KR20050047045A - Hybrid processing method for deodorization and the system therefor adopted real-time controller - Google Patents

Abstract

The present invention relates to a hybrid odor purifying treatment method and a system 100 in which selective adsorption reaction and photolysis reaction are combined to maintain complementarity, and more particularly, odor collecting means 10 and blower apparatus 13. Odor contaminants introduced by) are adsorbed at high concentration by a selective adsorbent that can selectively adsorb ammonia, methyl mercaptan, hydrogen sulfide, volatile organic compounds (VOC), etc. Odor pollutants which have not been removed or desorbed from the adsorbent by concentration gradient and atmospheric diffusion are secondarily environmentally friendly hybrid odor treatment methods and systems that completely decompose into harmless and odorless gases in photocatalytic / ultraviolet photolysis reaction zones.

The odor treatment method of the present invention is a composite technology combining photocatalytic photolysis technology with excellent initial reaction rate to odor gas and relatively low odor but excellent odor removal ability. Self-renewal is provided by the photoreaction zone, buffering the variation.

In order to further improve the hybrid reaction mechanism, the present invention provides a odor control system in which a semiconductor odor sensor for detecting odor gas is installed before, after, and inside the odor treatment system to collect information in real time. To optimize.

According to the present invention, it is possible to operate permanently using a new concept of continuous adsorption / desorption / photolysis hybrid processing method, rather than simple photolysis or adsorption effect method, and energy saving type by controlling energy required for operation using semiconductor odor sensor. By constructing the system, it is possible to considerably reduce the restriction of factors affecting the operation operation such as the concentration of odor gas and the treatment capacity, and also significantly alleviates the restrictions on location and mobility in facilities and operations. · Efficiently remove and decompose airborne pollutants including floating bacteria.

Description

Hybrid processing method for deodorization and the system therefor adopted real-time controller

The present invention relates to a hybrid odor purifying treatment method and system 100 according to the combination of the selective adsorption reaction and the photolysis reaction to complement each other,

More specifically, the malodor pollutant introduced by the malodor collecting means 10 and the blower 13 is primarily a selective adsorbent capable of selectively adsorbing ammonia, methyl mercaptan, hydrogen sulfide, volatile organic compounds, and the like (16). (17) (18) (19) are adsorbed and removed at high concentrations, and odor pollutants that are physically desorbed from the adsorbent due to the concentration gradient that has not been adsorbed by the adsorbent or are sharply formed are secondary to photocatalyst / ultraviolet rays. It is an environmentally friendly hybrid odor treatment method and system 100 that completely decomposes into a harmless and odorless gas in the photolysis reaction section (2).

According to the present invention, the semiconductor odor sensor 25, which is a odor control means, is provided inside, before, and after the odor removal system 100, and collects and analyzes operating variable information in real time, and uses the preconfigured control program. It is characterized by optimal control.

Recently, with advanced environmental regulations in advanced countries, environmental technology has become a key element of national competitiveness in the 21st century, and the development and commercialization of advanced environmental technology in response to this is becoming more important than ever. In addition, due to international pressures to protect the environment and strengthening environmental regulations by country, the environmental market is expected to rise rapidly in the coming decades.

The present invention relates to an odor control technology for removing odor pollutants discharged from industrial and living environments, such as the odor reduction section, among the environmental fields, and to operate the odor removal system optimally.

The odor removal technology currently applied to remove odors in industry can be largely divided into physical and chemical treatment methods and biological treatment methods, and it is difficult to say that all odors are completely processed, and in general, they require a low operating cost. The single treatment method using the odor control technique is preferred. However, when operating the odor removal system, the amount of odor gas, concentration, and composition are often changed depending on the operating conditions of the odor discharge facility and prevention facility. Enormous reality is an inevitable reality. In addition, since most cases do not obtain satisfactory treatment effects, efforts are being made in advanced countries such as Japan to achieve a stable odor removal effect by applying a combination of two or more odor removal technologies.

In addition, since the existing odor removal system and complex technology require a lot of facility cost and maintenance cost, there is a limit in establishing or systematically managing the odor removal system in economically poor domestic industries. Therefore, the necessity of developing a new odor removal system suitable for domestic industrial conditions is increasing.

The classification of deodorization technology that can remove odorous substances can be largely classified into physical, chemical and biological treatment methods, and the related technologies are classified and detailed in Table 1. Among these technologies, it is the most economical by comprehensively reviewing various data such as composition, concentration, temperature, air volume, humidity, working time, process change, working route, installation area, secondary pollutant, and fuel used in the odor generation. Select an effective and effective odor removal system.

In addition to the odor removal techniques shown in Table 1, it can be classified into concealment, separation, and destruction techniques of odorous substances, but concealment and separation techniques are somewhat unreasonable as ultimately treatment of odorous substances.

TABLE 1

The major odor removal technologies at home and abroad are as follows.

The biofilter is suitable for low concentration and high air volume, and has a merit of low operating cost and no secondary pollution since it uses microorganisms. However, there is a limit to the high temperature and high concentration of gas treatment, and the microorganisms are difficult to grow, which is subject to many limitations depending on the environment. On the other hand, the combustion method can be applied at high temperature and high concentration, but requires a relatively high initial investment cost compared to biofilters. In addition, when the concentration of the processing gas is low concentration or intermittent, there is a disadvantage in that the economic efficiency is much lower than the technology such as biofilters.

The soil deodorization system also has the advantages and disadvantages of simple equipment and low initial investment cost but wide installation area and unsuitable for high concentration and high temperature gas treatment.

Recently, the most commonly used methods are odor control technologies such as regenerative combustion, catalytic combustion, and biofilters. In the past, the adsorption method using activated carbon was most frequently used, but the use of adsorbents such as activated carbon was gradually reduced due to the high replacement cost. Since then, the use of simple direct combustion method has been applied in many sites in terms of operation management, and the regenerative combustion method and catalytic combustion method, which have improved the thermal efficiency of the direct combustion method, have also been in the spotlight. However, in the catalytic combustion method, the use of the catalyst is decreasing due to the excessive cost of catalyst replacement. This is because the catalyst technology resistant to catalyst poison has not yet gained the trust of the field.

In an attempt to solve the problem of the odor removal method, a photocatalyst photocatalytic reaction and / or a method using an adsorptive photocatalyst filter have been invented.

Among these technologies, Korean Patent Registration No. 0478803 describes an air purification treatment method and apparatus including a odor using a photocatalytic photoreaction of a fluidized photocatalyst carrier and an ultraviolet lamp, and Korean Patent Publication No. 2004-0102487 discloses a photocatalyst coating. An air purifying apparatus including a fluidized bed photochemical reactor using a supported carrier and a film type photochemical reactor using an adsorptive photocatalyst filter and a use thereof are described.

As described above, it is difficult to consider that the specific technology is the best among the odor removal systems introduced at home and abroad, and it is possible to remove odor most appropriate to the site environment by comprehensively analyzing the concentration, temperature, and air volume of the processing gas that is applied to the deodorization technology It is important to choose a technique.

Therefore, the present invention has been proposed to solve the above problems according to the prior art,

An object of the present invention is to provide a odor purification treatment method and apparatus for removing odor pollutants contained in the atmosphere by using a selective adsorbent and photocatalytic photolysis reaction to obtain clean air.

Characteristic of the purification method of the hybrid odor removing system according to the present invention for achieving the above object,

Rather than a simple single odor treatment method, even if the load fluctuates severely, the odor material is stably processed at high efficiency.

It is physically desorbed by adsorption method to selectively adsorb high concentrations of ammonia, mercaptan, hydrogen sulfide, VOC, and odor pollutant which could not be removed by adsorption method and concentration gradient formed sharply from fixed adsorption layer. In a hybrid type odor removal method incorporating an active oxidation process using a photocatalytic photolysis method capable of completely decomposing odor pollutants into a harmless and odorless gas,

The semiconductor odor sensor 25 is provided before, after, and inside the odor removal system 100 to collect information on operating variables and transmit the information to the main control means 200, thereby operating the odor control system optimally. It is characterized in that it provides a function to deliver a call, alarm means 26 or a message to the administrator when a defect occurs.

First, high concentrations of odor pollutants, which always contain the possibility of load fluctuations introduced into the odor removal system 100, are removed by more than half by the selective adsorption layers 16, 17, 18 and 19. Looking at the process in detail as follows.

In the adsorption process, the mass exchange process to purify gaseous contaminants is carried out in the solid phase, and these adsorption molecules are condensed on the adsorption surface or lose physical energy (Van der Waals) or chemical bonds generated by The gas is removed by

Two well known adsorption mechanisms are physical adsorption and chemical adsorption. Physical adsorption has a weak binding force to the solids of the gas molecules. The binding energy is similar to the attraction between liquid molecules. The adsorption process is exothermic and the heat of adsorption is usually slightly higher than the heat of vaporization of the adsorbate. The force that attracts gas molecules to the solid is easily lost when the temperature increases or the pressure decreases. These principles are used to regenerate adsorbents.

In the use of the adsorption method for odor gas treatment, the first thing to be determined is, of course, the selection of the target adsorbent. Of course, the selection of the appropriate adsorbent should be determined by securing various data and the engineer's judgment regarding the characteristics and the applicability of the adsorbent.The first important characteristic of the adsorbent is the adsorption capacity of the adsorbent as the adsorption capacity. isotherm).

The factors that most influence the adsorption capacity are the specific surface area of the adsorbent, the size and distribution of the pores, and the adsorption affinity between the malodorous gas to be removed or recovered and the surface of the adsorbent used. These effects will vary depending on the odor concentration in the atmosphere and the operating temperature.

The next property to be considered is Selectivity.

Factors affecting the selectivity are the size and distribution of the pores and the nature of the adsorbent surface. In particular, activated carbon is currently the most used adsorbent for the treatment of odor gas, and the most important influence on the pore size, distribution and surface properties of activated carbon is in the raw material of activated carbon and its manufacturing process.

On the other hand, the adsorption rate also becomes an important characteristic in the adsorption process. Most of the adsorption rate is governed by the movement through the film formed on the adsorbent surface and the diffusion process inside the pores. Therefore, it can be said that the size of the adsorbent, the flow rate and the size of the pores have a great influence on the adsorption rate, and the adsorption rate is more important than the adsorption capacity in the actual process.

As the adsorbent, activated carbon, silica gel, activated alumina, ion exchange resin, activated clay, bone char, synthetic zeolite and the like are mainly used.

Table 2 shows the selectivity of the various adsorbents.

TABLE 2

In order to better understand the adsorption phenomenon, it is necessary to examine the pore structure and the pore distribution, which are shown in FIG. 3a.

When looking at the pore diameter classification, DUBININ suggests micropores less than 20Å, transition pores (or meso pores) of 20 ~ 200Å, and macropores of 200Å or more, but IUPAC (International Union of Pure and applied Chemistry) Micro Pore with diameter of 20Å or less, Meso Pore with 20 ~ 500Å, and Macro Pore with 500Å or more are classified.

Since the surface of general activated carbon is nonpolar and the adsorption force is simply physical adsorption by van der Waals forces, it does not have sufficient adsorption to low boiling point components such as hydrogen sulfide and NH ₃ .

Therefore, activated carbon for removing odor gas having selective adsorption on specific components by chemically modifying activated carbon or impregnating chemicals has been widely used.

Alkali-impregnated activated carbon in which non-volatile inorganic caustic soda (NaOH) or sodium carbonate (NaCO ₃ ) is impregnated with activated carbon is called activated carbon for acid gas and acidic gases such as hydrogen sulfide (H ₂ S) or methyl mecaptan (CH ₃ SH) Oxidized by contact with and held in adsorption with elemental sulfur or sulfuric acid.

[Formula 1]

[Formula 2]

In addition, it is converted into methyl disulfide by catalytic oxidation with methylmecaptan.

[Formula 3]

However, when H ₂ S or methylmecaptan are removed under the coexistence of basic gas (mainly NH ₃ ), a halogen compound (mainly F) is attached to act as a catalyst to oxidize and adsorb.

Acid-impregnated activated carbon prepared by the addition of sulfuric acid (H ₂ SO ₄ ), which is a non-volatile inorganic acid, or phosphoric acid (H ₃ PO ₄ ), which is a weak acid, is called activated carbon for basic gas, and ammonia gas (NH ₃ ) or trimethylamine [(CH ₃ ) an odor component such as ₃ N] is not adsorbed ammonium salt, an amine salt.

[Formula 4]

[Formula 5]

Activated carbon for neutral gas surface-treated with halogen compounds (mainly F) is slack kit by oxidatively adsorbing methyl sulfide [(CH ₃ ) ₂ S], methyl disulfide [(CH ₃ ) ₂ S ₂ ] or hydrocarbons (CH ₄ ). I convert to sulfonic acid.

[Formula 6]

[Formula 7]

Looking at the odor gas adsorption characteristics by each impregnated activated carbon,

Activated carbon for acid gas selectively adsorbs hydrogen sulfide and methyl mecaptan. For basic gas, trimethylamine, monomethylamine and ammonia are selectively adsorbed, while neutral carbon activated carbon mainly adsorbs methyl disulfide and methyl sulfide. Has

In the present invention, in consideration of the applicability of the field, the non-woven fabric impregnated with the above-described functional group-supported activated carbon (Activated Carbon) in a polymer foam (Poly) including polyurethane to have a selective adsorption capacity.

The second technical problem to be achieved in the present invention is a problem of preferably applying a new photocatalyst material, which has recently been in the spotlight, to the odor removal system.

As a technology that can replace the existing environmental treatment process, many researches and devices for advanced oxidation method have been devised.

The OH radicals generated by the advanced oxidation process react very quickly and evenly with almost all environmental pollutants including organics / odorous gases, which can be useful in the oxidative decomposition of hardly degradable pollutants.

Among advanced oxidation methods, the oxidation system using semiconductor metal compound such as titanium dioxide (TiO ₂ ) which is harmless to the human body and chemically stable as a photocatalyst is capable of treating odors and suspended bacteria which are difficult to process by the prior art. Attention has recently been paid to the efficient removal of degradable compounds, especially odors and VOCs.

In a chemical reaction, a catalyst plays a role such as changing the reaction rate or initiating the reaction without changing itself. Therefore, photocatalyst is a kind of catalyst, which means that catalysis takes place with light energy.

Photocatalysts have the advantages of being able to safely and easily decompose various chemical substances only by the use of light energy and have characteristics such as antibacterial, sterilization and super hydrophilicity.

The environmental treatment method using a photocatalyst has advantages such as easy operation and operation of the process and easy application to the environmental treatment process currently used.

Therefore, the application field of the photocatalyst process having such an advantage can be said to be very broad.

The mechanism of photocatalytic oxidation by titanium dioxide (TiO ₂ ) and ultraviolet (UV) in the air and in aqueous solution is shown. The band gap energy (= 3.2) is applied to titanium dioxide (TiO ₂ ), the ultraviolet light emitted from the ultraviolet lamp 21. Supplying higher light energy (wavelength <387.5nm) leads to the emission of electrons from the valence band of titanium dioxide, which is filled with electrons, and to the conduction band.

At the same time, positive holes are produced in the valence band of titanium dioxide. The excited electrons are superoxide radical (O2 ^- ·) to react with the electron acceptor oxygen is adsorbed onto the surface of the catalyst to produce the hydroxyl radical (OH ·) generate and with superoxlde radical has high oxidizing power reacts with the water / water vapor molecules to do,

At the same time, holes generated on the surface of TiO ₂ react with water molecules or hydroxyl ions adsorbed on the catalyst to produce hydroxyl radicals, or directly react with organic compounds to decompose organic compounds.

Both electrons and holes generated in photocatalysts produce OH radicals through oxidation and reduction reactions, and the OH radicals produced in this way react with pollutants (ionic species and molecular species) in the air and water in various forms to decompose. Proceeds.

The OH radicals generated in the photocatalyst through the above process are completely decomposed to remove the organic compounds in the atmosphere with CO ₂ and H ₂ O as shown in Formula 8, and as shown in Formula 9, odors in the atmosphere Contaminants are decomposed and eliminated as odorless and odorless gases by OH radicals.As shown in Formula 10, suspended bacteria present in the atmosphere are killed by changes in genes (DNA) due to OH radicals and TiO ₂ / ultraviolet rays. This series of photocatalytic oxidation mechanisms is shown in Figure 4a.

[Formula 8]

[Formula 9]

[Formula 10]

However, if the expensive TiO ₂ photocatalyst is used in the form of powder directly in the photocatalytic photolysis reaction, TiO ₂ microparticles having a particle size of several μm to several nm are dispersed in the dust state, thereby separating and recovering TiO ₂ again. Problems on the

In order to solve the above problems, rather than directly using a titanium dioxide photocatalyst in the form of powder, to obtain the maximum reaction efficiency by surface coating and fixing to a substrate having a certain particle size and density so as not to flow out of the odor removal system, a simple filling stationary phase It is preferable to adopt a fluidization method rather than a fluidization method.

According to the present invention, the two odor removal methods, that is, the selective adsorption method and the photocatalytic photolysis reaction method can be said to be a complementary organic relationship,

High concentrations of odorous substances with the possibility of load fluctuations are primarily adsorbed and removed from the adsorption layer to reduce the load of the photocatalytic photoreaction zone to perform buffering of the entire system.

In the adsorption process, when the adsorbent reaches saturation of the adsorption capacity, regeneration or replacement is required.

The photocatalytic photoreaction forms a sharp concentration gradient between the two reaction zones before the adsorbent reaches its saturation capacity, gradually desorbs the odor pollutant adsorbed by the adsorbent, and decomposes it into harmless and odorless gas by photoreaction. Gives regeneration ability.

Finally, the problem to be achieved in the present invention is a problem of efficiently operating, maintaining and managing the hybrid odor removal system in which the adsorption method and the photocatalytic reaction method described above are combined under optimized operating conditions.

In order to solve the above problems in the present invention, a semiconductor odor sensor was adopted.

It is a real-time controlled system that operates the odor removal system under optimum operating conditions by collecting and analyzing information such as concentration, flow rate, pressure, temperature and humidity of odor gas flowing into the hybrid odor removal system in real time.

Sensor is a general term for a device that senses the physical and chemical quantities of a substance and converts it into electrical, mechanical, and optical signals.The demand for sensors increases exponentially as the industry develops. The field is also expanding.

In particular, semiconductor ceramic sensors using inorganic materials are most commonly used as sensing materials (materials), which are the core materials among various sensors. Firstly, ceramics are used when many sensors are used in harsh conditions such as high temperature, high humidity, and a reactive or corrosive atmosphere. Is the most reliable material. Second, the electromagnetic, photochemical, thermal, and mechanical properties of a material can generally be controlled by changing its composition, especially because the properties can be controlled by controlling the microstructure as well as the composition of ceramics. . As such, semiconductor sensors have a variety of component combinations in addition to structural and form diversity, and have been recently researched as an optimal sensor material for environmental pollutant gases (CO ₂ , NOx, SOx, etc.) that have been difficult to detect until now. .

At present, the measurement of air pollutants is almost done in the spectrometer-based analyzer, but it is impossible to access the general market due to the disadvantage of costly analysis procedure and maintenance. However, the semiconductor sensor is widely used for atmospheric environment measurement and process control because it has the advantages of simple structure, low cost by mass production by automation, easy maintenance and fast response speed.

Therefore, with the establishment of the base technology, it can be used to detect explosive gas, toxic gas, environmental gas, process gas, medical, air conditioning facilities, cooking control, process control such as process control, environmental measurement such as emission gas measurement and air quality measurement. It has the characteristics to develop applied technology, so it is a research field with great potential for future development.

In general, most of the semiconductor gas detection devices that have been put to practical use are sintered bodies. While the sintered body is easy to manufacture and has high response characteristics, it is difficult to fabricate precise devices, and thus the reproducibility of measured values is poor. That is, it can be used for qualitative detection, but it is difficult to produce quantitative results.

The oxide semiconductor applied to the semiconductor gas sensor is composed of grains and grain boundaries when viewed in a microstructure, and current flows through the grain boundaries. When semiconductor crystals are exposed to high temperatures of several hundred degrees Celsius in the atmosphere, oxygen in the atmosphere adsorbs the load charges on the surface of the semiconductor crystals, thereby creating potential barriers due to adsorbed oxygen at the grain boundaries of the semiconductor microcrystals, which impedes carrier movement do. This causes an increase in the sensor resistance, and if the reduction of adsorbed oxygen by the reducing gas such as combustible gas and the chemical adsorption of the detection gas itself to the sensor surface occur, the electrical potential decreases as the potential barrier is lowered. This aspect is shown in Figure 6a. By using this principle, gaseous substances such as hydrogen, carbon monoxide, hydrocarbons, alcohols, and malodorous substances are detected.

The technical problem to be achieved in the present invention is that the two odor removal methods of the adsorption method and the photocatalytic reaction method described above are preferably configured to maintain complementarity, thereby giving the self-regenerating ability of the adsorbent and stably stinks even under sensitive load fluctuations. Completes the hybrid odor removal system that can be removed,

It is a technical task to efficiently operate, maintain, and manage the hybrid hybrid odor removal system using optimized odor sensors.

The term 'hybrid' used in the present invention refers to a method of achieving one goal by combining two or more complementary methods, and the term 'real time controlled odor purification apparatus' refers to odors in the atmosphere. It is an artificial odor control system that is provided with a semiconductor odor sensor that can detect operating variables that change from time to time. The present invention is characterized by the above combined function.

Hereinafter, with reference to the accompanying drawings, a preferred embodiment of the hybrid type real-time control type malodor purification treatment method and apparatus according to the present invention will be described.

1 is a schematic configuration diagram of a hybrid odor removing system according to the present invention; 2 shows schematic schematic diagrams of a real-time malodor control system according to the present invention.

1 and 2, the malodor purifying apparatus 100 is divided into a selective adsorption reaction section (1) and a photocatalyst photolysis reaction section (2), and odor purification by information collected by sensing operating variables. Control systems 25, 26, 27, and 200 are provided to efficiently operate the treatment apparatus, and odor collecting and inflow means 10, 12 for introducing odor pollutants into the purification treatment apparatus. (13) (14), outlet means (24) for discharging the purified air to the outside, reactor separation means (20) and fixing means for facilitating the replacement of the environmental material of the malodor purification apparatus and the maintenance and repair of the apparatus. 15 are provided respectively.

Referring to the purification method of the odor purification apparatus 100 according to the present invention configured as described above are as follows.

First, harmful air in the air containing odor pollutants such as ammonia, mercaptans, hydrogen sulfide, aldehydes, volatile organic compounds (VOC), and harmful bacteria is collected by the mechanical force of the blower (13). It is collected by the malodorous substance inlet 10 which is a means, and is introduced into the malodor purifying apparatus 100 through the moving pipe 12 and the inlet means 14 which are the malodorous substance moving means. At this time, the dust present in the odor pollutant is first filtered by the dust filter 11 to minimize the defect rate of the odor removing device 100 and mechanical and electrical equipment (13) (25) (27) and to improve the stability It serves to ensure, the dust filter 11 is installed to facilitate the cleaning and replacement.

Odor contaminants introduced into the odor purifying apparatus 100 are selectively adsorbed and removed by the adsorption reaction section 1 at a high concentration, and are not removed by the adsorbent, or have a weak bonding force (for example, Odor contaminants adsorbed by physical adsorption and then desorbed by vivid odor farming tools between the two reaction zones formed by the photocatalytic photoreaction are purged of harmless and odorless gas by the next step, photocatalytic photoreaction section (2). Is processed.

The selective adsorbent constituting the adsorption reaction section (1) is manufactured to have a selective adsorption capacity for specific odor components by chemically modifying the surface of activated carbon or zeolite or by adhering chemicals.

Acid-impregnated activated carbon (16) prepared by adding non-volatile inorganic acid sulfuric acid (H ₂ SO ₄ ) or weak acid phosphoric acid (H ₃ PO ₄ ) to general activated carbon is called activated carbon for basic gas, and it is called ammonia gas (NH ₃ ) or trimethyl. Selectively adsorbs malodorous components such as amines [(CH ₃ ) ₃ N],

Alkali-impregnated activated carbon (17) (18) in which activated carbon is impregnated with sodium carbonate (NaOH) or sodium carbonate (NaCO ₃ ), which is activated carbon, is called activated carbon for acid gas, and hydrogen sulfide (H ₂ S) or methyl mercaptan (CH ₃ SH). Selective catalytic oxidation of acid gases such as) to adsorb elemental sulfur or sulfuric acid, while halogen compounds (primarily F) are impregnated to remove H ₂ S or methylmecaptan in the presence of basic gas (mainly NH ₃ ). Oxidation and adsorption by acting as a catalyst,

Activated carbon for neutral gas (19) prepared by surface treatment with a halogen compound (mainly F) is methyl sulfide [(CH ₃ ) ₂ S], methyl disulfide [(CH ₃ ) ₂ S ₂ ], and hydrocarbons (CH ₄ ). And the ability to selectively adsorb volatile organic compounds (VOCs).

To summarize the functions of the selective adsorbent described above,

Activated carbon 18 for acid gas selectively adsorbs hydrogen sulfide and methyl mercaptan, while activated carbon 17 for basic gas selectively adsorbs trimethylamine, monomethylamine and ammonia, while activated carbon 19 for neutral gas is mainly adsorbed. It has chemical properties to selectively adsorb volatile organic compounds, methyl disulfide and methyl sulfide.

In the present invention, in consideration of the applicability of the field, the non-woven fabric impregnated with the above-described functional group-supported activated carbon (Polymer), including the polyurethane (Form) to adopt a non-woven fabric to have a selective adsorption capacity, An illustration of the selective adsorbent according to the invention is shown in Figure 3b.

If the form of the selective adsorbent is manufactured in the form of non-woven fabric, not in powder form, as described above, the type and amount of the adsorbent can be easily selected according to the concentration distribution of each odor item at each odor discharge facility site and applied to the odor treatment device. In addition, there is an advantage that it is easy to replace the adsorbent.

In the odor purification treatment method of the next step, in the present invention, a photocatalytic photolysis reaction mechanism capable of purifying odor pollutants and harmful gases with a harmless and odorless gas was applied, which is illustrated in FIG. 4A.

The photocatalytic photolysis reaction section 2 is composed of a fluidized photocatalyst carrier 30 to a transparent photocatalyst carrier 31 to which a titanium dioxide (TiO ₂ ) photocatalyst 30 "is coated and cured on a substrate 30 'and an activation energy for the photocatalyst carrier. The photocatalyst is composed of an ultraviolet lamp 21 serving as a light source capable of supplying (hυ), and the photocatalyst is coated to cause photoreaction while preventing the photocatalyst carrier 30, 31 from leaving the photocatalytic reaction section 2. The photocatalyst filter layer 22 and the stencil 15 as a fixed medium are provided at the upper and lower ends of the photocatalytic photolysis reaction section 2, respectively.

When the expensive titanium dioxide (TiO ₂ ) photocatalyst is used in the form of powder directly in the photocatalytic decomposition reaction, TiO ₂ fine particles having a particle size of several μm to several nm are dispersed in the dust state, so TiO ₂ is separated and recovered again. There is a problem in the process to do,

In order to solve the above problems, surface coating and fixation on a carrier having a certain particle size and density so as not to flow out of the photocatalytic photolysis reaction section 2 of the odor purifying apparatus 100, rather than using a titanium dioxide photocatalyst in the form of a powder directly. In order to obtain the maximum reaction efficiency, it is reasonable to adopt a fluidization method rather than a simple filling stationary bed.

In the substrate to the carrier 30 'on which the titanium dioxide (TiO ₂ ) photocatalyst is coated,

As an organic and inorganic compound such as expandable polystyrene (styrofoam) having a density of 0.01 to 0.10 g / cm ³ that can be easily fluidized by only the air flow generated by the blower 13,

The particle size is about 3 ~ 20mm, which is optimal for fluidization and field applicability conditions. Spray the photocatalyst liquid in sol state that can be coated on the carrier 30 'even at room temperature. By coating in the same manner as the method or immersion method to cure at room temperature or medium temperature can be prepared fluidized photocatalyst carrier 30,

It is possible to obtain a photocatalyst carrier having a high content of titanium dioxide (TiO ₂ ) while increasing the number of coatings.

A cross-sectional view of the titanium dioxide (TiO ₂ ) fluidized photocatalyst carrier 30 according to the present invention is shown in FIG. 4B, where the titanium dioxide (TiO ₂ ) photocatalyst 30 ″ is coated on the fluidized substrate 30 ′. have.

Photocatalytic photoreaction is first initiated photocatalytic reaction by odor pollutants are adsorbed on the photocatalyst surface and then irradiated with light source

Foamed polystyrene (styrofoam), which is used as a substrate for the fluidized photocatalyst carrier 30, has not only an ability to adsorb odor gas but also an ability to absorb odor gas, thereby attracting malodorous harmful gases to the surface of the photocatalyst to fully serve as an initiator of the photocatalytic reaction. In view of the photocatalyst side, the fluidized photocatalyst carrier 30 used in the present invention may be referred to as a hybrid photocatalyst which is recently studied.

In addition, the application of styrofoam may have a large economic and industrial ripple effect in terms of recycling waste resources.

In the present invention, to obtain a reaction efficiency similar to that of the photocatalytic photolysis reaction apparatus in the form of powder, and to visually pursue the interior effect, it was intended to apply a fluidized bed reactor which is significantly superior in mixing and transfer phenomena compared to other reactors.

The fluidized photocatalyst carrier 30 prevents scale phenomenon such as contamination of the surface of the lamp during frequent collision with the ultraviolet lamp 21 while being actively fluidized in the photocatalytic reaction section 2 of the odor purifying treatment device 100. Also done.

In the case of inevitable application of the fluidization reactor in the field conditions or the operation of the process, in order to achieve the best photocatalytic efficiency in the fixed bed reactor, the photocatalyst is coated and fixed on the transparent film substrate through which ultraviolet rays can be transmitted to a certain extent in the same manner as described above. ),

Since the ultraviolet light emitted from the ultraviolet lamp 21 is uniformly radiated to the entire photocatalyst while passing through each transparent photocatalyst carrier 31 to a certain extent, the maximum photocatalytic efficiency can be obtained in the fixed bed reactor.

Exemplary diagrams of the fluidized photocatalyst carrier coated on the surface of titanium dioxide (TiO ₂ ) according to the present invention described above, and an exemplary diagram of the transparent photocatalyst carrier are shown in FIGS. 4C and 4D, respectively.

Pollutants including odors and volatile organic compounds in the air that could not be adsorbed or removed by the selective adsorption reaction section (1) of the odor purifying treatment apparatus (100) or desorbed from the adsorbent and introduced into the photocatalytic photolysis reaction section (2). Are actively brought into contact with the photocatalyst carrier 30 which is fluidized by the airflow of air generated from the blower 13.

Accordingly, the fluidized photocatalyst carrier 30 is higher than the band gap energy (3.2 eV) of the photocatalyst used as the activation energy from the ultraviolet lamp 21 provided horizontally in the center of the photocatalytic photolysis reaction section 2. It is irradiated with light energy (λ <387.5nm) and causes photochemical action to decompose hard-degradable pollutants including odors contained in air.

Here, an electronic ballast (not shown in the drawing) is provided for the stable power supply of the ultraviolet lamp 21.

In particular, the ultraviolet lamp 21 used as a light source is a black light blue (BLB) lamp that emits a UV-A wavelength band of 315 nm to 400 nm having the best wavelength absorption band of titanium dioxide (TiO ₂ ) photocatalysts developed to date.

A dark blue filter glass that absorbs visible light and efficiently transmits ultraviolet rays in the wavelength band, and phosphors having peaks of emission spectra around 360 nm are used.

The black light blue lamp used as a photochemical light source has two types, each emitting 352 nm and 368 nm as a main peak, and the present invention is irrelevant to which one is applied. The wavelength region diagram and the dominant wavelength can be seen in FIG. 5.

According to the present invention, the photolysis reaction using titanium dioxide photocatalyst (TiO ₂ ) and ultraviolet (UV) not only decomposes pollutants such as odors and VOCs into harmless and odorless gases, but also pathogenic bacteria, Bacillus bacteria, There is a function to kill by manipulating the gene (DNA) of harmful bacteria such as mold or oxidizing and deactivating molecular species. When the present invention is applied to facilities that require extremely air sterilization such as pigs, barns, hospitals and multi-use facilities, effective.

According to the present invention, the hybrid odor removal method, that is, the selective adsorption method and the photocatalytic photolysis reaction method can be said to be complementary organic relationship,

High concentrations of odorous substances with the possibility of load variation are primarily adsorbed and removed in the adsorption reaction section (1) to reduce the load of the photocatalytic photoreaction section (2) to perform a buffering function of the whole system.

In the adsorption process, when the adsorbent reaches saturation of the adsorption capacity, it is required to be regenerated (virtually impossible in the field) or to be replaced.

Photocatalytic photoreaction forms a sharp concentration gradient between the photocatalytic photoreaction section (2) and the adsorption reaction section (1) before the adsorbent reaches saturation of the adsorbent, thereby slowly desorbing the malodor pollutants adsorbed by the adsorbent. Deodorized pollutants desorbed are decomposed into harmless and odorless gases in the photocatalyst photoreaction section (2).

The photocatalyst photoreaction section 2 serves to sustain the adsorption capacity of the adsorbent by imparting the self regeneration capacity of the adsorbent in the same manner as described above.

Finally, the problem to be solved by the present invention is a problem of efficiently operating, maintaining and managing the hybrid odor removal system 100 in which the adsorption method and the photocatalytic reaction method described above are combined under optimized operating conditions.

In order to solve the above problems in the present invention, a semiconductor odor sensor was adopted.

The semiconductor sensor 25 is simple in structure, mass-produced by automation, inexpensive, easy to maintain, and fast in response, and is easy for atmospheric environment measurement and process control.

In some cases, a semiconductor sensor requires an amplifier, an analog-to-digital converter, a data logging system, or the like (not shown in the drawing).

The information collected and transmitted in the above manner is managed by a monitoring system and a computer, and can be remotely controlled by a complete control program.

It is a real-time odor control system that operates the odor removal system under optimum operating conditions by collecting and analyzing information such as concentration, flow rate, pressure, temperature, and humidity of the odor gas flowing into the hybrid odor removal system 100 in real time.

The measurement / analysis system, which is the basis of the control technology, consists of a gas sensor, a temperature sensor, a pressure sensor, a humidity sensor, etc., and is installed before, after, and in the reaction unit of the odor removing system to control the operating variables in real time. Based on the collected information, the optimal operating conditions of the odor removal system can be automatically adjusted by a preconfigured program to reduce power costs due to excessive operation and alarm and call functions in the event of a fault (26 It provides a total solution that can be done.

If the above-mentioned total solution is established, not only the limit of the factors affecting the operation operation such as the concentration of odor gas and the treatment capacity can be significantly reduced, but also the restrictions on the place and mobility can be substantially alleviated in the facility and operation. have.

An exemplary view of a semiconductor odor sensor according to the present invention described above is shown in FIG. 6B, and an embodiment of a real-time odor control system according to the present invention is shown in FIG. 6C.

Referring to the operation of the hybrid type malodor purifying treatment method and the malodor purifying apparatus according to the configuration described above as follows.

Figure 7a is an illustration of a hybrid odor removing system and performance test process according to the present invention.

(a) a hybrid odor removal system,

The size of the device is 400mm × 400mm × 1,200mm in height, and the selective adsorption reaction section consists of 6 sheets of selective adsorbent 400mm × 400mm × 5mm thick, and the photocatalytic photoreaction section is 400mm × 400mm × height It was composed of 3 sets of modules of 200mm, and the capacity of blower to determine the odor treatment capacity was 4.3m ³ / min.

(b) to produce a transverse vertical 1,000mm × 1,000mm × height 1,500mm size, that is a closed system (Closed System) of 1.5m ³ to scale the odor emission facility model, batch with respect to the typical ammonia (NH ₃₎ of the odorant ( Batch) performance tests and continuous performance tests were conducted.

(c) First, 700 ppm of ammonia gas was injected into the closed system once, and the hybrid odor removing system according to the present invention was operated.

The ammonia gas inside the sealed system was introduced into the reaction zone of the odor removal system by the blower installed under the odor removal system.

Adsorbed ammonia gas was immediately adsorbed and removed by the selective adsorbent which is the first adsorption reaction section, and the ammonia gas that was not adsorbed was harmless and odorless such as N ₂ and H ₂ O by UV / photocatalytic photoreaction in the photocatalytic reaction section. Decomposed to gas.

(d) In order to examine the reproducibility, the step (c) was performed twice more.

(e) The results of the above performance test, that is, the treatment ability of the ammonia odor of the odor removal system according to the present invention is shown in Figure 7b,

As can be seen in Figure 7b, the performance of the odor removal system for three consecutive times of ammonia gas in a batch closed system can be seen that 98% removal efficiency in 5 minutes uptime and 100% removal in 10 minutes uptime, The same was done three times in a row, from which the reproducibility and stable processing efficiency against load fluctuation could be examined.

(f) In order to investigate whether the odor removal method according to the present invention, that is, the selective adsorption reaction method and the photocatalytic photoreaction method is a hybrid system complementary to each other, continuously injecting 120 ppm of ammonia gas into the closed system for more than 6 days 7C shows the continuous treatment of the ammonia odor of the malodor removal system according to the present invention.

As can be seen in Figure 7c, ammonia gas flowing continuously 120ppm into the closed system was removed more than 98% in 5 minutes and lasted for 6 days.

If it is not a hybrid system, that is, if there is only an adsorption reaction, the 120 ppm of ammonia gas continuously injected would have prevented the selective adsorbents from reaching a saturation capacity in one to two days and thus no further ammonia removal efficiency.

However, the odor removal system according to the present invention shows continuous removal efficiency even after 1 to 2 days of operation,

This is because the ammonia gas adsorbed on the selective adsorbent is a low ammonia concentration section of the photocatalytic reaction section, that is, the ammonia gas adsorbed on the adsorbent is gradually desorbed by the concentration gradient between the adsorption reaction section and the photocatalytic reaction section. It can be considered that it decomposes into odorless gas.

In the field application of the hybrid odor removal system according to the present invention,

Process flow charts of the conventional odor removal system, that is, the general method and the recently applied ozone deodorization system are shown in Figs. 8A and 8B, respectively.

Conventional odor removal systems 400, 400 'and 400 " collect odors generated from odor discharge facilities 300 by odor collection facilities including local larynx, mucus, etc., and flow them into odor removal facilities. It removes odorous substances by reaction and releases air to outside air.

The conventional odor removal system as described above takes excessive power due to the pressure load of the odor collection facility and odor removal facility,

Most of the odor emission facility 300 should be maintained in a heated state, such as the air discharge to the outside air causes excessive heating costs,

In addition, the conventional odor removal system as described above has the disadvantage that secondary pollutants, including waste water, waste sludge, residual ozone and the like.

The present invention, which is invented to supplement the disadvantages of the conventional odor removal system as described above, is not a system for simply collecting and adsorbing and removing odor pollutants, but is a system for decomposing odor pollutants into harmless and odorless gases.

As illustrated in FIG. 9A, the odor collecting facility may be simplified, and the process flow may be configured to introduce the purified gas phase back into the odor discharge facility.

Such a method has an advantage that OH radicals and anions that may remain in the purified gas phase can be used for odor decomposition in spite of being generated in the complex hybrid reaction zone and used to decompose odor pollutants.

If, on site conditions, it is difficult to install the hybrid odor removal system according to the present invention inside the odor discharge facility, it may be installed outside the odor discharge facility as shown in FIG. 9B.

As described above, according to the present invention, a hybrid reaction mechanism combining a selective adsorption reaction method and a photocatalytic photoreaction method is combined to easily remove and decompose environmental pollutants such as odors, VOCs, and harmful bacteria in a short time, thereby providing clean air. You can get it.

The two odor removal methods complement each other, and the adsorption reaction section performs a buffering role to reduce the overload of the photocatalytic photoreaction section by rapidly removing and removing the pollutants with high load fluctuations in high concentration. The photocatalyst photoreaction zone forms a concentration gradient of contaminants significantly different from the adsorption reaction zone, and gradually desorbs the pollutants adsorbed on the adsorbent and decomposes them into harmless and odorless gases. It is effective in improving the life span of the adsorbent by supplying regeneration capacity.

In addition, the present invention can replace the existing complex air and odor purifying apparatus because the basic principle is simple, low cost and simple installation, so that it is easy to be industrially enlarged.

Hybrid odor removal system according to the present invention can reduce the power maintenance cost because there is almost no pressure load and the odor collecting facility is simplified,

In the present invention, the purified gas phase is introduced into the odor emission facility rather than the air discharge method to the outside, thereby reducing heating costs, and does not generate secondary pollutants including waste water, waste sludge, and residual ozone. It can be called an environmentally friendly odor removal system.

The odor control system incorporating the odor sensor according to the present invention has the effect of providing convenience in terms of not only controlling energy required for operation in real time but also managing and operating the odor control system.

Therefore, according to the present invention, it is very effective in terms of improving the polluted air and indoor air, which are becoming increasingly serious with recent industrial development.

1 is a schematic configuration diagram of a hybrid odor removing system according to the present invention,

2 is a schematic diagram of a real-time odor control system according to the present invention;

3a is a view showing the pore structure of a general adsorbent,

3b is an illustration of a selective adsorbent in accordance with the present invention;

Figure 4a is a view showing a typical photocatalytic photolysis reaction mechanism,

4b is a cross-sectional view of a fluidized photocatalyst carrier coated on a TiO ₂ surface according to the present invention;

Figure 4c is an illustration of a fluidized photocatalyst carrier coated on the TiO ₂ surface according to the present invention,

Figure 4d is an illustration of a transparent photocatalyst carrier coated on the surface TiO ₂ according to the present invention,

5 is a view showing a wavelength range diagram of a light source (ultraviolet lamp) according to the present invention;

6A is a view showing a reaction mechanism of the semiconductor odor sensor;

Figure 6b is an illustration of a semiconductor odor sensor according to the present invention,

6c is an embodiment of a real-time odor control system according to the present invention;

Figure 7a is an illustration of a hybrid odor removal system and performance test according to the present invention,

Figure 7b is a view showing the ammonia odor purification capacity of the odor removal system according to the present invention,

7c is a view showing the performance of continuously purifying the ammonia gas of the odor removal system according to the present invention,

8A is a view showing a process flow diagram of a general odor removal system;

8b is a view showing a process flow diagram of a conventional ozone deodorization system;

9A is a configuration diagram of a first embodiment of the odor removing system according to the present invention;

9B is a configuration diagram of a second embodiment of the malodor removing system according to the present invention.

<Description of the code | symbol about the principal part of drawing>

1: Selective adsorption reaction section 2: Photocatalytic reaction section

10: odor collecting means 11: dust filter

13: blower 14: retraction means

15: fixing means (sten net) 16: ammonia adsorbent

17: mercaptans adsorbent 18: hydrogen sulfide adsorbent

19: hydrocarbons / VOC adsorbent 20: reactor separation means

21: light source (ultraviolet lamp) 22: photocatalyst filter layer

23: coated photocatalyst 25: odor sensor

26: alarm function and calling means 27: control panel

30: fluidized photocatalyst carrier 31: transparent photocatalyst carrier

100: hybrid odor removal system

200: information collection, monitoring and control system

300: odor discharge facility 400: conventional odor removal system

Claims (1)

Odor; Volatile Organic Compound (VOC); Method for purifying polluted air containing harmful bacteria, By merging selective adsorption and photocatalytic photolysis reactions together, The selective adsorption section (1) absorbs and removes air pollutants with high load fluctuations in a high concentration at first, and minimizes load variation of contaminants in the photocatalytic photoreaction section (2). , And The photocatalyst photoreaction section (2) not only decomposes contaminants that have not been removed in the adsorption section (1) into a harmless and odorless gas by photochemical reaction, but also forms a concentration gradient of contaminants with the adsorption section (1) significantly. In the air pollutant purifying treatment method and apparatus for gradually desorbing the pollutant adsorbed on and decomposing the pollutant desorbed into the photocatalytic photoreaction zone into a harmless and odorless gas by photochemical reaction of photocatalyst / ultraviolet ray. The selective adsorbent constituting the adsorption reaction section (1) is manufactured and provided in the form of a nonwoven fabric to selectively adsorb the specific malodorous component by chemically modifying the surface of activated carbon or zeolite and / or by adhering chemicals. The photocatalytic photolysis reaction section 2 is composed of a fluidized photocatalyst carrier 30 to a transparent photocatalyst carrier 31 to which a titanium dioxide (TiO ₂ ) photocatalyst 30 "is coated and cured on a substrate 30 'and an activation energy for the photocatalyst carrier. In the form of an ultraviolet lamp 21 serving as a light source capable of supplying (hυ) and being provided in a modular form, The fluidized photocatalyst carrier 30 has a density of 0.01 to 0.10 g / cm ³ and a particle size of ^{3 to 20} mm that can be easily fluidized by only the air flow generated by the blower 13. It is manufactured by coating and curing photocatalyst on the surface of organic and inorganic compound and fluidizing in photoreaction section (2), purifying and treating air pollutants while actively contacting air pollutants, In order to desirably manage and operate the hybrid odor purifying treatment system 100, semiconductor sensors 25 capable of detecting operating variables are installed before, after, and in response to the odor removing system to provide information on operating variables in real time. It is possible to collect and to automatically adjust the optimum operating conditions of the odor removal system by a preconfigured program based on the collected information to reduce the power cost due to over-driving and to alarm and call function 26 when a fault occurs. Odor purifying treatment method and a odor purifying treatment system characterized in that it provides a total solution (TotalSolution) that can be.