WO1998001217A1 - Procede et equipement de decompositions d'hydrocarbures fluores - Google Patents

Procede et equipement de decompositions d'hydrocarbures fluores Download PDF

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Publication number
WO1998001217A1
WO1998001217A1 PCT/JP1996/001857 JP9601857W WO9801217A1 WO 1998001217 A1 WO1998001217 A1 WO 1998001217A1 JP 9601857 W JP9601857 W JP 9601857W WO 9801217 A1 WO9801217 A1 WO 9801217A1
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Prior art keywords
gas
reaction vessel
reaction
carbon
treated
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PCT/JP1996/001857
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English (en)
Japanese (ja)
Inventor
Chiaki Izumikawa
Kazumasa Tezuka
Kazuto Ito
Hitoshi Atobe
Toraichi Kaneko
Original Assignee
Dowa Mining Co., Ltd.
Dowa Iron Powder Co. Ltd.
Showa Denko K.K.
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Application filed by Dowa Mining Co., Ltd., Dowa Iron Powder Co. Ltd., Showa Denko K.K. filed Critical Dowa Mining Co., Ltd.
Priority to PCT/JP1996/001857 priority Critical patent/WO1998001217A1/fr
Publication of WO1998001217A1 publication Critical patent/WO1998001217A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

Definitions

  • the present invention relates to a method for efficiently decomposing fluorocarbons, especially perfluorocarbon or hydrofluorocarbon having about 1 to 5 carbon atoms, and a simple apparatus therefor.
  • Japanese Unexamined Patent Publication No. Hei 6-293350 discloses that magnets are heated by applying a microwave to the inside of the applicator, and the fluorocarbon is decomposed by contacting the gas with the heated magnets. A method for doing so is disclosed.
  • Japanese Unexamined Patent Application Publication No. Hei 7-244255 discloses that a mixture of a carbonaceous material and an oxide or salt of an alkaline earth metal is irradiated with a microphone mouth wave to generate heat, and the heat is generated. Disclosed is a method for decomposing alpha by contacting fluorocarbon gas with the mixture. Purpose of the invention
  • an object of the present invention is to develop an industrial method for efficiently decomposing carbon fluorides having no chlorine group, such as perfluorocarbon and hide-mouth fluorocarbon. Disclosure of the invention
  • the above-mentioned problem is that the gas of perfluorocarbon or hydrofluorocarbon is added to a reactant composed of a carbonaceous solid material and an alkaline earth metal compound at a temperature of 300 or more and at a temperature of 200 or more. It was found that the solution can be achieved by contacting in the presence of gaseous oxygen of vol.% or less (not including 0%). More specifically, a gas to be treated containing perfluorocarbon or fluorocarbon is continuously placed in a reaction vessel that is fully immersed in a reaction (1) consisting of a carbonaceous solid material and an alkaline earth metal compound.
  • the exhaust gas after the reaction is continuously or intermittently discharged from the reaction vessel while being transported intermittently or intermittently, so that the oxygen concentration in the gas to be treated becomes 20 vol.% Or less.
  • Oxygen into the gas to be treated before entering the reaction vessel (1), and transferring the heat required to decompose the perfluorocarbon or the hydrofluorocarbon from the outside of the reaction vessel to the reaction zone, or Inside the container It was found that the carbon fluoride gas could be efficiently decomposed by transmitting it from the side to the reaction zone.
  • CO may coexist in the exhaust gas.
  • a heat-resistant alloy or a corrosion-resistant alloy such as stainless steel or a nickel-based alloy can be used. If the material is resistant to fluorine or hydrogen fluoride, the ceramic can be used. Boxes (for example, ceramics using aluminum fluoride) can also be used. Then, this reactor is installed in a furnace that can maintain the temperature of the furnace atmosphere at a required temperature, and the heat in the furnace can be transferred to the reactants in the container through the container wall.
  • a reaction vessel loaded with a reaction ⁇ ⁇ composed of a carbonaceous solid material and an alkaline earth metal compound is provided.
  • a gas inlet for gas to be treated provided in the reactor, a gas outlet provided for discharging gas after reaction from inside the reaction vessel, a furnace for accommodating the reaction vessel, and an atmosphere temperature in the furnace.
  • an exhaust gas oxidizer connected to piping and a device for decomposing carbon fluorides consisting of As the reaction vessel, one composed of a heat-resistant alloy or a corrosion-resistant alloy as described above can be used.
  • a carbon fluoride-containing gas source for example, a carbon fluoride-containing gas generated in a semiconductor manufacturing process and containing an appropriate amount of oxygen can be used.
  • Figure 1 is an equipment layout diagram showing an example of an apparatus for implementing the method of the present invention.
  • Fig. 2 shows another example of the exhaust gas path section of the device for implementing the method of the present invention. It is a device arrangement system diagram.
  • FIG. 3 is a device arrangement system diagram showing another example of the target gas introduction section for implementing the method of the present invention.
  • FIG. 4 is a schematic cross-sectional view of a reaction vessel part showing an example of heating a reaction vessel from inside the reaction vessel according to the method of the present invention.
  • FIG. 5 is a schematic sectional view of a reaction vessel part showing another example of heating a reactant from inside the reaction vessel according to the method of the present invention.
  • FIG. 6 is a diagram showing an example of performing heat exchange between the gas to be treated before entering the reaction vessel and the exhaust gas flowing out of the reaction vessel in carrying out the present invention.
  • Fig. 7 shows the inflow of CFC and the amount of CFC when the trifluorene (CFC) is decomposed in the case where the oxygen concentration in the gas to be treated is 0% and 10%. It is a figure showing the relation of the decomposition rate.
  • Figure 8 shows the flow rate of PFC and the decomposition rate of PFC when perfluoroethane (PFC) was decomposed when the oxygen concentration in the gas to be treated was 0% or 10%.
  • FIG. 8 shows the flow rate of PFC and the decomposition rate of PFC when perfluoroethane (PFC) was decomposed when the oxygen concentration in the gas to be treated was 0% or 10%.
  • FIG 9 shows the difference in the decomposition rate of perfluoroethane (PFC) when the heating method for the reactants is electric heater heating and when microwave heating is used.
  • PFC perfluoroethane
  • the present invention is a method for decomposing perfluoro-open carbon or hydrofluorocarbon having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, wherein the decomposed fluorine is absorbed by a reactant and the decomposed carbon ( Furthermore, hydrogen) migrates into the exhaust gas.
  • the perfluorocarbon or hydrofluorocarbon which can be suitably decomposed in the present invention is, for example, a substance which can be easily vaporized at room temperature (for example, a substance which is vaporized by accompanying an inert gas such as nitrogen gas). including) where, CF 4, C 2 F s , C 3 F 8, C - C 4 F 8 Etc., or a CHF 3.
  • a gas of perfluorocarbon or hydrofluorocarbon is added to a reactant composed of a carbonaceous solid material and an alkaline earth metal compound. It is important that the contact be made at a temperature of 0 ° C or higher and in the presence of 2 Ovol.% Or less (excluding 0%) of gaseous oxygen.
  • the carbonaceous solid material, one of the materials constituting the reactant is one or two selected from the group consisting of coke powder, charcoal charcoal, coal, raw pitch, charcoal, activated carbon, and carbon black. The above can be used, and the form is preferably powdery.
  • Alkaline earth metal compounds which are the other materials constituting the reactant include calcium, magnesium, rhodium or strontium oxide, calcium, magnesium, barium or strontium hydroxide, and One or two or more compounds selected from the group consisting of calcium carbonate, magnesium, barium and stomium carbonate or nitrate can be used, and preferably, calcium oxide is used. , Hydroxide, carbonate, or nitrate. Of these, quicklime, slaked lime, and limestone are advantageous because they are easy to handle.
  • reactants can be used by directly charging a powdery or granular carbonaceous solid material and a powdery or granular alkaline earth metal compound in a reaction vessel. It is preferable that the solid material and the powdered alkaline earth metal compound are mixed and this mixture is granulated into granules of a size that is easy to handle. As a result, the carbon and the alkaline earth metal compound are brought close to each other, and the specific surface area (surface area per unit weight) of the reactant is increased, thereby increasing the chance of contact with the gas to be treated. it can. For granulation, water or an organic binder is used, and the granulated product is dried or fired to obtain a granulated product having sufficient strength and porosity.
  • the coal used as raw material Solid carbon and alkaline earth metal are present in the granulated product, even though they may change to a solid material or a powdered alkaline earth metal compound or its morphology and compound type or other. As long as the components are present in the required ratio, they can contribute to the decomposition reaction of the present invention.
  • charcoal is used as a carbonaceous solid material
  • slaked lime is used as a raw earth metal compound
  • these powders are blended in a required ratio.
  • Water is added and kneaded.
  • Particle size eg 1 to 1 Omm, preferably!
  • pellets are produced during the firing process.
  • Most of the volatile components are removed, and slaked lime is completely transformed into oxidized calcium, so that highly pure pellets containing carbon (C) and calcium oxide (CaO) as main components can be obtained.
  • the thus obtained reactant composed of C and Ca0 has sufficient strength and is a porous material having a large specific surface area, so that it can be suitably used for carrying out the method of the present invention.
  • the weight ratio of the two materials is determined. Speaking of which, it is better to have the latter half more.
  • the molar ratio of carbon (C) in the carbonaceous solid material to the oxide (MO) of alkaline earth metal (M) in the alkaline earth metal compound 0.9 to 2,3, preferably 0.9 to 1.9, more preferably 4 to 1.9.
  • perfluorocarbon or hydrofluorocarbon is a compound that is more stable than fluorofluorocarbon and hydrofluorocarbon, and is not easily decomposed.
  • perfluorocarbon or hydrofluorocarbon is brought into contact with the reactant according to the present invention at a temperature of 300 ° C. or more in the presence of oxygen, it can be decomposed efficiently.
  • the lower limit of the required temperature is perfluorocarbon It depends on the type of bonfire or hydrofluor. If the required temperature is maintained, some decomposition occurs even in the absence of oxygen, but the decomposition efficiency is poor.
  • chlorine-containing fluorocarbon gas such as fluorocarbons, the presence of oxygen does not significantly contribute to the decomposition even when the same reactant is used. There is a phenomenon in which decomposition proceeds more.
  • the oxygen concentration in the gas to be treated is 0.5 to 20 vol.%, Preferably 2 to 15 vol.%, And more preferably 5 to 10 vol.%.
  • Air can be used as the oxygen source in the gas to be treated. Sometimes it may be a source of oxygen for oxygen C 0 2.
  • an inert gas such as nitrogen gas is used. It is convenient to supply the reactants continuously or intermittently as a carrier.
  • the carbon fluoride is diluted with an inert gas, which acts to carry away heat but does not substantially participate in the reaction.
  • oxygen concentration in the gas to be treated means the oxygen concentration in the total gas containing such an inert carrier gas when the gas contains such an inert carrier gas.
  • FIG. 1 shows an example of an apparatus for implementing the method of the present invention.
  • 1 in the figure is a metal reaction vessel (tube), which contains carbonaceous solid material and aluminum.
  • Reactant 2 consisting of lithium earth metal compound is loaded.
  • a reaction vessel 1 having a tubular shape is a vertical type, and a reactant 2 is mounted on a permeable floor 3 fixed in the vessel.
  • a tube made of stainless steel or nickel alloy can be used as the metal tube of the reaction vessel 1.
  • the reaction vessel 1 is set in a ripening furnace 4.
  • the heating furnace 4 shown in the figure uses an electric heater 5 that uses a heating element that generates heat when energized as a heat source.
  • the electric heater 5 raises the temperature of the furnace / atmosphere 6 to a required temperature.
  • the heat in the furnace is transferred to the reactant 2 via the metal reaction vessel wall.
  • the heat source is not limited to electric heaters as long as the temperature of furnace-atmosphere 6 can be raised to the required temperature.
  • high-temperature gas such as combustion exhaust gas can be used as the heat source.
  • the reaction vessel 1 installed in the heating furnace 4 is provided with the gas to be treated 7, and the gas to be treated 7 is connected by piping to the carbon fluoride vessel 8 containing PFC or HFC. Is done.
  • the carbon fluoride container 8 can be indirectly heated by the heating means 9 if necessary, and this heating increases the gas pressure in the carbon fluoride container 8.
  • the gas discharge pipe 10 from the container 8 is provided with a flow control valve 11.
  • an oxygen gas cylinder 12 and a nitrogen gas cylinder 13 are separately provided. From these, oxygen gas and nitrogen gas are supplied to flow control valves 14 and 15, respectively.
  • Oxygen gas is added to the carbon fluoride gas by leading it to the gas header 118 via the interposed gas discharge pipes 16 and 17 and leading the carbon fluoride to this header 118.
  • nitrogen gas as a carrier is mixed, and the gas to be treated mixed by the header 18 is sent to the gas to be treated inlet 7 of the reaction vessel 1 through the gas supply pipe 19. .
  • the present invention is not limited to this example, and a mixed gas obtained by premixing carbon fluoride, nitrogen and oxygen is prepared in one container, and this mixed gas is directly sent to the gas inlet 7 to be treated. Okay, put nitrogen gas in carbon fluoride container 8 The carbon fluoride is forcibly sent out of the container by this nitrogen gas. Oxygen gas may be added to the discharge line. In any case, the oxygen gas introduction pipe is connected to the vessel 8 itself or to the pipe from the vessel 8 to the gas guide 7 to be treated.
  • an exhaust gas pipe 21 is connected to the gas outlet 20 of the reaction vessel 1, and the exhaust gas pipe 21 is connected to a halogen absorption bin 22.
  • a gas discharge pipe 23 is attached to this bin 22.
  • a sampling pipe 24 is attached to the exhaust gas pipe 21, and the gas sampled by the sampling pipe 4 is sent to the gas separator 25.
  • FIG. 2 shows an example in which an exhaust gas oxidizer 26 is connected to the exhaust gas pipe 21 of the exhaust gas coming out of the reaction vessel 1. It is those substantially entire amount of the exhaust gas passing through the exhaust gas oxidizing apparatus 2 6 Yoko was made to pass through the catalyst layer 2 7, promoting the oxidation reaction from C 0 to C 0 2 in the catalyst layer 2 7 Oxidizing catalyst is installed.
  • a catalyst in which a noble metal catalyst such as platinum or palladium is supported on a heat-resistant carrier, or a hopcalite catalyst can be used.
  • an oxygen introduction pipe 28 for adding oxygen to the exhaust gas before entering the exhaust gas oxidizing apparatus 26 is connected, and a flow control valve 29 of the oxygen introduction pipe 28 causes a flow from the oxygen source 30 to be stopped.
  • a line 35 for introducing nitrogen gas 34 is provided in the exhaust gas line 21 upstream of the position where oxygen is introduced, and nitrogen gas 34 is mixed in the exhaust gas from this line 35. by the so as to introduce a C 0 concentration lower to whether we oxygen in the exhaust gas, even if the C 0 concentration in the exhaust gas was high summer, such as burns C 0 or C 0 2 oxygen introduction position The phenomenon can be suppressed.
  • Air can be used as the oxygen source 30 added to the exhaust gas.
  • the exhaust gas that has passed through the exhaust gas oxidizer 26 is sent to the halogen absorption bin 2 along the same route as in Fig. 1.
  • the temperature of the furnace atmosphere 6 in 4 is also detected by the temperature sensor 33, and the temperature of the heating furnace itself is appropriately controlled based on the detected value.
  • Fig. 3 shows an example in which used PFC or HFC used in the semiconductor manufacturing process is decomposed according to the present invention. Spent PFC or HFC from the semiconductor manufacturing process is usually extracted as carbon fluoride containing oxygen and nitrogen. This oxygen-containing carbon fluoride 37 is generally sent via a line 38 to a routine treatment step 36. To apply the present invention, the carbon fluoride supply pipe 38 is connected to the gas inlet 7 of the reaction vessel 1.
  • a branch pipe 40 is attached from the supply pipe 38 via a three-way valve 39, and this branch pipe 40 is connected to the gas inlet 7 to be processed.
  • a nitrogen gas supply pipe 41 is connected to the branch pipe 40 so that nitrogen gas can be sent from the nitrogen gas source 42 into the branch pipe 40 at a variable flow rate.
  • the source gas is supplied by supplying a necessary amount of nitrogen gas from the nitrogen gas source 42. It can be conveyed toward the processing gas inlet 7 at substantially the same flow rate.
  • the used PFC or HFC is usually extracted as a gas containing oxygen and nitrogen, and the oxygen content in the used gas does not usually exceed 20% by volume. Therefore, the method of the present invention is very advantageous for the decomposition of used PFC or HFC discharged in the semiconductor manufacturing process.
  • FIGS. 4 and 5 show an example of the present invention in which a heating source is installed inside the reaction vessel 1 so that ripening is transmitted to the reactant 2 from inside the vessel.
  • reference numeral 44 denotes a heat-resistant furnace material surrounding the reaction vessel 1
  • reference numeral 7 denotes an inlet for the gas to be treated into the vessel
  • reference numeral 20 denotes a gas outlet from the vessel.
  • a heating element 43 which generates heat when energized, is arranged inside a layer of the reactant 2, and the heating element 43 is covered with a corrosion-resistant heat-resistant cover. According to this example, since heat is transferred from the inside of the packed bed of the reactant 2, the heating rate for raising the reactant to the desired temperature can be increased, and the heat loss is reduced.
  • the inside of the reaction vessel 1 is divided into a packed bed of the reactant 2 and a heating bed, and the gas to be treated introduced into the vessel 1 passes through the heating bed and then to the packed bed of the reactant. It is made to flow.
  • a heating element 46 that generates heat when energized is attached to the container lid 45.
  • the gas to be treated is given heat when passing through the heating layer and is also transferred to the reactant 2.
  • the electric heater since the electric heater is placed in the container, there is an advantage that the heat utilization efficiency is high and the heat generating body 46 does not contact the reactant or the gas after the reaction, so that the deterioration is small.
  • Fig. 6 shows an example of the present invention in which a heat exchanger 48 for exchanging heat between the gas to be treated before being introduced into the reaction vessel 1 having a heating source and the exhaust gas discharged from the reaction vessel 2 is arranged. It is a thing. By arranging this heat exchanger 48, the sensible heat of the exhaust gas is imparted to the gas to be treated, so that the maturation can be recovered, so that the heat consumption of the heating source can be reduced.
  • the decomposition reaction 1 is terminated. The end point of the reaction can be known from the time when the detection of carbon fluorides or other fluorine compounds in the exhaust gas has started.
  • Fig. 7 shows that, as in the comparative example described later, trichloro-trifluorethane (CFC) containing chlorine as a constituent was converted to a concentration of 10 vol.% Of CFC and a gas flow rate of 0.15 liter. Torno content, molar ratio of CZC a0 in the reactant: 1.6 7. Maximum temperature of the reactant: 800 ° C, when the oxygen concentration in the gas to be treated is 0% and 1 ()% This shows the relationship between the inflow of CFC and the CFC decomposition rate during the decomposition treatment of.
  • CFC trichloro-trifluorethane
  • the decomposition rate of CFC is as described below, and the inflow of CFC is the integrated amount (g) of CFC that has flowed into the reaction vessel until the indicated decomposition rate. From the results shown in Fig. 7, it can be seen that in the decomposition treatment of chlorofluorocarbon containing chlorine as a component, the decomposition rate drops sharply if the target gas contains oxygen.
  • Fig. 8 shows that, as in Example 1 described later, perfluoroethane (PFC) was mixed with PFC concentration: 10 vo%, gas flow rate: 0.15 liter / min, and C Assuming that the Ca ratio is 1.67 and the maximum temperature of the reactant is 800, the PFC is decomposed when the oxygen concentration in the gas to be treated is 0% and 10%. The relationship between the inflow of PFC and the decomposition rate of PFC was shown. Things.
  • the reaction conditions in Fig. 8 are the same as those in Fig. 7, except that trichloro-trifluorene is replaced by perfluorene as the gas to be decomposed.
  • the decomposition rate drops sharply if the gas to be treated does not contain oxygen.
  • Fig. 9 shows the difference in the decomposition rate of perfluoroethane (PFC) when the heating method is electric heater heating as in the example and when the heating method is microphone mouth wave separately. It is.
  • the reaction conditions were as follows: concentration of carbon fluoride: 1 Ovol.%, Gas flow rate: 0.15 liter Z, oxygen concentration: 10 vol.%, CZC of reactant The molar ratio of a0 is set to 1.67.
  • Microwave o-wave heating is performed by forming the reaction tube of the later-described embodiment from a ceramic material having microphone mouth-wave transmission, and applying this to an microwave oven.
  • the reactor had the same capacity as the example described later, except that it was installed inside the reactor.
  • the method of the present invention was carried out using an apparatus having the same principle as that shown in FIG.
  • a tubular furnace electric capacity 20 KW
  • a heating element using a Kanthal alloy
  • an austenitic system with an inner diameter of 28 mm and a length of 100 Omm was used.
  • a reaction tube made of stainless steel (SUS304) was penetrated, and 100 g of a granular reactant prepared using charcoal and slaked lime as raw materials was charged into the furnace center of the reaction tube.
  • This reactant was prepared by mixing charcoal with a particle size of 250 m or less and slaked lime with a particle size of 250 or less at a weight ratio of 1: 3, mixing with a Henschel mixer, adding water, and granulating. After drying at 110 ° C for 4 hours, heat-treating at 800 ° C for 8 hours in a nitrogen atmosphere, and dehydrating and firing. It is a pelletized pellet.
  • the raw material used was charcoal with a fixed carbon content of 78%, volatile matter of 9%, ash content of 3% and water content of 10%, and slaked lime used as a raw material of JIS 9001 standard.
  • Table 1 shows the reaction conditions and reaction results of each test (Na 1 to 5).
  • the decomposition rate after 30 minutes the amount of decomposition of carbon fluoride, and the Ca ⁇ consumption rate of the reactant shown in the column of reaction results were determined as follows.
  • the amount of carbon fluoride remaining in the exhaust gas was measured from the exhaust gas sample 30 minutes after the start of the reaction, and the amount of carbon fluoride in the exhaust gas with respect to the amount of carbon fluoride in the gas to be treated was 100 minutes. Expressed as a percentage.
  • the amount of carbon fluoride decomposed by the end of the reaction was the time when the decomposition rate dropped to 95%.
  • the decomposition rate every 30 minutes was calculated from the exhaust gas analysis value every 30 minutes, and the value obtained by multiplying the amount of carbon fluoride that flowed in each 30 minutes by the decomposition rate at that time was used for that 30 minutes.
  • the amount of decomposition of carbon fluoride (g) was defined as the integrated value of the amount of decomposition from the start of the reaction until the decomposition rate decreased to 95%.
  • Example 1 The same tests as in Example 1 (Nos. 6 to 9) were performed, except that the oxygen concentration in the gas to be treated was kept constant at 5 vol.% And the reactants were used with different molar ratios of CZCaO. .
  • the molar ratio of CZC a0 in the reactant was determined by analyzing the pellets produced in the same manner as in Example 1 by changing the blending amounts of charcoal and slaked lime. The amount was measured and determined from these measurements.
  • the test results are also shown in Table 1. This result indicates that the amount of decomposition of perfluoroethane up to the end of the reaction is affected by the molar ratio of C7Ca0. In this example, it can be seen that the best results were obtained when the molar ratio of C / Ca0 was about 1.7.
  • Example 1 The same test as in Example 1 was conducted except that perfluoromethane was used instead of perfluoroethane. At that time, the oxygen concentration was changed to 0% (No. 10) and 10% (No. 11). Table 1 shows the test results. It can also be seen that the amount of decomposition up to the end of the reaction was significantly increased by the addition of oxygen.
  • Example 2 The same test as in Example 1 was performed except that trifluoromethane (CHF 3 ) was used instead of perfluoroethane.
  • CHF 3 trifluoromethane
  • the concentration of carbon fluoride and the concentration of oxygen were both constant at 5 vol.%
  • the gas flow rate was 0.12 liter Z
  • the maximum temperature of the reactants was changed ( ⁇ 12 to 17) using the sample No. 7 (Fig. 7). The results are shown in Table 1.
  • the maximum reaction temperature was 40 (decomposition rate after 30 minutes was lower than TC, whereas almost 100% was degraded at 400 ° C or higher. [Comparative Example]
  • Trichlorotrifluoroethane containing chlorine as a constituent was subjected to the same decomposition treatment as in Example 1.
  • Table 1 also shows the reaction conditions and the reaction results. In this case, the amount of decomposition increased when oxygen was not present in the gas to be treated (Comparative Example No. 1), and the amount of decomposition was rather reduced when oxygen was present (Comparative Example 2).
  • Example 4 The same test as in Example 4 was carried out except that 1,1,1,2 tetrafluoroethane (C 2 H 2 F 4 ) was used instead of trifluoromethane (C HF 3 ) (Test # ⁇ 20) . At that time, the maximum temperature of the reactant was set to 35 (TC. The results are shown in Table 1. The decomposition rate was close to 100% even at 350 ° C.
  • perfluorocarbon or hydrofluorocarbon can be completely decomposed by a simple treatment method, and the decomposed fluorine can be fixed as a harmless substance.
  • the method for decomposing carbon fluorides of the present invention is simple because of the simplicity of the decomposer, the high efficiency of decomposition, the ease of post-treatment of decomposition products, and the low cost of the reactants. It has an effect that is not available in particular, and can make a great contribution to the decomposition of used perfluorocarbon or hydrofluorocarbon generated in the semiconductor manufacturing process.

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Abstract

Procédé de décomposition d'hydrocarbures fluorés consistant à mettre en contact les gaz d'hydrocarbures perfluorés ou hydrofluorés avec un réactif constitué par des matériaux carbonés solides et par un composé de métal terreux alcalin à une température égale ou supérieure à 300 °C en présence d'un pourcentage en volume égal ou inférieur à 20 % (excepté 0 %) d'oxygène gazeux.
PCT/JP1996/001857 1996-07-04 1996-07-04 Procede et equipement de decompositions d'hydrocarbures fluores WO1998001217A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7138551B2 (en) 2004-11-05 2006-11-21 E. I. Du Pont De Nemours And Company Purification of fluorinated alcohols
JP2007153733A (ja) * 2005-11-14 2007-06-21 Kenichi Akishika 炭素含有アルカリ土類金属酸化物およびそれを用いた有機ハロゲン化物の分解処理方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
JPS6135849A (ja) * 1984-07-27 1986-02-20 Ube Ind Ltd ドライエツチング排ガス処理剤
JPH0312220A (ja) * 1989-06-09 1991-01-21 Du Pont Mitsui Fluorochem Co Ltd 塩弗化アルカンの接触分解方法
JPH08187302A (ja) * 1995-01-06 1996-07-23 Dowa Mining Co Ltd フロン分解法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6135849A (ja) * 1984-07-27 1986-02-20 Ube Ind Ltd ドライエツチング排ガス処理剤
JPH0312220A (ja) * 1989-06-09 1991-01-21 Du Pont Mitsui Fluorochem Co Ltd 塩弗化アルカンの接触分解方法
JPH08187302A (ja) * 1995-01-06 1996-07-23 Dowa Mining Co Ltd フロン分解法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7138551B2 (en) 2004-11-05 2006-11-21 E. I. Du Pont De Nemours And Company Purification of fluorinated alcohols
JP2007153733A (ja) * 2005-11-14 2007-06-21 Kenichi Akishika 炭素含有アルカリ土類金属酸化物およびそれを用いた有機ハロゲン化物の分解処理方法

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