl) and chlorine dioxide through a chemical reaction (including a chlorine dioxide generator for generating ClO _2), and chlorine dioxide using an ejector block for the generated chlorine dioxide (ClO ₂₎ in order to concentrate the water (ClO ₂₎ concentrate Means for obtaining the chlorine dioxide (ClO ₂ ) solution is a means for quickly transferring through a storage tank having a circular screw or stepped flow to induce a rapid flow so that the chlorine dioxide produced first is discharged first, the existing facilities of the odor source reactor And a means for injecting the chlorine dioxide solution into the odor generating source by grafting the supply line of the chlorine dioxide solution. Have the purpose to.

Chlorine dioxide (ClO ₂ ) has been used as a disinfectant and disinfectant in the food processing industry as a representative disinfectant, and has been widely used as a disinfectant and drinking water treatment in the wastewater treatment industry.

Chlorine dioxide shows high reaction properties for certain substances, such as sulfur, amines, melcaptans, and cyanide, and gel deodorants containing chlorine dioxide are commercially available.

The present invention, even in the use of expensive electrolytic chlorine dioxide generator to use stabilized chlorine dioxide in the conventional water treatment field chlorine dioxide (ClO2) by the long-term storage causes side reactions such as chlorate (ClO 3-) by-products It solves the problem that is generated in large quantities and also provides chemical reaction type chlorine dioxide generator that can provide more efficient and cheaper product while solving the problem that activated chlorine dioxide has low water solubility and severe change over time. To provide a odor removing device using chlorine dioxide (ClO2) having a system that can quickly transfer the chlorine dioxide generated at the same time to the treatment object.

The present application is an odor removing device for reducing odor using chlorine dioxide (ClO ₂ ) in an industrial site having various odor generating sources. Sodium chlorite (NaClO ₂ ) or sodium hypochlorite (NaClO) or the like is hydrochloric acid (HCl). And a chlorine dioxide generator for generating chlorine dioxide (ClO ₂ ) through a chemical reaction with, and to obtain the chlorine dioxide (ClO ₂ ) concentrate using an ejector block to concentrate the generated chlorine dioxide (ClO ₂ ) in water. Means, Means for rapidly transferring the chlorine dioxide (ClO ₂ ) solution through a storage tank having a circular screw type or stepped flow to induce a rapid flow so that the chlorine dioxide produced first is discharged first, to the existing facilities of the odor source reactor Provided is a odor removing device comprising a means for grafting the supply line of chlorine dioxide solution to the injection of odor generating source, Chlorine dioxide (ClO ₂₎ generator, the pressure (differential pressure, negative pressure) sensor is chlorine dioxide installation (ClO ₂₎ to control the water supply amount in accordance with the amount of chlorine dioxide to zoom (ClO ₂₎ generating odor to stabilize the yield of the device is , Chlorine dioxide (ClO ₂ ) storage tank of the present application provides a odor removal device having a structure in which the fluid is sequentially discharged is formed in a skew type or step by using a stainless material, synthetic resin or synthetic fiber material.

The specific embodiments of the technical idea of the present application will be disclosed through the accompanying drawings as the technical configuration for describing the technical idea of the present invention.

In the present Figure 1 to obtain the activated chlorine dioxide (ClO ₂₎ to be used in the present application, to absorb it to the water makes the chlorine dioxide (ClO ₂₎ solution, it is made of chlorine dioxide (ClO ₂₎ solution, first the production of chlorine dioxide Figure 1 shows the flow process diagram to be applied to the reaction target by quickly transferring through the storage tank to induce a rapid flow to be discharged first.

Chlorine dioxide (ClO ₂ ) is generated by using the flow of [A] in the dashed line in the process chart. Referring to an embodiment for illustrating a specific application example, 15% hydrochloric acid in a chlorine dioxide generator is described. (HCl) 1 volume ratio with 12% tea acid soda (NaClO) was reacted with 2 volume ratio generate a Cl2 gas and be a way to produce a 27% hypochlorite soda (NaClO ₂₎ ClO ₂ gas were mixed at a 1.5 volume ratio here proposed Can be.

Referring to the process of generating the chlorine dioxide gas in more detail, the pressure sensor is installed in the chlorine dioxide generator is hydrochloric acid (HCl) and hypochlorite by using a change in the pressure sucked into the ejector block according to the change in the water supply amount ( NaClO), sodium chlorite (NaClO ₂ ) by varying the input amount of water and chemicals to adjust the supply of the chlorine dioxide can be generated in a certain concentration and yield even if the pressure changes, for example, When the water flow rate is 20 l / min and the pressure is -10 kg / cm 2, 15% hydrochloric acid 20ml / min, 12% sodium hypochlorite 40ml / min, 27% sodium chlorine 30ml / min When introduced at each flow rate, the concentration of chlorine dioxide (ClO ₂ ) is 4100mg / l and purity is 95.5%.

As another example, when the water flow rate is 40 l / min and the pressure is -40 kg / cm 2, 15 ml of hydrochloric acid is 40 ml / min, 12% sodium hypochlorite is 80 ml / min and 27% sodium chlorite is 60 ml. / min each of the flow rate of chlorine dioxide (ClO ₂ ) concentration of 4050mg / ℓ, it can be seen that the purity is generated at 94.8% bar, based on the data flow control valve of the pressure pressure -10㎏ / ㎠ If the pressure is -1, adjust the initial supply and increase the chemical supply flow by 3.3% .When the pressure is -40㎏ / ㎠, set the chemical supply by varying the supply to 200% of the initial supply. Chlorine dioxide generator can be provided to obtain a constant yield of chlorine dioxide even if the water flow rate is changed, and the pressure (differential pressure, negative pressure) sensor is installed in the chlorine dioxide generator to vary the chemical intake according to the water supply And can drive by stabilizing yield It is ...

The ClO ₂ gas produced above is grafted to the water supply line ejector block for transporting the high pressure water, diluted with water, and becomes a chlorine dioxide (ClO ₂ ) solution, which induces a rapid flow so that the chlorine dioxide produced first is discharged first. By using a storage tank to be quickly transferred to the reaction target may be made to the process of applying to the odor generating reaction target.

In the present application, the generated chlorine dioxide is used locally to enhance the odor removal effect in the entire contents without remaining only in partial effects. In FIG. 1, the supply line of the chlorine dioxide solution is supplied to an existing facility of the odor generating reactor. It shows the process flow chart which can maximize the use effect of chlorine dioxide by means of spray injection into odor generating source by grafting.

2 shows a storage (transport) tank of chlorine dioxide generated, and FIG. 2A shows a storage (transport) tank in which a skew-type rotary pipe is incorporated, and in FIG. A storage (transport) tank provided by forming a guide plate in a cascade is provided. The storage tank may be selected from a stainless steel material, a synthetic resin material, or a synthetic fiber.

In order to achieve a structure in which the fluid introduced through the flow guide plate formed in the skew type, rotating pipe, or stepped with an angle is sequentially discharged without accumulation, chlorine dioxide (ClO ₂ ) is used. In order to prevent a large amount of by-products such as carcinogens caused by long-term storage, the chlorine dioxide (ClO ₂ ) solution flowing in the storage (transport) tank with a skew-type rotary pipe in FIG. A structure for sending the odor-generating reactor to the odor generating tank without giving a motive for causing a side reaction by rapidly rotating the skewed rotary pipe after moving up through the pipe is illustrated. In FIG. The flow path is formed by forming a plurality of steps of flow path guide plates that form a guide flow path in the form of The chlorine oxide (ClO ₂ ) solution is zigzag in the upper flow path guide plate and is sent to the next flow path guide plate through the flow path of the multi-stage flow guide plate. It illustrates the structure for sending.

In order to prevent side reactions, the inside of the storage (transport) tank is preferably maintained at room temperature, and shaded so as not to be directly exposed to light because chlorine dioxide may be decomposed when exposed to light.

The upper part of the storage (transport) tank shows a structure in which a pressure control valve is installed to measure and regulate the internal pressure of the storage (transport) tank.

In FIG. 3a, a chlorine dioxide solution supply pipe is connected to a defoaming facility pipe of an existing wastewater treatment facility, and the chlorine dioxide is diluted in the vesicle water sprayed from the top of the odor source storage tank through the vesicle nozzle and sprayed from the top of the odor source. 3b shows a supply line of the chlorine dioxide solution to an existing facility of a odor source reactor as an embodiment structure for supplying the stored activated chlorine dioxide evenly over the entire odor source area to supply the odor source material more effectively. As an embodiment of the method of injecting odor into the odor generating source by grafting the odor removal device using chlorine dioxide (ClO ₂ ) grafting the supply line of the chlorine dioxide solution to the air supply line for transferring air to the acid generator of the odor generating reactor Due to the high pressure Which shows an embodiment of injection added to the odor source with an air supply line and chlorine dioxide (ClO ₂₎ solution, using the ejector principle due to the pressure difference occurs in the supply line of the chlorine dioxide solution and air to the water diffuser.

Hereinafter, in order to determine the reactivity of chlorine dioxide (ClO ₂ ) to the malodorous substances, the concentration of chlorine dioxide per odor source was added to determine the odor removal effect. The reactivity of chlorine dioxide is shown in Table-1. .

TABLE-1

division Responsive pH response range Chlorine Dioxide Consumption Remarks Mercaptans RSH (R silver alkyl group) ClO ₂ Deodorization 5-9 4.5 × S content → Organic emulsions RSR ClO ₂ Deodorization 5-9 4.5 × S content → Organic emulsions RSSR ClO2 Deodorization 5-9 4.5 × S content → Secondary amines R2NH ClO ₂ Deodorization 5-9 4.5 × N content → Tertiary amines R3N ClO ₂ Deodorization 5-9 10.0 × N content P →

In addition, chlorine dioxide of the present application to the odor-causing substances in the sewage as an experiment to investigate the effect of reducing the odor to the GAS generated after the source to reduce the odor pollutant source from the inflow stage, first of all simple in the field In order to determine the odor reduction effect, the concentration of chlorine dioxide was injected into the influent source and the odor reduction of each sample was compared by the direct functional method. In addition, for accurate quantitative analysis, fresh sludge generated from the initial settler and influent water were sampled, and the gas generated before and after oxidation treatment of chlorine dioxide (ClO ₂ ) was measured.

1) Experiment Method

After collecting the incoming raw water, divided the sample into 5 samples, and treated chlorine dioxide (ClO ₂ ) with 0.2mg / L, 0.4mg / L, 0.6mg / L, and 0.8mg / L, respectively. Each sample was evaluated by smelling directly at the site and measuring the degree of odor.

Table-2 Pollution Degree of Samples (Direct Sensory Method)

                                                               (Unit: mg / L)

division Influent Fresh sludge Remarks BOD 130 3100 COD 75 1800 SS 95 3700 T-N 31 4500 stink 4 degrees (strong odor) 5 degrees (very strong odor) Direct sensory method (regulation standard: 2 degrees or less)

2) Experiment result

Table-3 Odor after chlorine dioxide treatment (direct functional method)

division Odor level before ClO ₂ treatment Odor after before ClO ₂ treatment Remarks 0.4mg / L 0.6mg / L 0.8mg / L 1.0mg / L S-1 4 4 3 3 One S-2 3 3 3 2 One S-3 3 3 3 2 One S-4 4 4 3 2 One Average 3.5 3.5 3 2 One Odor Very strong odor (4) Strong Odor (3) Regular odor (2) Detect (1) Odorless (0)

As can be seen from the above experimental data, when the chlorine dioxide injection rate is 0.4, the odor can be felt 3 degrees strong, and when 0.8 mg / L is injected, the odor is hardly detected and more than 1.0 mg / L. When injected, you can see the result that does not smell.

The present invention has the effect of reducing the initial investment cost, glass management of the odor removal method, by activating chlorine dioxide generated directly into the odor generating source, fundamentally remove odorous substances, easy storage, and provides a odor remover without secondary pollution. .

In addition, the chlorine dioxide used in the present application is used locally in the parcel water supply line or the reaction tank to remove the air bubbles generated in the odor source reaction tank in order to enhance the odor removal effect extensively throughout the contents without remaining only in partial effects. By applying the chlorine dioxide solution supply line to the acid facility line for supplying air, the ejector principle is generated by the generation of the differential pressure between the parcel water supply line (or air supply line) and the chlorine dioxide solution supply line that are transported at high pressure. The chlorine dioxide (ClO ₂ ) solution is injected into the odor generating source by using a defoaming device (or an acid generator) to maximize the use effect of chlorine dioxide.

Claims (3)

In the odor removal device for reducing odor by using chlorine dioxide (ClO ₂ ) in industrial sites having various odor generating sources, Sodium chlorite (NaClO ₂ ) or sodium hypochlorite (NaClO), etc. include a chlorine dioxide generator that generates chlorine dioxide (ClO ₂ ) through a chemical reaction with hydrochloric acid (HCl), Means for obtaining the chlorine dioxide (ClO ₂ ) concentrate using an ejector block to concentrate the generated chlorine dioxide (ClO ₂ ) in water, Means for rapidly transferring the chlorine dioxide (ClO ₂ ) solution through a storage tank having a circular screw or stepped flow to induce a rapid flow so that the chlorine dioxide produced first is discharged first, The odor removal device using chlorine dioxide (ClO ₂ ) comprising a means for grafting the chlorine dioxide solution supply line to the existing facilities of the odor generating source reaction tank and injection into the odor generating source. The method of claim 1, Chlorine dioxide (ClO _2), the pressure in generator (differential pressure, negative pressure) sensor is provided characterized by controlling the rate of water supply to stabilize the chlorine dioxide (ClO ₂₎ generating yield the zoom depending on the amount of generation of discrete flame small (ClO ₂₎ Deodorizing apparatus using chlorine dioxide (ClO ₂ ) to. The method of claim 1, Chlorine dioxide (ClO ₂ ) storage tank is formed by using a stainless steel, synthetic resin or synthetic fiber skew or stepwise to form a structure in which the incoming fluid is sequentially discharged using chlorine dioxide (ClO ₂ ) Deodorizer.

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