KR20120133292A - Apparatus for purifying or catalytically removing waste gas containing fluorinated compounds - Google Patents

Apparatus for purifying or catalytically removing waste gas containing fluorinated compounds Download PDF

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KR20120133292A
KR20120133292A KR1020110051893A KR20110051893A KR20120133292A KR 20120133292 A KR20120133292 A KR 20120133292A KR 1020110051893 A KR1020110051893 A KR 1020110051893A KR 20110051893 A KR20110051893 A KR 20110051893A KR 20120133292 A KR20120133292 A KR 20120133292A
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South Korea
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fluorine compound
compound gas
gas
storage tank
catalytic
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KR1020110051893A
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Korean (ko)
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장원철
권원태
가명진
문규동
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주식회사 코캣
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2047—Hydrofluoric acid

Abstract

PURPOSE: An apparatus for separating and catalytically removing waste gas containing fluorinated compounds is provided to treat exhaust gas containing fluorinated compounds of high concentration according to the charging amount of a catalyst. CONSTITUTION: An apparatus for separating and catalytically removing waste gas containing fluorinated compounds includes a pre-treatment unit, a heat exchanging and mixing unit, a catalytically decomposing unit, and a wet type post-treatment unit. The pre-treatment unit stabilizes and stores waste gas containing fluorinated compounds. The pre-treatment unit includes a separating unit(102) concentrates and regenerates a part of the waste gas. The heat exchanging and mixing unit includes a mixer(201) dilutes non-regenerated waste gas from the pre-treatment unit at high temperatures. The catalytically decomposing unit includes a catalytic reactor(301) catalytically reacts the diluted waste gas at high temperatures. The wet type post-treatment unit removes byproducts from gas from the catalytically decomposing unit.

Description

Apparatus for purifying or catalytically removing waste gas containing fluorinated compounds}

The present invention relates to a safe treatment method focusing on proper separation and catalysis in connection with the development of a system capable of treating fluorine oxide, which is a representative material of global warming, and more specifically, SF 6 , CF 4 , The present invention relates to an apparatus for treating pollutants such as NF 3 .

In order to address global warming, the UNFCC was signed in Rio in Brazil in March 1994. Each country was obliged to establish, report and implement emissions reduction measures. In March, Kyoto, Japan, discussed again, 38 developed countries decided to reduce greenhouse gas emissions by an average of 5.2% from 2008 to 2012. Three major mechanisms to effectively implement greenhouse gas reductions, the Clean Development System (CDM), the Joint Implementation System (JI), and the Emissions Trading System (ET) have been ratified and implemented. It will be designated as a mandatory country for reduction. In particular, the global warming index of carbon dioxide (GWP) is 1, whereas sulfur hexafluoride (SF 6 ): 23900, CF 4 : 6500, C 2 F 6 : 9200, C 3 F 8 : 7000 For example, CHF 3 : 8700 and NF: 12000-20000 have not only a very high global warming index, but also demands more than 90% of the Destruction and Removal Efficiency (DRE).

In this situation, the global warming potential (SF) 6, which is 23,900 times higher than that of carbon dioxide, a representative cause of global warming, as well as all stages of consumption, emission, and disposal in response to regulations on the use and disposal of CF 4 and NF 3 . Database construction is required and various ways to reduce it are being researched and studied.

In general, the fluorine compound gas treatment method includes separation, recovery, and decomposition, and recently, the focus is on combustion, pyrolysis, plasma decomposition, and catalytic decomposition in order to treat SF 6 , which is relatively low in concentration. The processing facility in the semiconductor manufacturing process is a reduction technology that decomposes more than 90% of the discharged PFCs without decomposing 5-80% after use, but it is economical, but it can reduce PFCs in large quantities.

As a pyrolysis technology in Korea, the Korea Environmental Industry and Technology Institute announced in 2010 that it has certified 'high-volume sulfur hexafluoride and fluoride gas high efficiency direct decomposition technology' as green technology. This technology is pyrolysis of sulfur hexafluoride in the high temperature reactor at 1250-1350 ℃ and rapid cooling to remove it.There is no fear of generating secondary pollutants such as dioxins, and it has a high capacity (more than 30 m 3 / min) In addition to the sulfur fluoride treatment, it is characterized by the ability to remove more than 95% sulfur hexafluoride depending on the temperature conditions. However, since pyrolysis at high temperature requires maintaining a temperature of 1000 ° C or more from the viewpoint of energy, there is an economical disadvantage. In order to solve this problem economically, efforts have been made to lower the reaction temperature through a catalyst.

In particular, among the technologies for removing SF 6 , which is a representative greenhouse gas, technologies for reducing the reaction through catalysts include Hitachi, Kanken, Ebara and Showa Denko of Japan to treat PFCs gas generated in semiconductor processes. Companies such as these have the achievements in technology development and commercialization. However, the SF 6 gas removal technology using such catalytic decomposition is a technology that is limited to only small devices (about 200 L / min) in the semiconductor field worldwide, and is commercially available only in the semiconductor manufacturing process mainly in Japan. In addition, in the field of heavy electric and large-capacity decomposition treatment, many technologies for recovery and separation / refining have been studied, but the technical development of high concentration SF 6 treatment technology and apparatus for heavy electric equipment is sluggish. Accordingly, the present invention relates to a stable SF 6 gas removal technology and a stable by-product as a large-capacity gas treatment technology for heavy electric insulation gas treatment.

Currently, SF 6 gas treatment generated from electric power infrastructure facilities such as heavy electric machines, transmission and distribution facilities, and power equipment manufacturers. High concentrations of SF 6 gas with a purity of 95% or less are difficult to install large-capacity treatment devices on site. It is impossible to process, and equipped with high concentration greenhouse gas treatment facilities at one point in Korea, recruiting waste SF 6 gas at the site of heavy electric and electric equipment, and then moving to the aggregated decomposition facility by tank lorry to separate and catalyst high concentration SF 6 There is a need for an integrated large-capacity batch system for processing greenhouse gases, which is treated in cracking treatment facilities.

Currently, there is a large-scale pyrolysis system for the treatment of greenhouse gases in semiconductor exhaust gas, which is a pyrolysis method using LPG gas that removes low concentrations of PFCs waste gas. This method requires the removal of high concentration greenhouse gas, waste greenhouse gas. There is a problem in that the separation device for regenerating and the problem of treating the waste gas remaining after the regeneration, the problem of treating the by-products of the greenhouse gas, the corrosion of the equipment.

Accordingly, the present invention has been made to improve the problems of the prior art, and provides a separation device for separating and regenerating a high concentration of fluorine compound gas and a catalytic decomposition device for treating waste gas remaining after regeneration, and by-products of fluorine compound gas. It is an object of the present invention to provide a device that must prevent corrosion of processing equipment and equipment.

In order to achieve the above object, the aggregated fluorine compound gas separation and catalytic decomposition treatment apparatus according to the present invention is to move and collect the high concentration fluorine compound gas, and then stabilized and stored at a constant concentration, separated and concentrated before the decomposition treatment to regeneration treatment Pretreatment means; Heat exchange and mixing means for diluting the low temperature, high concentration fluorine compound gas untreated by a pretreatment means to a high temperature; Catalytic decomposition means for removing the fluorine compound gas by heating the hot dilute fluorine compound gas by a heating device and then injecting reaction water and then catalytically decomposing the fluorine compound gas; And wet post-treatment means for removing by-products of the cracked fluorine compound gas from the catalytic cracking means.

The pretreatment means includes a storage tank for receiving and stabilizing the fluorine compound gas from the moving tank moved from the outside, and vacuuming the pipe between the storage tank and the separation device to facilitate the separation of the high concentration of fluorine compound gas from the storage tank. Including a vacuum pump, a fluorine compound gas separation device, a piping configuration to recover the untreated fluorine waste gas storage tank from the separation device,

The heat exchange and mixing means for high temperature dilution of the low temperature high concentration fluorine compound gas is a heat exchanger for heating the air for dilution using heat discharged from the high temperature catalytic reaction, the flow rate when moving from the fluorine compound waste gas storage tank to the mixer It includes a flow meter for controlling, a high temperature dilution air from the heat exchanger and a mixer for high temperature dilution of the low temperature fluorine compound gas controlled by the flow meter,

The decomposition means for heating and catalytically decomposing the fluorine compound gas is heated to the catalytic reaction temperature by using the heat discharged from the heating apparatus, and after the reaction water is input, the high-temperature diluted fluorine oxide gas discharged from the mixer is inputted. It includes a catalytic reactor which is subjected to catalytic decomposition while passing through the catalytic reaction layer,

The wet post-treatment means for removing the by-products of the fluorine compound gas is such that the by-products of the fluorine compound gas decomposed through the catalytic reactor can be wet-treated in advance in the pipe before moving to the gas cleaning device. A pre-added injection nozzle, a cleaning device capable of removing residual by-products, and a cooling device for controlling the temperature of the reaction water and the cooling water of the cleaning device to a low temperature.

That is, according to one embodiment of the present invention, there is provided a pretreatment means (a) for collecting, stabilizing and storing fluorine compound-containing waste gas, concentrating and regenerating a part of the waste gas at a high concentration, 100); (b) heat exchange and mixing means (200) for diluting the non-regenerated waste gas from the pre-processing means to a high temperature; (c) catalytic cracking means (300) for catalytically reacting the non-regenerated waste gas diluted with the high temperature at a high temperature; And (d) a wet post-treatment means (400) for removing by-products in the fluorine compound gas discharged from the catalyst decomposing means.

According to another embodiment of the present invention, there is provided a method of regenerating a fluorine compound gas, comprising: (a) a storage tank 101 for receiving and stabilizing a fluorine compound gas from an external transfer tank; A pretreatment means (100) comprising a separation device (102) for withdrawing unreacted residual unregenerated fluorocompound gas to the storage tank;

(b) a fan (106) for introducing outside air from the outside, a mixer (201) for mixing the outside air and the fluorine compound gas partially introduced into the storage tank, (200) for mixing the fluorine compound gas partially introduced into the storage tank with the heated outside air and diluting the fluorine compound gas to a high temperature, the heat exchanger including a heat exchanger (203)

(c) a catalytic reactor (301), a heating device (302) for heating the highly diluted fluorine compound gas to a catalytic reaction temperature before the fluorine compound gas diluted at high temperature in the mixer is introduced into the catalytic reactor, And a reaction water injection unit (303) for introducing the reaction water into the catalytic reactor together with the fluorine compound gas.

(d) a wet post-treatment means (400) for removing by-products in the fluorine compound gas discharged from the catalyst decomposing means.

In the heat exchanger, heat exchange is performed between the outside air introduced from the outside-air inlet fan and the high-temperature exhaust gas discharged from the catalytic reactor.

According to another embodiment of the present invention, the pre-processing unit further includes a vacuum pump 104 for applying a vacuum to the pipe between the storage tank and the separator, Thereby facilitating the separation of the fluorine compound gas at a high concentration from the storage tank by removing impurities inside and outside the piping.

According to another embodiment of the present invention, the pre-processing means further includes a cylinder 105 for storing the fluorine compound gas that has been concentrated and regenerated at the high concentration.

According to still another embodiment of the present invention, the pre-treatment unit further includes a fan 106 for introducing outside air. A fan 106 for introducing outside air is installed to treat the remaining amount of the fluorine compound gas remaining in the storage tank 101 after regenerating the fluorine compound gas at a high concentration in the storage tank 101, The remaining amount is introduced into the catalytic reactor 301 to carry out the catalytic cracking treatment.

According to still another embodiment of the present invention, the pretreatment means further comprises a valve (107) for opening the vent line and the vent line below the separating device. A decompositionally treating apparatus is disclosed. In order to remove dust and moisture from the storage tank 101 after the fluorine compound gas is regenerated at a high concentration in the storage tank 101, 101 to open the valve 107 and discharge it through the bottom vent line of the storage tank 101 to the outside.

According to another embodiment of the present invention, the separation apparatus adsorption reactor 1021, the filter apparatus 2022, the pressure regulator 1023, the pressure meter 1024, the temperature regulator 1025, the temperature meter 1026, Disclosed is an apparatus for separating and catalytically decomposing fluorine compound gases including a plurality of separation membrane modules (1027, 1028), a regenerated fluorine compound gas flow meter (1029), and an unregenerated fluorine compound gas flow meter (1030).

Here, the adsorption reactor and the filter device respectively remove acidic substances, moisture and dust in the fluorine compound gas introduced from the storage device. The pressure regulator and the temperature regulator adjust the pressure and temperature of the introduced fluorine compound gas based on the pressure measured from the pressure meter and the temperature measured from the temperature meter, The separation yield of the plurality of separation membrane modules is controlled according to the concentration and flow rate of the compound. Further, the regenerated fluorine compound gas flow meter adjusts the amount of the fluorine compound gas that has been concentrated and regenerated by the high concentration into the cylinder, and the non-regenerated fluorine compound gas meter detects the flow of the non-regenerated fluorine compound gas into the storage device Adjust the amount to be recovered.

According to another embodiment of the present invention, the heat exchanging and mixing means further comprises a flow meter (202) for regulating the amount of the fluorine compound gas introduced into the storage tank A separation and catalytic cracking treatment apparatus is disclosed.

According to another embodiment of the present invention, in order to maintain a high temperature of the mixed gas in which the outside air changed to a high temperature through the heat exchanger and the fluorine compound gas flowing through the flow meter is maintained at a high temperature, And a pore-sealing material is filled with the pore-forming material by mixing means in the mixer.

In addition, according to another embodiment of the present invention, the introduced outside air from the outside air inlet fan 204 passes from one side to the opposite side of the heat exchanger, and the hot exhaust gas discharged from the catalytic reactor And the heat exchange is performed while passing from the lower part to the upper part of the heat exchanger.

According to another embodiment of the present invention, the wet post-treatment means 400 includes an acidic reaction substance storage tank 404, a cooling water storage tank 405, an alkaline reaction substance storage tank 406, The means 400 further comprises a reactant injection device 403 through which the exhaust gas discharged from the catalytic reactor can pass.

(1) an acidic reaction substance storage tank, (2) a cooling water storage tank, and (3) an alkaline reaction substance storage tank, respectively, as the exhaust gas discharged from the catalytic reactor passes therethrough. (2) cooling water, and (3) an alkaline reaction material are sequentially injected into the reactant injecting apparatus, and sequentially (1) the by-product in the exhaust gas is reacted with the acidic reaction material at a high temperature, (2) the temperature of the exhaust gas is lowered, and (3) the by-product in the exhaust gas reacts with the alkaline reaction material at a low temperature in a gas-liquid method.

According to another embodiment of the present invention, the wet post-treatment means 400 includes a cleaning device 401 through which the exhaust gas discharged from the catalytic reactor can pass after the reactant injection device, Disclosed is an apparatus for separating and catalytically decomposing gaseous fluorine compounds, characterized by further comprising a reaction water storage tank (407) for supplying water and a cooler (408) for cooling the reaction water.

In addition, according to another embodiment of the present invention, the lumped fluorine compound gas separation and catalytic decomposition treatment apparatus is a first pipe leading from the catalytic reactor to the heat exchanger, or a second connecting from the heat exchanger to the reactant injection device Disclosed are a lumped fluorine compound gas separation and catalytic cracking treatment apparatus characterized by being insulated from a pipe or both of these pipes. The adiabatic pipe 402 is a catalytic reactor to maintain the exhaust gas temperature at a high temperature in order to prevent low temperature poisoning of the reactor and the pipe due to the by-product discharged from the catalytic reactor 301 through the heat exchanger 203 ( The pipe connected from the heat exchanger 203 to the stopper of the reactant injector 403 is insulated from 301.

In addition, the catalyst for catalytic reaction which can be used in the present invention and the like are also disclosed as follows.

According to one aspect of the present invention, there is provided a process for producing a toner, which comprises mixing at least one carrier selected from gamma-alumina, cetal-alumina, alpha-alumina, the catalyst for the SF 6 to remove such a manner that the parts by weight of gallium and zinc, 1-80 parts by weight of the impregnation are disclosed.

According to one embodiment, the gallium is derived from a gallium nitrate solution (Ga (NO 3 ) 3 ), a gallium chloride solution (GaCl 3 ), a gallium sulfate solution (Ga 2 (SO 4 ) 3 ) It is. The zinc may be zinc nitrate solution (Zn (NO 3 ) 2 ), zinc chloride solution (ZnCl 2 ), gallium sulfate solution (ZnSO 4 ), zinc carbonate ([ZnCO 3 ] 2 [Zn (OH) 2 ] 3 ) Or a mixture of two or more thereof.

According to another embodiment, the catalyst is post-treated with 0.2-1 M sulfuric acid solution. By this post treatment, the durability of the catalyst can be greatly improved.

According to another aspect of the present invention, there is provided a process for preparing a catalyst for removing SF 6 , comprising: (a) impregnating and drying a mixed solution of a gallium precursor and a zinc precursor in a carrier; and (b) firing the dried catalyst. A method is disclosed.

(B) impregnating the carrier with a mixed solution of (a) a gallium precursor and a zinc precursor; (b-1) firstly calcining the dried catalyst; (b-2) the method of manufacturing steps, and (b-3) SF 6 catalyst for removing comprises the step of the secondary sintering the acid-treated catalyst is disclosed that.

According to one embodiment of this aspect, the gallium precursor and the zinc precursor may be used in an amount of 1-80 parts by weight of gallium and 1-80 parts by weight of zinc, based on 100 parts by weight of the carrier.

According to another embodiment, the carrier can be gamma-alumina, theta-alumina, alpha-alumina, beta-alumina, boehmite, bosemite or a mixture of two or more thereof. The gallium precursor may be a gallium nitrate solution (Ga (NO 3 ) 3 ), a gallium chloride solution (GaCl 3 ), a gallium sulfate solution (Ga 2 (SO 4 ) 3 ) or a mixture of two or more thereof. The zinc precursor may be zinc nitrate solution (Zn (NO 3 ) 2 ), zinc chloride solution (ZnCl 2 ), gallium sulfate solution (ZnSO 4 ), zinc carbonate ([ZnCO 3 ] 2 [Zn (OH) 2 ] 3 ) or a mixture of two or more thereof.

According to another embodiment, the method for preparing the catalyst for removing SF 6 may further include (c) molding the catalyst calcined in the step (b) or (b-3) using a binder have.

Another aspect of the present invention relates to an exhaust gas purifying apparatus comprising (A) an exhaust gas inlet, (B) a water inlet, (C) a gas mixture for vaporizing the injected water and mixing the vaporized water vapor and the introduced exhaust gas at a first high temperature (D) a catalytic reaction section through which the mixed gas passes, and a second heating means which maintains the catalytic reaction layer at a second high temperature; (E) the temperature of the heat exchanger to lower, and (F) directed to a SF 6 liquid removing apparatus comprising a cleaning section for cleaning the lower the temperature the gas mixture.

(B) introducing water; (c) vaporizing the injected water and supplying the vaporized water vapor and the introduced exhaust gas at a first high temperature (D) passing the mixed gas through a catalytic reaction layer maintained at a second high temperature, (e) lowering the temperature of the mixed gas passing through the catalytic reaction layer, and (f) the present invention relates to SF 6 removal comprises washing liquid to lower the gas mixture.

In such an apparatus and method, according to one embodiment, the catalyst is added to at least one carrier selected from gamma-alumina, theta-alumina, alpha-alumina, beta- alumina, boehmite or boehmite, 1 to 80 parts by weight of gallium and 1 to 80 parts by weight of zinc are impregnated. The gallium may originate from a gallium nitrate solution (Ga (NO 3 ) 3 ), a gallium chloride solution (GaCl 3 ), a gallium sulfate solution (Ga 2 (SO 4 ) 3 ) or a mixture of two or more thereof. The zinc may be zinc nitrate solution (Zn (NO 3 ) 2 ), zinc chloride solution (ZnCl 2 ), gallium sulfate solution (ZnSO 4 ), zinc carbonate ([ZnCO 3 ] 2 [Zn (OH) 2 ] 3 ) Or a mixture of two or more thereof. In addition, the catalyst may be post-treated with a 0.2-1.0 M sulfuric acid solution.

According to another embodiment, the first high temperature at which the vaporized water vapor and the exhaust gas are mixed may be 250-350 캜. When the temperature was out of the range, no conversion effect was observed at 500-550 ° C.

According to another embodiment, the content of the vaporized water vapor in the mixed gas may be 2 to 18% by volume.

According to another embodiment, the second high temperature at which the catalytic reaction layer is maintained may be 350-900 ° C. When it is out of this temperature range, it was confirmed that the removal efficiency is greatly reduced or the conversion activity of the catalyst is greatly reduced by the catalyst phase change.

According to another embodiment, the wet cleaning part preferably comprises cooling water and an alkali-based additive. This is because it is possible to more effectively remove by-products generated through the catalytic reaction layer.

According to another aspect of the invention relates to optimization of the SF 6 decomposition catalyst. According to one embodiment, an exhaust gas inlet (1) through which an exhaust gas containing SF 6 gas is introduced; A water injection part (2) for causing a hydrolysis reaction; A gas mixing part (4) for vaporizing the water injected through the water injecting part and mixing the water with the exhaust gas introduced through the exhaust gas inlet; A catalytic reaction part including a gas mixture of vaporized water vapor and exhaust gas and a heating device for setting a temperature of the catalytic reaction layer to a desired high temperature; A wet cleaning unit 10 for removing by-products generated while passing through the catalytic reaction layer; And the SF 6 treatment device including a discharge port (11) to export the treated off-gas is disclosed.

The present invention can efficiently remove the waste gas remaining after the pre-treatment and pre-treatment, and after the pre-treatment to efficiently collect and regenerate a large amount of fluorine compound gas generated from power infrastructure, such as semiconductors and heavy electric equipment, transmission and distribution facilities, power equipment manufacturers, etc. In this process, by-products of the fluorine compound gas generated in this process can be effectively treated through a washing apparatus, and the durability of the equipment can be improved through an insulation and a cooler to prevent corrosion of the catalytic reactor and the downstream equipment.

The aggregated fluorine compound separation and catalytic decomposition treatment apparatus according to the present invention is widely used throughout the industry for the separation and removal of global warming materials for treating waste gas of fluorine which is disposed of after recycling and regeneration of fluorine that is disposed of as waste resources. By creating a Clean Development Mechanism (CDM) as much as the reduced greenhouse gases, future carbon emissions trading (EU ETS) projects are possible, creating added value that can turn profits from the cost of processing greenhouse gas materials into profits. And low carbon green growth policies.

Figure 1 is a schematic diagram showing the configuration of an aggregated fluorine compound separation and catalytic decomposition treatment apparatus according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing the configuration of a separation device according to an embodiment of the present invention.

Hereinafter, an apparatus for separating and catalytically treating a fluorine-containing gas according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. 1 is a schematic view showing the configuration of an apparatus for separating and catalyzing the gathering fluorine compound gas according to an embodiment of the present invention. Gathering fluorine compound gas separation and catalytic decomposition treatment apparatus according to an embodiment of the present invention includes a pre-treatment means 100, heat exchange and mixing means 200, catalytic decomposition means 300 and wet after-treatment means (400). .

First, the pre-treatment means 100 is a vehicle tank lorry or a large amount of waste fluorine gas, that is, less than 95% After condensing in the storage tank 101 by the movable mobile tank 103, the fluorine compound gas secured in the storage tank 101 is moved to the separator 102 to be separated into high concentrations into fluorine compounds that can be recycled. To store and move to the cylinder 105, and the waste fluorine compound which has not been regenerated is moved to the storage tank 101 and stored. That is, the storage tank 101 serves as a buffer for stabilizing waste fluorine compound gas of various concentrations collected and collected from the external mobile tank 103 or the small mobile high pressure vessel, and is not separated from the separator 102. It serves to store fluorine gas.

As described above, after treating the high concentration waste fluorine compound gas in the storage tank 101, in order to process the remaining amount of fluorine compound gas remaining in the storage tank 101 by installing a fan for the outside air storage tank 101 The outside air is introduced from the lower part and the remaining amount is sent to the catalytic reactor 301 for catalytic decomposition.

In addition, as described above, after treating the high concentration waste fluorine compound gas in the storage tank 101, in order to remove the dust (dust) and water in the storage tank 101 by installing a fan 106 for the outside air storage tank The outside air is introduced from the upper portion 101 to open the valve 107 and discharged to the outside through the bottom vent line of the storage tank 101.

The vacuum pump 104 between the storage tank 101 and the separation device 102 so as to apply a vacuum to the pipe in which the fluorine compound gas is introduced before the fluorine compound gas is introduced into the separation device 102 in the storage tank 101. After installing a vacuum to remove outside air and trace impurities in the pipe, the fluorine compound gas in the storage tank 101 is introduced into the separator 102 to improve the separation yield of the fluorine compound. .

Secondly, as shown in FIG. 2, which is a schematic diagram showing the configuration of the separator 102 shown in FIG. 1, the separator 102 is an acid-based material in the fluorine compound gas introduced from the storage tank 101. , Moisture and dust are removed while passing through the adsorption reactor 1021 and the dust removal filter device 1022, and the membrane module 1027 and the membrane module according to the concentration and flow rate of the fluorine compound flowing into the separator 102 In order to control the pressure and temperature of the inlet fluorine compound to control the separation yield of (1028) through the pressure gauge (1024) and thermometer (1026) using a pressure regulator (1023) and a temperature controller (1025) After the adjustment, the high concentration of fluorine compound gas flowing into the separation membrane module 1027 and the separation membrane module 1028 and passing through the separation module is separated and passed through the fluorine compound flowmeter 1029 to flow into the cylinder 105, and the separation module Pass through The fluorine compound and impurities that are not installed are installed to flow into the storage tank 101.

The adsorption reactor 1021 removes the acid (SO 2, etc.) mixed in the fluorine compound gas introduced from the storage tank 101 by using an alkali-based adsorbent and a zeolite-based adsorbent, and then removes the dust to the filter device 1022. Inflow.

The dust removal filter 1022 is a dust removal filter capable of a filtration type filter capable of removing dust of 0.001-1 μm or less in order to remove dust in the fluorine compound gas and dust of an adsorbent particle of 0.001-1 μm or more. Install device 1022.

The separation membrane modules 1027 and 1028 have a separation efficiency of 20-90% for separating and concentrating high concentration of waste fluorine compound gas, and less than 95% of fluorine compound gas is separated and concentrated at a high concentration of 95% or more. And stored in the cylinder 105, and the fluorine compound waste gas (gas less than 95%) that does not pass through the separation module flows into the storage tank 101 to be separated in the catalytic decomposition reactor 301 for decomposition. In the above, the separation efficiency is a kind of separation yield, which means that the separation efficiency passed through the separation module is 20-90% according to the purity of the gas to be separated. If the purity is high, the separation yield is low, and if the purity is low, the separation yield is increased.

The separation device 102 is used together with the catalytic cracking reactor 301 to separate and concentrate less than 95% fluorine oxide gas to 95% or more as a separation module, and to dispose of the waste fluorine oxide gas that cannot be reused by the catalytic decomposition method. Provides the ability to

Third, the heat exchange and mixing means 200 in the storage tank 101 of the pretreatment means 100 through the flow meter 202 to move a constant amount of a high concentration of fluorine compound gas to the mixer 201, room temperature The outside air is transferred to the heat exchanger 203 through the outside air inlet fan 204, converted to a high temperature outside air, and then moved to the mixer 201 and mixed with a predetermined amount of fluorine compound gas to produce a high temperature low concentration fluorine compound gas. It is moved to the catalytic reactor 301.

The heat exchanger 203 of the present invention passes the outside air at room temperature from the air inlet fan 204 from the right side to the left side in the heat exchanger 203 through a pipe, and is discharged through the catalytic reactor 301. Exhaust gas is a method of indirectly heating the outside air at room temperature through a high-temperature exhaust gas while passing from the lower portion of the heat exchanger 203 to the upper portion.

The mixer 201 heat-insulates the entire mixer to maintain the temperature of the mixed gas mixed with the fluorine compound gas introduced through the heat exchanger 203 and the fluorine compound gas introduced into the high temperature through the heat exchanger 203, and the mixer ( 201) A perforating network is installed as a mixing means or a certain amount of perforating material is filled.

Fourth, the catalytic cracking means 300 is a heating device 302 and the reaction water to facilitate the oxidation and hydrolysis catalytic reaction of the fluorine compound gas mixed at a high temperature and low concentration in the mixer 201 in the catalytic reactor 301 Injection section 303; And the catalyst modules 3011 and 3012 on which the catalyst is loaded are sealed to the inner wall of the catalyst reactor 301 so that the fluorine compound gas can be removed in the catalyst reactor 301. And at least one catalyst group for causing the fluorine compound gas introduced into 301 to be oxidized, hydrolyzed, oxidized and gasoline-reacted.

As shown in FIG. 3, which is a cross-sectional view of the catalyst module installed in the catalytic reactor 301 shown in FIG. 1, the catalyst modules 3011 and 3012 have pellet or ball type catalysts in the catalyst module in a square plate. Tie-type zigzag-type catalyst module 3012 into a box-type catalyst reactor 301 or a honeycomb layer of catalyst module 3011 into a catalyst reactor 301 to be installed in a catalytic reactor 301 Process the gas.

The catalyst modules 3011 and 3012 are made of stainless steel and ceramic materials in consideration of the corrosiveness caused by by-products of the fluorine compound gas.

The catalysts supported in the catalyst modules 3011 and 3012 are mainly solid acid catalysts, and are made of metal additives such as Ni, Co, P, Fe, Ti, Zn, La, Ce, Ga, etc. using alumina as a base catalyst as a carrier. Catalyst or phosphate-based catalyst, zirconia-based catalyst, silica-based catalyst, or a catalyst in which inorganic acids such as sulfuric acid, phosphoric acid and boric acid are supported on alumina, or zeolite, γ-Al 2 O 3 , SiO 2 -Al 2 O 3 , V 2 O 5 / Al 2 O 3 , TiO 2 -SiO 2, fluorinated (fluorinated) TiO 2, Pt / ZrO 2 -TiO 2, Cr 2 O 3 / ZrO 2, BPO 4 , etc. of the catalyst alone or in combination of two or more The catalyst prepared by laminating and mixing is put into the catalyst modules 3011 and 3012 to be oxidized and hydrolyzed.

The production form of the catalyst includes a pellet, a ball, a honeycomb form, and in particular, the pellet bar method includes a claw and a star form, an inner penetrating state, etc., which have changed the pellet side line, and the decomposition effect becomes more penetrating into the pellet. Is further improved.

Catalytic decomposition is a phenomenon in which gas molecules adhere and oxidize and hydrolyze on a solid surface. In general, contaminated gas containing fluorine compound gas is decomposed only when it is heated and hydrolyzed at the reaction temperature of 1000 ℃ or higher, but when a catalyst is used, oxidation and hydrolysis occurs at the reaction temperature of 500-800 ℃, resulting in lower reaction temperature. As a result, the catalytic energy consumption can be more economical than conventional pyrolysis.

In this way, the fluorine compound gas introduced into the catalyst modules 3011 and 3012 is removed by hydrolysis and partial oxidative decomposition through the fluorine compound decomposition action of the catalyst together with the water injected through the reaction water injection unit 303. For example, in the case of fluorine compound gas, the main reaction is represented by the following Chemical Formula 1.

[Formula 1]

SF 6 + 3H 2 O → SO 2 + 6HF

2NF 3 + 3H 2 O → NO + NO 2 + 6HF

CF 4 + 2H 2 O → CO 2 + 4HF

2CHF 3 + 2H 2 O + O 2 → 2CO 2 + 6HF

C 2 F 6 + 3 H 2 O + 1/2 O 2 → 2CO 2 + 6 HF

C 3 F 8 + 4H 2 O + O 2 → 3CO 2 + 8HF

In this decomposition reaction, the complex pollutants from which fluorine compounds (SF 6 , CF 4 , NF 3 ) gas are removed are decomposed into gases such as water vapor, HF, and S that are easily dissolved in the washing water, and some nitrogen oxides (NO, NO 2 ) and the like are introduced into the post-treatment means 400.

Fifth, the aggregated fluorine compound gas separation and catalytic cracking treatment apparatus according to the present invention is a post-treatment means for dissolving and removing the contaminated reaction product generated during the catalytic decomposition by the catalytic cracking means (300) It further includes. The contaminating reaction product includes at least one of sulfur oxides (SO 2 ), fluorine compounds (HF), and nitrogen oxides (NO, NO 2 ).

1 is a schematic view showing a processing means of the facility. The post-treatment means 400 is configured to pass through the reactant injection device 403 through the heat insulation pipe 402, and then discharged to the chimney 410 through the cleaning device 401.

In order to prevent the low temperature poisoning of the reactor and the piping due to the by-products discharged from the catalytic reactor 301 through the heat exchanger 203, the heat insulating pipe 402 is connected to a catalytic reactor 301 are connected to a pipe connected to the heat exchanger 203 and a pipe connected to the reactant injector 403 interrupter are insulated.

The reactant injector 403 includes three injectors, the upper end of which is connected to a reactant storage tank 404 that stores an acidic substance, and a stopper reactant storage tank that stores cooling water and reactant water ( It is connected to the 405 is installed, the lower end is connected to the reactant storage tank 406 for storing the alkaline material is installed.

The cleaning device 401 is a reaction water storage tank 407 and the storage tank 407 that stores the reaction water to neutralize and cool the acid and alkaline flue gas and the treated water reacted in the reactant storage tank 403 Connected to the cooler 408 for cooling the reaction water is installed, the exhaust gas in which the cooling and contaminants are cleaned in the cleaning device 401 is installed to be discharged to the chimney 410 through the fan 409.

The material of the cleaning device 401 is made of stainless steel and FRP (Fibre-reinforced plastic) with light and corrosion resistance. FRP, the main material, is a ship-making material. The production method of equipment is made of padding, drying, and padding, which is resistant to corrosion and easy to replace and repair in case of partial leakage. It is easy to change the configuration of equipment.

The cooler 408 operates below the exhaust gas temperature of 39 ° C. in order to prevent the reactant of the exhaust gas of the scrubber 401 from being deteriorated due to the high temperature, and to prevent the fumes of exhaust gas, and to produce the scrubber 401. In order to ensure a safe FRP safety temperature is connected to the cooling water storage tank 405, the reaction water storage tank 407 is installed.

The wet post-treatment means 400 is injected with reactants in the reactant storage tank 404 which stores acidic substances to remove by-products discharged from the catalytic reactor 301 through the heat exchanger 203 and the adiabatic pipe 402. By supplying to the apparatus 403 by the gas-liquid contact to the high temperature reaction of the by-products supplied from the catalytic reactor 301, the cooling water is supplied from the cooling water storage tank 405 to the reactant injection device 403 in order to lower the temperature of the exhaust gas By lowering the exhaust gas temperature by the gas-liquid contact, by supplying the reactant injector 403 from the reactant storage tank 406 for storing alkaline substances by the gas-liquid contact by-products supplied from the catalytic reactor 301 by low-temperature wet reaction To be processed.

The by-products reacted while passing through the reactant injector 403 are neutralized with the reaction water while passing through the scrubber 401, and the exhaust gas temperature is lowered to a temperature at which white smoke does not occur. And is discharged through the chimney 410.

Exhaust gas containing sulfur oxide (SO 2 ), fluorine compound (HF), nitrogen oxides (NO, NO 2 ), and the like in the catalytic reaction means 300 is injected through the heat exchanger 203 and the adiabatic pipe 402. It is introduced into the apparatus 403, and reacts with and removed from the reaction water injected from the acidic reactant storage tank 404, the coolant storage tank 405, the alkaline reactant storage tank 406, the reaction water storage tank 407. In this case, SF 6 , CF 4 , NF 3 The sulfur oxide (SO 2 ), fluorine compound (HF), nitrogen oxide (NO, NO 2 ) generated during the catalytic decomposition is represented by the following formula. Chemical reaction by the nitrogen compound (NO, NO 2 ) absorption is represented by the following formula (2).

[Formula 2]

NO + NO 2 + 2H 2 SO 4 → 2NOHSO 4 + H 2 O

The nitrogen compound (NO, NO 2 ) reaction is an acid series such as sulfuric acid stored in the reactant storage tank 404 at the rear end of the heat exchanger 203 and the top of the reactant injector 403 so that the exhaust gas reaction temperature may be higher than 250 ° C. Inject the reaction.

The exhaust gas containing NOHSO 4 is injected into the cooling water in the cooling water storage tank 405 at the stop of the reactant injector 403 to reduce the exhaust gas temperature, NOHSO 4 is an absorption chemical reaction occurs as shown in the following formula (3) ,

(3)

NOHSO 4 + H 2 O → HNO 2 + H 2 SO 4

2HNO 2 ↔ H 2 O + NO + NO 2

3HNO 2 ↔ H 2 O + 2NO + HNO 2

2NO 2 + H 2 O ↔ HNO 3 + HNO 2

3NO 2 + H 2 O ↔ 2HNO 2 + NO

The H 2 SO 4 , HNO 3 is absorbed and treated in the cooling water, and some HNO 2 , NO, NO 2 are stored in the alkali (Na-based, Ca-based, Mg-based, ammonia-based) reactant storage tank 406 The alkali-based reactant is injected from the lower part of the reactant injector 403, and the alkali-based reactant and the by-products (HNO 2 , NO, NO 2 ) undergo an absorption chemical reaction as shown in the following formula (4).

[Formula 4]

2NO 2 + 2NaOH → NaNO 2 + NaNO 3 + H 2 O

2NO 2 + 2NH 4 OH → NH 4 NO 2 + NH 4 NO 3 + H 2 O

4NO 2 + 2Ca (OH) 2 → Ca (NO 2 ) 2 + Ca (NO 3 ) 2 + 2H 2 O

Ca (OH) 2 + NO + NO 2 → Ca (NO 2 ) 2 + H 2 O

Mg (OH) 2 + NO + NO 2 → Mg (NO 2 ) 2 + H 2 O

HNO 2 + NH 3 (aq) → NH 4 NO 3

The sulfur oxide (SO 2 ) treatment method is represented by the following formula (5).

[Chemical Formula 5]

S + O 2 → SO 2

SO 2 + 1/2 O 2 → SO 3

SO 3 + H 2 O → H 2 SO 4

SO 2 + 2 NaOH → H 2 O + Na 2 SO 3

SO 2 + Na 2 SO 3 + H 2 O → 2NaSOH 3

The fluorine compound (HF) is represented by the following formula (6).

[Formula 6]

HF + H 2 O → HF (Aq)

The reaction water storage tank 407 stores the cooling water and alkali-based reaction water as the reaction water to neutralize the acidic waste water, and nitrogen oxides (NO, NO 2 ), When sulfur oxides (H 2 SO 4 ), fluorine compounds (HF), etc. are dissolved, the acidity of the reaction water solution may be changed from alkali to neutral, so that clean alkali-based reactants stored in the alkali-based reactant storage tank 406 are piped. Through the reactant injection device 403 through the reaction water storage tank 407, the contaminant neutralized in the reaction water storage tank 407 when the pH of the waste water is neutral, the waste water through the final outlet valve 411 Discharged to the treatment plant.

The integrated fluorine compound gas separation and catalytic decomposition treatment apparatus is modularized so that pipes and respective devices can be separately manufactured to facilitate replacement of the catalytic reactor 301 and the heat exchanger 203 due to fluorine gas by-products. .

Although the present invention has been described as a specific preferred embodiment, the present invention is not limited to the above embodiment. In addition, the present invention will be described in detail with reference to the following Examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example  1: Preparation of Catalyst

22 mL of a gallium nitrate solution (Ga (NO 3 ) 3 ) and 8 mL of a zinc sulfate solution (ZnSO 4 7H 2 O) were mixed with 35 mL of deionized water, and this was impregnated with gamma- 40 parts by weight of gallium and 5 parts by weight of zinc were mixed with each other, and the mixture was dried at room temperature for 24 hours to prepare a catalyst. Then, the prepared catalyst was dried at 120 ° C. for 4 hours, then heated at a rate of 10 ° C./min and calcined at 700 ° C. for about 2 hours. In order to mold the catalyst raw material as described above, alumina sol of inorganic binder series was used and 5 parts by weight of alumina sol was mixed with 100 parts by weight of alumina and kneaded to prepare a tablet type catalyst.

Example  2

In order to simulate the gas containing flue gas, SF 6 , N 2 , and Air were injected with a fixed amount of gas using a mass flow controller. A water inlet for supplying water to the pipe through which the exhaust gas flows is installed, and then a predetermined amount of water can be introduced into the pipe using a metering pump. The water inlet was installed at the upstream of the catalytic reactor and the preheating period was set so that the introduced water could be vaporized and mixed well with the exhaust gas, and the set temperature was maintained at 250-350 ° C. A mixing chamber was installed in front of the catalytic reactor so that the gas and the vaporized water were mixed well. The catalyst prepared above was pulverized and loaded on a standard size range of 150-250 μm suitable for the experiment to obtain a uniform size catalyst. Then, 1.2 g of the catalyst was filled in the catalytic reactor, and a heater was installed outside the catalytic reactor Thereby constituting a catalytic reaction unit.

The reaction conditions and the gas composition are as shown in Table 1. Since the reaction gases passing through the catalytic reaction layer contain toxic by-products, the temperature was lowered through the heat exchanger and then introduced into the wet scrubber. The wet scrubbing zone effectively treated various kinds of acidic gases generated as byproducts by treating the gas with water containing caustic soda. In the catalytic cracking process of SF 6 , the concentration of the reaction gas and the product gas at the outlet of the reactor was measured using a gas chromatography equipped with a thermal conductivity detector connected on-line. The removal efficiency of SF 6 was calculated from Equation 1 Respectively.

[Equation 1]

Sulfur hexafluoride removal efficiency SF 6 Conversion) =

Figure pat00001

- F SF6in : concentration of sulfur hexafluoride before reaction

- F SF6out : concentration of sulfur hexafluoride after reaction

Temperature (℃) 300-900 Space velocity (mL / g - cat .? H) 5,000 Gas composition (vol%) SF 6 0.5 H 2 O 12.5 O 2 - N 2 Balance

SF 6 is efficiently removed as the temperature is increased in the process conditions as shown in Table 1 containing H 2 O, already exhibits a conversion effect at 450 ℃, showing a conversion rate of 98% at 650 ℃, already at 700 ℃ It was confirmed that the conversion was 100%.

Comparative example  1-2

In Comparative Example 1, a catalyst was prepared in the same manner as in Example 1, except that a zinc sulfate solution (ZnSO 4 7H 2 O) was not added, and a gallium-based catalyst having a weight of 40 wt% based on the weight of alumina was prepared. The experiment was carried out in the same manner as in Example 2. On the other hand, in Comparative Example 2, a catalyst was prepared in the same manner as in Example 1, except that a gallium nitrate solution (Ga (NO 3 ) 3 ) was not added and a catalyst in which Zn reached 5 wt% based on the weight of alumina. The experiment was carried out in the same manner as in Example 2.

Unlike the case of Example 2, Comparative Example 1 and Comparative Example 2 did not show a conversion effect at 450 ℃, it was confirmed that does not reach 100% conversion even at 700 ℃.

Example  3

The catalyst prepared in Example 1 was treated with sulfuric acid to carry out pretreatment with sulfuric acid to reduce poisoning of the catalyst by acidic gas generated as a byproduct. The procedure of Example 1 was repeated except that the sintered catalyst was impregnated with secondary sulfuric acid. In order to increase the acid strength of the solid acid catalyst, the calcined catalyst was impregnated with 5.5 mL of a 0.2 M sulfuric acid aqueous solution and then dried at room temperature for 24 hours. Thereafter, the dried material was dried at 120 ° C. for 4 hours, then heated to 10 ° C. per minute and calcined at 700 ° C. for 2 hours to prepare a sulfuric acid-treated catalyst according to the present invention.

Although there was no significant difference in the initial catalytic decomposition performance, it was confirmed that the sulfuric acid pretreatment catalyst is more durable in terms of long term poisoning through long time operation, thereby maintaining a higher conversion rate for a longer time.

Comparative example  3

A catalyst was prepared in the same manner as in Example 1, and the reaction apparatus was the same, but a bypass line was connected to a gas pipe to be discharged without passing through a wet processing apparatus. After passing through the catalyst layer, the conversion of SF 6 was confirmed, . The results are shown in Table 2.

Example 2 Comparative Example 3 Conversion Rate SF 6 98% 98% density SO 2 0-3 ppm 1,000-1,500 ppm SO 2 F 2 10-20 ppm 1,900-2,600 ppm

Comparative example  4

The catalyst was prepared in the same manner as in Example 1 except that the experiment was conducted under the condition that no water was introduced under the experimental conditions of Example 2. As a result, it was confirmed that the conversion rate did not reach 60% when no water was introduced, while the conversion rate reached almost 100% when water was introduced.

Description of the Related Art
101: storage tank 102: separator
103: moving tank 104: vacuum pump
105: cylinder 106: fan
107: valve 201: mixer
202: flow meter 203: heat exchanger
204: fan 301: catalytic reactor
302: heating device 303: reaction water injection unit
401: cleaning device 402: heat insulation pipe
403: reactant injector 404: reactant storage tank (acid series)
405: cooling water storage tank 406: reactant storage tank (alkali series)
407: reaction water storage tank 408: cooler
409: fan 410: chimney
411 valve 1021 adsorption reactor
1022: filter unit for removing dust 1023: pressure regulator
1024: pressure gauge 1025: temperature controller
1026: thermometer measuring instrument 1027: membrane module
1028: membrane module 1029: separation fluorine compound flow meter
1030: unseparated gas mass flow meter

Claims (13)

(a) pretreatment means (100) for collecting and stabilizing and storing waste gas containing fluorine compounds, concentrating and regenerating some of them in a high concentration, and storing the remaining non-regenerated waste gas again;
(b) heat exchange and mixing means (200) for diluting the non-regenerated waste gas to a high temperature from the pretreatment means;
(c) catalytic cracking means (300) for catalyzing the non-regenerated waste gas diluted to a high temperature at a high temperature;
(d) wet post-treatment means (400) for removing by-products in the fluorine compound gas discharged from said catalytic decomposition means. (a) a storage tank 101 for receiving and stabilizing fluorine compound gas from an external mobile tank, and a portion of the fluorine compound gas introduced from the storage tank is concentrated and recycled to a high concentration, and the remaining non-regenerated fluorine compound gas is not recycled. Pre-treatment means (100) including a separation device 102 for recovering to the storage tank;
(b) an outside air inlet fan 106 for introducing outside air from the outside, a mixer 201 for mixing the outside air and the fluorine compound gas introduced into the storage tank, and heated to a high temperature before the outside air enters the mixer A heat exchanger and mixing means (200) including a heat exchanger (203) for mixing the fluorine compound gas introduced into the storage tank with the heated outside air and diluting it to a high temperature;
(c) a catalytic reactor 301, a heating device 302 for heating the hot dilute fluorine compound gas to a catalytic reaction temperature before the fluorine compound gas diluted to a high temperature in the mixer flows into the catalytic reactor, and the high temperature dilution Catalytic decomposition means (300) comprising a reaction water inlet (303) for introducing the reaction water into the catalytic reactor with the fluorine compound gas;
(d) an aggregated fluorine compound gas separation and catalytic cracking apparatus comprising wet post-treatment means 400 for removing by-products in the fluorine compound gas discharged from said catalytic cracking means,
In the heat exchanger, a heat exchange is performed between the outside air introduced from the outside air inlet fan and the high temperature exhaust gas discharged from the catalytic reactor. 3. The method of claim 1 or 2, wherein the pretreatment means further comprises a vacuum pump 104 for applying a vacuum to the pipe between the storage tank and the separator device. Catalytic cracking apparatus.
The vacuum pump serves to facilitate the separation of high concentration of fluorine compound gas from the storage tank by removing external air and trace impurities in the pipe at the beginning of operation. 4. The apparatus of claim 3, wherein the pretreatment means further comprises a cylinder (105) for storing the fluorine compound gas which has been concentrated and recycled to a high concentration. [5] The apparatus of claim 4, wherein the pretreatment means further comprises a fan 106 for introducing an outside air. 6. The apparatus of claim 5, wherein the pretreatment means further comprises a valve (107) for opening the vent line and the vent line below the separator. The method of claim 6, wherein the separator adsorption reactor 1021, the filter device 2022, the pressure regulator 1023, the pressure gauge 1024, the temperature controller 1025, the thermometer measuring instrument 1026, a plurality of membrane modules ( 1027 and 1028, a fluorine compound gas separation and catalytic cracking treatment apparatus comprising a regenerated fluorine compound gas flow meter (1029), a non-regenerated fluorine compound gas flow meter (1030),
The adsorption reactor and the filter device to remove the acidic substances, water and dust in the fluorine compound gas introduced from the storage device, respectively,
The pressure regulator and the temperature controller adjust the pressure and temperature of the incoming fluorine compound gas on the basis of the pressure measured from the pressure gauge and the temperature measured from the thermometer instrument, the concentration of the fluorine compound in the gas flowing from the separator And adjusting the separation yield of the plurality of membrane modules according to the flow rate,
The regenerative fluorine compound gas flow meter controls the amount of the concentrated fluorine compound gas that is concentrated and recycled into the cylinder,
And the non-renewable fluorine compound gas flow meter controls the amount of non-regenerated fluorine compound gas recovered to the storage device. The method of claim 7, wherein the heat exchange and mixing means further comprises a flow meter 202 for controlling the amount of fluorine compound gas flowing into the storage tank portion fluorine compound gas separation and catalytic decomposition treatment Device. The mixer of claim 8, wherein the mixer is thermally insulated to maintain a high temperature of the mixed gas mixed with the fluorine compound gas introduced through the heat exchanger and the outside air changed to a high temperature through the heat exchanger. A lumped fluorine compound gas separation and catalytic cracking apparatus characterized in that the perforated network is installed or the perforated material is filled with the mixing means. 10. The method of claim 9, wherein the outside air introduced from the outside air inlet fan 204 passes from one side of the heat exchanger to the opposite side, and the hot exhaust gas discharged from the catalytic reactor is carried out at the bottom of the heat exchanger. Aggregated fluorine compound gas separation and catalytic decomposition treatment device characterized in that the heat exchange is performed while passing through the upper portion. The method of claim 10, wherein the wet post-treatment means 400 is an acidic reactant storage tank 404, a coolant storage tank 405, an alkaline reactant storage tank 406, and the wet post-treatment means 400 Further comprising a reactant injection device 403 through which the exhaust gas discharged from the catalytic reactor can pass,
As the exhaust gas discharged from the catalytic reactor passes, the (1) acidic reactants, (2) from the (1) acidic reactant storage tank, (2) cooling water storage tank, and (3) alkaline reactant storage tank, respectively. (3) cooling water and (3) alkaline reactants are sequentially introduced into the reactant injector, and each of the by-products in the exhaust gas is removed by high temperature reaction with the acidic reactants in a gas-liquid contact manner, respectively (2) Wherein the temperature of the exhaust gas is lowered, and (3) the by-products in the exhaust gas are removed by low temperature reaction with the alkaline reactants in a gas-liquid manner. 12. The method of claim 11, wherein the wet post-treatment means 400 is a washing device 401 through which the exhaust gas discharged from the catalytic reactor can pass after the reactant injection device, the reaction for supplying the reaction water to the cleaning device Collecting fluorine compound gas separation and catalytic decomposition treatment device further comprises a water storage tank (407), a cooler (408) for cooling the reaction water. The apparatus of claim 12, wherein the lumped fluorine compound gas separation and catalytic cracking apparatus comprises: a first pipe leading from the catalytic reactor to the heat exchanger, or a second pipe running from the heat exchanger to the reactant injection device, or two of them. Gathering fluorine compound gas separation and catalytic decomposition treatment device characterized in that all two pipes are insulated.
KR1020110051893A 2011-05-31 2011-05-31 Apparatus for purifying or catalytically removing waste gas containing fluorinated compounds KR20120133292A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101482612B1 (en) * 2013-10-02 2015-01-14 한국과학기술연구원 Apparatus and method for recovery of sulfur hexafluoride
KR101514449B1 (en) * 2013-11-04 2015-05-04 세이브기술 (주) Apparatus for concentrating and pyrolyzing sulfur hexafluoride
CN115430251A (en) * 2021-06-04 2022-12-06 玛特普拉斯有限公司 Electronic industrial waste gas treatment device

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101482612B1 (en) * 2013-10-02 2015-01-14 한국과학기술연구원 Apparatus and method for recovery of sulfur hexafluoride
KR101514449B1 (en) * 2013-11-04 2015-05-04 세이브기술 (주) Apparatus for concentrating and pyrolyzing sulfur hexafluoride
CN115430251A (en) * 2021-06-04 2022-12-06 玛特普拉斯有限公司 Electronic industrial waste gas treatment device

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