KR200291899Y1 - Hybrid apparatus for removing voc and a bad smell by electromagnetic beam and adsorbent - Google Patents

Abstract

The present invention invents the adsorbent or ceramic of granular activated carbon that can adsorb volatile organic compounds and various harmful gases in the reactor to which electron beam is irradiated as a catalyst carrier, thereby contaminating pollutants by the combined action of electron beam, adsorbent and catalyst. The present invention relates to a hybrid removal device of volatile organic compounds / odorous substances containing an electron beam and a catalyst for removal.

The present invention is formed on the side and the bottom of each of the inlet and outlet pipes for the introduction and discharge of various harmful gases, there is a support network in which a plurality of small sphere-shaped adsorbents are seated therein, the electron beam is irradiated on the top Titanium irradiation window is attached so that the remaining electrons of the irradiated electron beam can be decomposed again to various harmful gas molecules adsorbed on the adsorbent, and the circular form of the adsorbent reduces the activation energy required for volatile organic compounds. It is characterized in that the catalyst plate is mounted at a certain height.

According to the present invention, a ceramic or adsorbent is provided to the electron beam as a catalyst carrier so that the decomposition by the electron beam, the decomposition by the adsorbent, and the thermal decomposition by the catalyst are complementary to various pollutants, odors, and volatile organic compounds. As a result, it utilizes less energy, as well as large-scale facilities such as petrochemical processes, painting processes, paint plants, oil refineries, sewage treatment plants and waste combustion treatment plants, which emit various harmful gas substances such as volatile organic compounds, odors or dioxins. Even in a small facility, it is very effective to remove the hazardous gaseous substances and it is very economical because it consumes relatively little energy to remove the pollutants.

Description

HYBRID APPARATUS FOR REMOVING VOC AND A BAD SMELL BY ELECTROMAGNETIC BEAM AND ADSORBENT}

The present invention relates to a hybrid removal device of volatile organic compounds / odorous substances containing an electron beam and a catalyst, and more specifically, an adsorbent of granular activated carbons capable of adsorbing volatile organic compounds and various harmful gases in a reactor to which an electron beam is irradiated or The present invention relates to a hybrid removal device of volatile organic compounds / odorous substances containing an electron beam and a catalyst to install a ceramic as a carrier of a catalyst to remove contaminants by a complex action of the electron beam, the adsorbent, and the catalyst.

As is well known, the structure of the emission source is changing due to the advancement of the industry and the increase in the use of automobiles and various coating materials, and accordingly, the types of air pollutants are also diversified.

In particular, volatile organic compounds (VOCs) have long been treated as air pollutants with harmful effects on human health and the environment. Volatile organic compounds (VOCs) are very diverse and widespread, with thousands of chemicals. They are also highly flammable and can cause safety accidents caused by fire explosions.

VOCs include organic compounds including BTEX (bezene, toluene, ethylbenzen, xylene) and PCE, TCE, CHC, halogenated and non-halogenated chlorine, accounting for the majority of VOC compounds. It is a compound with high chemical reactivity and carcinogenicity, which is absolutely required for regulation and economic control method is urgently needed.

In addition, volatile organic compounds (VOCs) are known as pollutants that are highly mobile and cause odors in the atmosphere, as well as are highly anesthetic. In addition, since it has potential toxicity and carcinogenicity, and ozone is formed by photochemical reaction with nitric oxide and other compounds, environmental pollution caused by these is of particular interest.

In order to solve the above problems, each workplace has been struggling with the selection and application of appropriate prevention technologies, and above all, economic feasibility and safety of the workplace.

First of all, volatile organic compounds emitted from painting and petrochemical facilities account for almost all of the volatile organic compounds, except for the exhaust gas generated by automobile operation. Is absolutely necessary recently.

However, since there are many kinds of volatile organic compounds emitted from these facilities, it is technically difficult to control them all with the same method and facility. Therefore, materials having similar physical and chemical properties are selected and controlled according to their characteristics. Is required.

Since the combustion method of the prior art is operated at a high temperature, THERMAL NOx may be generated and carbon dioxide (CO 2), which is a greenhouse gas, is generated.

In addition, there is a problem in that additional cleaning facilities need to be installed additionally when treating the halogen compound, it costs a lot of fuel.

In the catalytic oxidation method, the application range is limited depending on the properties of the gas to be treated. The life of the catalyst is about 3-5 years, which requires a catalyst exchange and a high facility cost.

On the other hand, the adsorption technology gradually decreases the adsorption capacity according to the regeneration time of the adsorbent. Therefore, the cost of the adsorbent needs to be changed frequently. Also, the pretreatment system requires the filtration of particulate matter. The disadvantage is the increased cost.

Recently, the method of removing contaminants using electron beams has been introduced. The method of removing contaminants using electron beams is dry at room temperature, so it is expected that a secondary wastewater treatment facility is not required. medium. The situation is applied only to large-capacity facilities. If a pollutant removal device using an electron beam is used in a small structure, research on various methods to increase the efficiency must be preceded.

Therefore, in order to solve the above problem, the applicant has filed a patent application No. 10-2001-456842 (designated name: VOC removal apparatus and method thereof, August 14, 2001). The conventional VOC removal apparatus described above will be described in detail with reference to the accompanying drawings.

1A and 1B illustrate a VOC removing apparatus according to a conventional embodiment.

Referring to this, the volatile organic compound removing device 100 according to the conventional design provides a cylindrical closed frame 120, the upper surface of the frame 120 is an electron beam irradiation window made of titanium alloy (not shown) The inner circumferential surface of the frame 120 is provided with a reflecting member 120a so as to easily reflect the electron beam.

In addition, an electron beam accelerator 110 for irradiating an electron beam to a position spaced a predetermined distance from the upper surface of the electron beam irradiation window is provided. On the other hand, the inlet pipe 122 through which the volatile organic compound flows is formed in a predetermined portion of the outer peripheral side of the frame 120, and the outlet pipe 124 through which the volatile organic compound flows out is formed in the predetermined portion.

In addition, an adsorbent support net 128 for seating the adsorbent 130 at a position spaced a predetermined distance from the bottom surface of the frame 120 is configured, and at the edge of the support net 128 from the frame 120 An annular support protrusion 126 protruding therein is formed to fix the support net 128 at a predetermined height.

At this time, the adsorbent 130 is described. As an example of the adsorbent 130, the gaseous activated carbon has a large specific surface area and a small diameter pore structure, and has a high adsorption affinity for low concentration gas. In addition, since its surface is hydrophobic, its adsorption affinity to water vapor is low, and harmful gas substances such as volatile organic compounds and odors mixed in air can be efficiently removed. Activated charcoal co-exists with a portion where irregularly dispersed fine crystals of graphite structure and a methylene ring portion. In addition, the internal pore structure is developed to have a distinctly large specific surface area of 3,000㎡ / g.

When activated carbon is in contact with a solid surface in a fluid phase for a long time, certain components of the fluid phase are collected on the solid surface and the concentration of the inside of the fluid phase is different from that of the solid surface. This phenomenon is Adsorption, where the relationship between the concentration in the fluid phase and the solid surface concentration is balanced if the chemical potential of the phase is appropriate and a relationship called Adsorption Equilibrium Relation is established.

In addition, this relationship is much influenced by temperature. Adsorption on activated carbon is carried out by the following principle. Activated carbon particles have a dual structure of micropores (2 nm or less) that dominate the adsorption and macropores (several micrometers) formed as a gap between the microparticles. The diameter of the granular activated carbon is several mm, and since the adsorbate molecules reach and reach the adsorption point inside the particles, the adsorption takes place through various paths. One of them is a series diffusion which is moved by diffusion into the fluid filling the macropores and diffuses and adsorbs within the micropores. Another type of diffusion is surface diffusion, in which molecules on the surface of the adsorbent are moved to adjacent adsorption points.

Hazardous gases such as volatile organic compounds adsorbed by this principle are decomposed by electron beam irradiation. In addition, since the electron beam irradiation increases the kinetic energy of the molecules themselves, the adsorbed molecules are irradiated again by the electron beam and decomposed secondaryly while the desorption from the surface of the adsorbent is repeated.

That is, the volatile organic compounds introduced through the inlet pipe 24 are primarily decomposed by the electron beam irradiated from the upper part of the frame 120, and desorbed by the adsorbent 130 seated on the support net 128. It is concentrated and repeated repeatedly, and secondary decomposition is performed by the electron beam, and residual gas from which volatile organic compounds have been removed is discharged through the outlet pipe 124.

At this time, when the volatile organic compound is intermittently adsorbed and concentrated by the adsorbent 130, when the electron beam is irradiated from the top, the decomposition efficiency of the volatile organic compound is higher.

However, the volatile organic compound removal device using the electron beam and the adsorbent is easy to remove the volatile organic compounds when the energy of the electron beam to be irradiated in the adsorption, desorption, and removal of volatile organic compounds (VOC), When the energy of the electron beam is small, it has been found that adsorption and desorption dominate rather than removal of volatile organic compounds.

In particular, the volatile organic compound removal device composed only of electron beams, such as methane has a problem that it is very difficult to decompose a material having a stable structure with a small bonding energy (bonding energy).

The present invention has been made in view of the above-described prior art. The present invention proposes an electron beam and an adsorbent or ceramic of granular activated carbons capable of adsorbing volatile organic compounds and various harmful gases in a reactor to which electron beams are irradiated. It is an object of the present invention to provide a hybrid removal device of a volatile organic compound / odorous substance containing an electron beam and a catalyst to efficiently remove contaminants even under small electron beam energy by a complex action of an adsorbent and a catalyst.

1A and 1B are views illustrating a VOC removing apparatus according to a conventional embodiment,

Figure 2 is a perspective view showing the appearance of a hybrid removal device of volatile organic compounds / odorous substances containing an electron beam and a catalyst according to an embodiment of the present invention,

Figure 3 is a side cross-sectional view showing a hybrid removal device of volatile organic compounds / odorous substances containing an electron beam and a catalyst according to an embodiment of the present invention,

4 is a graph showing a comparison of removal rates of volatile organic compounds when the ceramic catalyst is mounted and unmounted according to the electron beam irradiation dose according to an embodiment of the present invention;

5 is a graph showing a comparison of removal rates of volatile organic compounds between a platinum-supported ceramic catalyst and a general ceramic catalyst according to an embodiment of the present invention;

6 is a graph showing a comparison of removal rates between ceramic catalysts and ternary ceramic catalysts according to an embodiment of the present invention.

* Description of the symbols for the main parts of the drawings *

200: removal device, 210: electron beam accelerator,

220: frame, 222: inlet pipe,

224: outflow pipe, 230: adsorbent,

232: catalyst plate.

In order to achieve the above object, according to a preferred embodiment of the present invention, the inlet pipe and the outflow pipe which is introduced and discharged various harmful gases are formed on the side and the lower surface, respectively, a plurality of small sphere-shaped adsorbents therein The supporting network is settled, and the titanium irradiation window is attached so that the electron beam can be irradiated on the upper part so that the remaining electrons of the irradiated electron beam can be decomposed again to the various harmful gas molecules adsorbed on the adsorbent, The present invention provides a hybrid removal device for volatile organic compounds / odorous substances including an electron beam and a catalyst, wherein the catalyst plate is mounted at a predetermined height to reduce the activation energy required for the volatile organic compounds.

Preferably, the adsorbent provides a hybrid removal device of a volatile organic compound / odorous substance containing an electron beam and a catalyst, characterized in that the catalyst can be supported therein.

Preferably, the present invention provides a hybrid removal apparatus for volatile organic compounds / odorous substances containing an electron beam and a catalyst, characterized in that the ceramic may be configured in the form of a plate carrying a catalyst instead of the adsorbent.

Hereinafter, the present invention will be described in detail with reference to the drawings.

2 is a perspective view showing the appearance of a hybrid removal device of a volatile organic compound / odorous substance including an electron beam and a catalyst according to an embodiment of the present invention, Figure 3 is an electron beam and a catalyst according to an embodiment of the present invention Side cross-sectional view showing a hybrid removal device of volatile organic compounds / odorous substances included.

Referring to this, the hybrid removal apparatus 200 of volatile organic compounds / odorous substances including an electron beam and a catalyst according to an embodiment of the present invention provides a cylindrical frame 220, the upper surface of the frame 220 An electron beam irradiation window 212 made of a titanium alloy is provided, and a reflection member (not shown) is coated on the inner circumferential surface of the frame 220 so that the electron beam can be easily reflected.

In addition, an electron beam accelerator 210 for irradiating an electron beam to a position spaced a predetermined distance from the upper surface of the electron beam irradiation window 212 is provided. On the other hand, an inlet pipe 222 through which various volatile organic compounds are introduced from the outlet of the factory through various pipes is formed at a predetermined portion of the outer side of the frame 220, and the residual gas of the volatile organic compounds removed at the lower portion thereof is formed. Outflow pipes 224 are formed, respectively.

In this case, if the volatile organic compound is completely removed from the inside of the frame 220, the gas flowing out through the outlet pipe 224 becomes clean air than the normal atmosphere.

In addition, an adsorbent support network 228 for seating the adsorbent 230 at a position spaced a predetermined distance from the inner bottom surface of the frame 220 is configured, and a lower portion of the support network 228 is in close contact with the support network 228. In this state, a circular catalyst plate 232 is provided.

In addition, a fixing jaw 226 protruding from the inner wall of the frame 220 to support the catalyst plate 232 at a predetermined height is formed under the catalyst plate 232.

The hybrid removal device 200 of the volatile organic compound / odorous substance including the electron beam and the catalyst having the above-described structure includes the decomposition activation action of the pollutant by the electron beam, the repeated adsorption / desorption action by the adsorbent 230, The thermal decomposition action by the catalyst 232 causes a hybrid decomposition / removal action.

At this time, the catalyst 232 is not activated by itself, but when activated by an external energy source will cause a strong thermal decomposition action. Therefore, the electron beam irradiated from the upper side of the hybrid removal device 200 of the volatile organic compound / odorous substance containing the electron beam and the catalyst of the present invention causes a primary decomposition action to the contaminants adsorbed on the adsorbent 230 The remaining energy is to act as the activation energy of the catalyst 232.

Meanwhile, the catalyst contained in the catalyst plate 232 may be mixed inside the adsorbent 230 exemplified in the hybrid removal apparatus of the volatile organic compound / odorous substance including the electron beam and the catalyst according to an embodiment of the present invention. . That is, the adsorbent 230 serves as a carrier of the catalyst.

In addition, instead of the adsorbent 230, a ceramic-based material may be configured to include the catalyst as a carrier.

In the case of an electron beam, even though its binding energy is much higher than that of methane, unstable odors such as styrene and VOC materials having a functional group such as a double bond (eg, methyl group) can be easily decomposed. In fact, the more functional groups, the easier the electron beam can deal with odors and VOC materials through radical reactions such as OH-radicals.

TABLE 1

property methane benzene toluene O-xylene m-xylene p-xylene Coupling Energy (Kcal / mol) 104 1,433 1,739 2,045 2,045 2,045 Reaction Constant for OH Radicals 0.00836 × 10 ^-12 1.28 × 10 ^-12 6.19 × 10 ^-12 14.7 × 10 ^-12 24.5 × 10 ^-12 15.2 × 10 ^-12

However, the unit of reaction constant is cm <3> / mol / sec, and it is the table discharged in the temperature environment of 298k.

Table 1 shows the change of the reaction constant with OH-radical according to the binding energy change of each volatile organic compound. Even in the case of volatile organic compound with high binding energy, the volatile organic compound containing the activated carbon catalyst according to the present invention It can be seen that the disassembly and removal is made easily through the removal device of the.

More specifically, methane (CH ₄ ) is a simple cyclic without a double bond, and benzene (Benzene: C ₆ H ₆ ) has two double bonds and has a ring shape. In addition, toluene (C ₇ H ₈ ) has a bond of (C ₆ H ₅ ) -CH ₃ , and o-xylene (C ₈ H ₁₁ ) is (CH ₃ )-(C ₆ H ₅ )-(CH ₃ ) has a bond, m-xylene (C ₈ H ₁₁ ) has a bond of (CH ₃ )-(C ₆ H ₅ )-(CH ₃ ), p-xylene (p-xylene: C ₈ H ₁₁ ) has a bond of (CH ₃ )-(C ₆ H ₅ )-(CH ₃ ).

As shown in Table 1, the volatile organic compound having such a bonding structure is decomposed through a radical reaction such as OH-radical. As shown in Table 1, even if the binding energy is large, it can be seen that the decomposition of the volatile organic compound having a large reaction constant with OH-radical is easily decomposed, and the more group groups, the more decomposes.

4 is a graph showing a comparison of removal rates of volatile organic compounds when the ceramic catalyst is attached and unmounted according to the electron beam irradiation dose according to an embodiment of the present invention.

Referring to this, FIG. 4 is a graph showing the removal rate of the volatile organic compounds identified by constructing the ceramic catalyst in the volatile organic compound removal device of the present invention shown in FIGS. 2 and 3, wherein the general reactor in which only the electron beam is irradiated While the irradiation dose is increased in direct proportion to an angle, the ceramic catalyst is composed of the catalyst plate 232, and when the irradiation dose of the electron beam is increased, the removal reaction of the volatile organic compound is further activated.

This removal reaction is shown because the ceramic catalyst becomes active at a constant temperature, thereby further reducing the activation energy (= energy required for the removal reaction) for the main removal section of the removal reaction. Therefore, the electron beam, the activated carbon, and the catalyst, which are the means for removing the volatile organic compounds of the present invention, play a complementary role and facilitate the removal of the volatile organic compounds.

In particular, in the case of the volatile organic compound removal device including the catalyst, it is possible to easily remove a material having a low binding energy but stable structure, such as methane.

For example, when it is desired to simultaneously remove substances such as methane, ethane, propane, benzene, toluene, xylene and styrene, it can be seen that a hybrid process of an electron beam and a catalyst can be used to more effectively remove volatile organic compounds. Herein, materials such as methane, ethane, and propane have much lower binding energy than materials such as benzene, toluene, xylene, and styrene, and the chemical structure is relatively stable. In this case, the catalyst is removed and decomposed. You can expect

On the other hand, materials such as toluene, xylene, and styrene have a larger bond energy than the above three materials, but at least one functional group (group group) is unsaturated, and a double bond is unsaturated. Can be. In fact, this can be confirmed by experiments. For example, even in the case of aromatic substances such as benzene, toluene, xylene, and styrene, the binding energy is high in the order of benzene <toluene <xylene <styrene. On the other hand, it can be seen that the catalyst is more easily decomposed in order of decreasing binding energy, that is, in order of benzene> toluene> xylene> styrene. Therefore, the present invention is proposed to have an optimum decomposition rate by employing a hybrid removal device of the catalyst and the electron beam.

However, since the number of functional groups increases toward the right side, it can be seen that the decomposition of benzene <toluene <xylene <styrene is performed well by the electron beam.

5 is a graph showing a comparison of removal rates of volatile organic compounds between a platinum-supported ceramic catalyst and a general ceramic catalyst according to an embodiment of the present invention.

2 and 3, the catalyst plate 232 provided at the bottom of the inside of the volatile organic compound removal apparatus 200 shown in FIGS. 2 and 3 is volatile together with the activated carbon positioned at the top thereof and the electron beam irradiated from the electron beam accelerator 210. When the electron beam irradiated from the electron beam accelerator 210 is irradiated for a predetermined time to the volatile organic compound adsorbed on the adsorbent 230, heat is generated on the surface of the adsorbent 230 and the temperature is increased. .

At this time, when the temperature of the surface of the adsorbent 230 is raised to 200 ~ 250 ℃, the catalyst constituting the catalyst plate 232 is activated to reduce the activation energy required for the activation of the entire reaction to promote the reaction. Reduction of the activation energy during the removal reaction is made by exothermic reaction of the catalyst plate 232 itself, the catalyst plate 232 is activated by external energy to cause a strong pyrolysis reaction.

Therefore, in the hybrid removal device 200 of the volatile organic compound / odorous substance containing the electron beam and the catalyst according to the present invention, the electron beam action, the adsorption decomposition action, and the thermal decomposition action by the catalyst are complementary to each other.

6 is a graph showing a comparison of removal rates between ceramic catalysts and ternary ceramic catalysts according to an embodiment of the present invention.

Referring to this, as illustrated in FIG. 5, the removal reaction of the volatile organic compound using the electron beam, the adsorbent, and the catalyst has a close relationship with the radiation dose of the electron beam since the current input to the electron beam accelerator is closely related to the ceramic catalyst and the three-way current. It is a graph comparing the removal reaction rate of the catalyst.

As a result of electron beam treatment using a ceramic platinum (pt) catalyst or a ceramic ternary catalyst, it can be seen that when the platinum catalyst is applied as illustrated in FIG. 6, the removal rate is higher than that of the ternary catalyst. In particular, it can be seen that the removal rate of 20% or more is improved when the electron beam and the catalyst are applied simultaneously than when only the electron beam is applied. In this case, not only platinum or a ternary catalyst is used as the catalyst of the present invention, but all metal catalysts are included.

In addition, when the electron beam is irradiated by bringing the structure of the adsorbent 230 into close contact with the upper surface of the catalyst plate 232 as shown in the present invention, the removal rate of the volatile organic compound is higher. In this case, since a material such as ceramic, which is a carrier of the catalyst, has a tendency to accumulate heat, it can be seen that it is more advantageous to increase the temperature inside the reactor.

In the process of removing a volatile organic compound using a volatile organic compound removal device including an activated carbon catalyst according to the present invention, first, the volatile organic compound to be treated is introduced into the removal device 200 through the inlet pipe 222. do.

Then, the volatile organic compound is attached to the surface of the adsorbent 230 seated at a predetermined height inside the removal apparatus 200. At the same time, the electron beam accelerator 210 is driven to irradiate a predetermined electron beam irradiation dose to the surface of the adsorbent 230.

In the lower portion of the adsorbent 230, a ceramic platinum catalyst or a ceramic tertiary catalyst for reducing the activation energy required for the volatile organic compound removal reaction is composed of a circular catalyst plate 232, the methane by the catalyst plate 232 Volatile organic compounds having a stable structure, such as the like, are easily decomposed through reaction with OH-radicals.

On the other hand, the hybrid removal device of the volatile organic compounds / odorous substances containing the electron beam and the catalyst according to an embodiment of the present invention is not limited to the above embodiments only, various modifications can be made without departing from the technical spirit of the Do.

As described above, the hybrid removal device of the volatile organic compound / odorous substance containing the electron beam and the catalyst according to the present invention provides a ceramic or adsorbent as a carrier of the catalyst to the electron beam to decompose by the electron beam, decompose by the adsorbent, Pyrolysis by catalysts complements various pollutants, odors, and volatile organic compounds, resulting in petrochemical processes, coating processes, paint plants, refineries, and other hazardous gaseous substances such as volatile organic compounds, odors, and dioxins. Large facilities such as factories, sewage treatment plants, and waste-fired treatment plants, as well as small facilities that use less energy, can effectively remove the harmful gaseous substances and are very economical because they consume relatively little energy to remove pollutants. .

Claims (3)

Inflow and outflow pipes are provided on the side and the bottom of each harmful gas inflow and outflow. Titanium irradiation window is attached so that the residual electrons of the irradiated electron beam can be decomposed again on various harmful gas molecules adsorbed on the adsorbent, and the catalyst plate is formed in a circular shape and reduces the activation energy required for volatile organic compounds. Hybrid removal device of volatile organic compounds / odorous substances containing an electron beam and a catalyst, characterized in that mounted in height. According to claim 1, wherein the adsorbent is a hybrid removal device of volatile organic compounds / odorous substances containing an electron beam and a catalyst, characterized in that the catalyst can be carried therein. 3. The hybrid removal device of volatile organic compound / odorous substance including an electron beam and a catalyst according to claim 2, wherein the ceramic may be formed in a plate shape in which a ceramic is supported instead of the adsorbent.