KR101178179B1 - Method, reagent and apparatus for treating emissions containing chlorine trifluoride and other inorganic halogenated gases - Google Patents

Abstract

The present invention provides a method and apparatus for treating inorganic halogenated gas-containing exhaust gas that can sufficiently handle an inorganic halogenated gas-containing exhaust gas containing a large amount of chlorine trifluoride, and an inorganic halogenated gas-containing exhaust gas having high processing capacity and long life. It is an object to provide a gas treating agent.

The first processing part 10 which fills a chlorine trifluoride decomposition agent, and the 2nd processing part 20 which fills a chlorine removal agent are included. The 1st processing part 10 is arrange | positioned upstream of a 2nd processing part, and exhaust gas is comprised so that it may pass first through the 1st processing part 10 first, and then pass through a 2nd processing part.

Description

METHOD, REAGENT AND APPARATUS FOR TREATING EMISSIONS CONTAINING CHLORINE TRIFLUORIDE AND OTHER INORGANIC HALOGENATED GASES} Method for treating exhaust gas containing inorganic halogenated gas containing chlorine trifluoride

1 is a schematic illustration showing a first embodiment of a processing apparatus of the present invention;

2 is a schematic view showing a second embodiment of the processing apparatus of the present invention.

※ Explanation of symbols for main parts of drawing

1, 100: processing apparatus 10: first processing unit

20: second processing unit 14: chlorine trifluoride disintegrant layer

24: chlorine remover layer

110: first treatment part (chlorine trifluoride decomposition layer)

120: second treatment portion (chlorine remover layer) 130: heat insulation portion (insulation material layer)

The present invention 3 chlorine trifluoride (ClF ₃₎ containing relates to a processing method and processing apparatus for an exhaust gas containing inorganic halide gas, in particular exhaust when the dry cleaning and the like inside the device by the ClF ₃ in semiconductor manufacturing process The present invention relates to a treatment method and a treatment apparatus for harmless exhaust gas containing inorganic halogenated gases such as ClF ₃ , SiF ₄ , SiC 1 ₄ , BF ₃ , BCl ₃ , PF ₃ , PCl ₃ , F ₂ , and Cl ₂ .

Recently, due to the requirement for ultra-LSI miniaturization and improvement in production efficiency, thin film components attached to the inner surface of a vessel or pipe in a thin film forming apparatus such as a CVD apparatus or a PVD apparatus are automatically converted into a gas such as chlorine trifluoride (ClF ₃ ). The cleaning method is used. As the diameter of the wafer to be processed increases, the amount of aeration of ClF ₃ gas increases, which tends to prolong the cleaning use time. However, ClF ₃ is very toxic with a TLV of 0.1 ppm. In addition, among the exhaust gas discharged after auto cleaning, in addition to ClF ₃ , SiF ₄ , SiCl ₄ , BF ₃ , BCl ₃ , PF ₃ , PCl ₃ , F ₂ , Cl _2, etc., which are simultaneously discharged as by-products during thin film cleaning It also contains harmful inorganic halogenated gases.

As the treatment of ClF ₃ , a dry scrubbing method using a wet scrubber with alkaline aqueous solution, soda lime, activated alumina or the like is generally performed. However, even using treatment agents such as soda lime or activated alumina alone, ClF ₃ could not be removed to below the TLV value, and chlorine was released by reaction with the treatment agent, resulting in SiF ₄ , SiCl ₄ , BF ₃ , BCl ₃ , PF There was a problem in that inorganic halogenated gases such as ₃ , PCl ₃ , F ₂ , and Cl ₂ could not be sufficiently removed.

Therefore, the present inventors use a treatment method in which an alkali agent such as iron oxide and calcium hydroxide is used in combination to prevent the glass of chlorine to remove ClF ₃ to a TLV value or less and to sufficiently remove other inorganic halogenated gases. -177). However, it has been found that there is still room for improvement in order to sufficiently process a large amount of ClF ₃ .

Therefore, the present inventor has proposed a treatment method (Japanese Patent Laid-Open No. 11-70319) which is brought into contact with an anion exchange resin after contacting with an oxide of iron or a synthetic zeolite in order to sufficiently treat a large amount of ClF ₃ again. However, due to the temperature increase due to the heat of reaction of the treatment agent and the exhaust gas due to the prolonged cleaning time, the performance of the anion exchange resin was reduced after a long time, and it was found that it is necessary to cool the treatment agent by performing N ₂ purge after cleaning. Since the N ₂ purge requires a long time of 6 hours or longer, there is a problem that the switching of the semiconductor process from the cleaning process to the deposition process is delayed and the production efficiency is lowered. In addition, new N ₂ purge lines for cooling need to be assembled in the unit.

[Patent Document 1]

Japanese Patent Publication No. 6-177

[Patent Document 2]

Japanese Patent Application Laid-Open No. 11-70319

An object of the present invention is that an inorganic halogenated gas capable of sufficiently processing an inorganic halogenated gas-containing exhaust gas containing a large amount of acidic gas in addition to a large amount of chlorine trifluoride due to a long cleaning time by chlorine trifluoride in a semiconductor manufacturing process or the like. The present invention provides a method for treating gas-containing exhaust gas.

In addition, the object of the present invention is to treat inorganic halogenated gas that can sufficiently treat inorganic halogenated gas-containing exhaust gas containing chlorine trifluoride (ClF ₃ ) and other acidic gases even after long time treatment. An apparatus and a processing agent are provided.

According to the present invention, 3 a chlorine trifluoride inorganic halide gas-containing exhaust gas containing (ClF _{3) 3} chlorine trifluoride (ClF ₃₎ minutes, and contacts the release, then the inorganic halide gas-containing exhaust gas, comprising a step of contacting the chlorine scavenger A method of treating gas is provided. 3 a chlorine trifluoride (ClF ₃₎ inorganic halide gas-containing exhaust gas containing, three chlorine trifluoride (ClF ₃₎ disintegrating the contact thereby, removed by fixing, by chemical reaction of fluorine atoms to the disintegrating and the other acid gases Fix to disintegrant. At this time, free chlorine gas (Cl ₂ ) is produced. Subsequently, the exhaust gas containing free chlorine gas is contacted with a chlorine remover to remove the free chlorine gas, and the chlorine atom is removed from the exhaust gas as a harmless salt.

Exhaust gases treated by the present invention include, in addition to chlorine trifluoride (ClF ₃ ), silicon tetrafluoride (SiF ₄ ), silicon tetrachloride (SiCl ₄ ), boron trifluoride (BF ₃ ), and boron trichloride (BCl ₃ ) It is preferable to contain at least one acidic gas selected from phosphorus trifluoride (PF ₃ ), phosphorus trichloride (PCl ₃ ), fluorine gas (F ₂ ) and chlorine gas (Cl ₂ ). These exhaust gases are preferably exhaust gases generated from a cleaning process in a semiconductor manufacturing process, for example, a process of cleaning the inside of a chamber after film adhesion such as a Poly-Si film or a SiN film in a semiconductor manufacturing apparatus.

Next, for example, 3 present in the chlorine trifluoride (ClF _3), if brought into contact with the exhaust gas containing the three sulfur-based reducing agent as synthetic zeolite and a chlorine scavenger as chlorine trifluoride disintegrants (Na ₂ S ₂ O ₃₎ for example, The processing method of the invention will be described.

First, when the exhaust gas containing chlorine trifluoride is contacted with a synthetic zeolite, the following formula 1

As described above, the fluorine atom is fixed by chemical reaction with the Al ₂ O ₃ portion of the synthetic zeolite, and the chlorine atom is liberated as chlorine gas (Cl ₂ ).

Subsequently, when this exhaust gas is contacted with a chlorine remover, the following formula 2

As described above, the chlorine atom is reacted with a sulfur-based reducing agent (Na ₂ S ₂ O ₃ ) to produce a harmless salt (NaCl) and is removed from the exhaust gas.

In the above formulas 1 and 2, although a synthetic zeolite containing an Al ₂ O ₃ moiety as the chlorine trifluoride decomposition agent and a sulfur-based reducing agent of Na ₂ S ₂ O ₃ is used as the chlorine removing agent, it can be used in the present invention. Chlorine trifluoride decomposing agent and chlorine removing agent are not limited to these. The chlorine trifluoride decomposer that can be used in the present invention may be one capable of fixing fluorine atoms by decomposing chlorine trifluoride. For example, an oxide of trivalent iron containing Fe ₂ O ₃ as a main component is preferable. Can be mentioned. Synthetic zeolites, however, have a greater amount of decomposition treatment of chlorine trifluoride than iron oxides, and have a high decomposition capability and condensation and liquefaction in the treatment layer of chlorine trifluoride which causes a sudden rise in temperature or pressure due to a rapid decomposition reaction. It is particularly preferable because it can prevent the accumulation of.

As a synthetic zeolite which can be used as the chlorine trifluoride decomposition agent of the present invention, one having a high aluminum content is preferable. For example, preferably containing 0.5 to 10 mol parts of SiO ₂ per 1 mol parts of Al ₂ O _3, more preferably containing 1 to 5 mol parts of SiO ₂ per 1 mol parts of Al ₂ O _3, and it is particularly preferable to contain 2.5 mol parts of SiO ₂ per 1 mol parts of Al ₂ O _3. As such a synthetic zeolite, the X type | mold synthetic zeolite high in the decomposition ability of chlorine trifluoride is mentioned preferably. More specifically, as the synthetic zeolite which can be used in the present _{invention, Na 2 O · Al 2 O} 3 · 2 ~ 3SiO 2 · nH ₂ O in the X-type synthetic zeolite, in particular _{Na 2 O · Al 2 O 3} · 2.5SiO 2 X-type synthetic zeolites having a chemical formula of nH ₂ O and the like are preferable. In the formula, sodium oxide is substituted with other alkali metal oxides such as potassium oxide or earth alkali metal oxides such as calcium oxide, for example, Li-X type, K-X type, Mg-X type, Ca -X-type or Ba-X-type synthetic zeolite may be sufficient.

The synthetic zeolite as the chlorine trifluoride decomposition agent used in the present invention preferably has an average pore diameter of 4 to 100 kPa, more preferably 4 to 20 kPa, particularly preferably 10 kPa, and the specific surface area is preferably 600. It is-900 m <2> / g, More preferably, it is 600-700 m <2> / g, Especially preferably, it is 650 m <2> / g. When the average pore diameter and the specific surface area of the synthetic zeolite are in the above ranges, an advantage is obtained that the activity is higher and the decomposition ability of chlorine trifluoride is high.

Moreover, the chlorine removal agent which can be used in this invention should just be a thing which can produce a harmless salt by reducing free chlorine gas, For example, anion exchange resin etc. are mentioned preferably. However, sulfur-based reducing agents are particularly preferred because they have a high throughput of chlorine, have high heat resistance compared with anion exchange resins, and have a high processing capacity at high temperatures.

Examples of the sulfur-based reducing agent used as the chlorine removing agent in the present invention include sulfite, dithionite, tetrathionate, thiosulfate, and the like, and these may be used alone or in combination of two or more thereof. You may also For example, a combination of sulfite and thiosulfate can be preferably used. In particular, sodium sulfite, potassium sulfite, sodium thiosulfate, potassium thiosulfate and the like can be preferably used.

The shape of the chlorine trifluoride decomposing agent and the chlorine removing agent used in the present invention is not particularly limited as long as the operability and the handleability thereof are good, and may be in any form, such as a granular / rod shape or a plate shape.

In the present invention, the chlorine trifluoride decomposing agent and the chlorine removing agent have a large contact area with the halogen atom in the exhaust gas in order to efficiently proceed the chemical reaction with the chlorine trifluoride and to efficiently fix the fluorine atom and the chlorine atom. It is more preferable. Moreover, it is preferable that it is a range which does not raise a ventilation resistance at the time of passing an exhaust gas. As a synthetic zeolite as a chlorine trifluoride which satisfies these conditions, a spherical or columnar shape in the range of 4 to 20 mesh is preferable, a spherical shape or columnar in the range of 8 to 20 mesh is more preferable, and a 14 to 20 mesh range It is especially preferable that it is spherical. The sulfur-based reducing agent as the chlorine remover is preferably a cylinder in the range of 1.6 to 3.2 mmφ, more preferably a columnar in the range of 1.6 to 2.4 mmφ, and particularly preferably a 1.6 mmφ columnar pellet.

In the processing method of this invention, it is preferable that the temperature at the time of gas processing is the range of normal temperature-150 degreeC, It is more preferable that it is the normal temperature-200 degreeC range, It is especially preferable that it is normal temperature. When the gas treatment temperature is set to a high temperature exceeding 200 ° C., the material and structure of the treatment apparatus need to be made heat resistant, which is not economical. Moreover, in order to make it into a low temperature below normal temperature, it is necessary to lower temperature using cooling apparatuses, such as a cooler, and since processing cost becomes high, it is unpreferable.

Moreover, according to this invention, the processing agent of the inorganic halogenated gas containing exhaust gas containing chlorine trifluoride which consists of a combination of a chlorine trifluoride decomposition agent and a chlorine removal agent is provided. Here, it is preferable that the chlorine trifluoride decomposition agent and the chlorine removing agent are not mixed so that they can be used separately during the exhaust gas treatment.

In the treatment agent of the present invention, the chlorine trifluoride decomposing agent is preferably the above-described synthetic zeolite, and particularly preferably the X-type synthetic zeolite. Moreover, it is especially preferable that a chlorine removal agent is the said sulfur type reducing agent.

In the treatment agent of the present invention, the ratio of the amount of the chlorine trifluoride decomposer to the chlorine remover varies depending on the amount of chlorine trifluoride treated, but the ratio of the chlorine trifluoride decomposer to the chlorine remover is from 1: 1 to 1: 0.6. It is preferable that it is the range of.

Moreover, according to this invention, it contains the 1st process part which fills a chlorine trifluoride decomposer, and the 2nd process part which fills a chlorine remover, The said 1st process part is arrange | positioned upstream of the said 2nd process part, It is characterized by the above-mentioned. An apparatus for treating inorganic halogenated gas-containing exhaust gas containing chlorine trifluoride is provided. In the waste gas processing apparatus of the present invention, the first processing unit and the second processing unit may be disposed so as to first pass the exhaust gas through the first processing unit and then through the second processing unit. For example, when the 1st processing part is arrange | positioned at the upper end and the 2nd processing part is arrange | positioned, what is necessary is just to comprise so that the flow of waste gas may flow in a downward flow. On the contrary, when the 1st processing part is arrange | positioned at the lower end and the 2nd processing part is arrange | positioned at the upper end, what is necessary is just to comprise so that it may flow with the flow of waste gas upstream. In addition, when the 1st processing part and the 2nd processing part are arrange | positioned in parallel, what is necessary is just to comprise so that exhaust gas may pass through a 2nd processing part after passing through a 1st processing part.

In the processing apparatus of this invention, it is preferable to further provide a heat insulation part between a 1st processing part and a 2nd processing part. As the heat insulating material, porous and inert components such as silica gel, natural zeolite, alumina and the like can be used. By providing such an insulator, the inlet concentration of the exhaust gas is increased or the aeration time is prolonged, and even if the temperature rise due to the reaction with the chlorine trifluoride decomposition agent in the first treatment unit is severe and becomes a high temperature near 200 ° C, the second treatment unit Thermal degradation of the chlorine remover can be prevented.

In addition, according to the present invention, there is provided a columnar shape having an exhaust gas treatment inlet and a process gas outlet, wherein the first treatment portion is formed by filling a chlorine trifluoride decomposing agent on the exhaust gas treatment inlet side and chlorine on the process gas outlet side. Provided is a treatment apparatus for an inorganic halogenated gas-containing exhaust gas containing chlorine trifluoride having a second treatment portion formed by filling a remover and having a heat insulation portion formed by filling a heat insulating material between the first treatment portion and the second treatment portion. .

In the present invention, the amount of the chlorine trifluoride decomposing agent in the first treatment portion varies depending on the amount of chlorine trifluoride treatment, but is typically 50% by volume to 70% by volume, preferably about 60% by volume. The filling amount of the chlorine removing agent in the 2 treatment part is typically 25 to 45% by volume, preferably about 35% by volume. When the amount of the chlorine trifluoride decomposing agent and the chlorine removing agent is in the above-described range, the advantage that high treatment performance can be obtained also for the inorganic halide gas coexisting in addition to the chlorine trifluoride.

Although the exhaust gas treating apparatus and the exhaust gas treating method of the present invention are described with reference to the drawings, the present invention is not limited thereto.

1 shows a first embodiment of the exhaust gas treating apparatus of the present invention. In this embodiment, two filling columns are used, and one filling layer is arranged inside each filling column. That is, the exhaust gas processing apparatus 1 shown in FIG. 1 has the 1st column 10 as a 1st processing part which fills a chlorine trifluoride decomposition agent, and the 2nd column as a 2nd processing part which fills a chlorine remover ( 20), and the first column 10 as the first processing unit is disposed upstream of the second column 20 as the second processing unit. The first column 10 is filled with an exhaust gas inlet 12 through which the exhaust gas flows from the exhaust gas source through the L _IN , a chlorine trifluoride decomposer layer 14 and trifluoride; The primary process gas outlet 16 through which the gas after the primary process which passed the chlorine disintegrant layer 14 is made to flow is provided. The second column 20 is filled with a primary process gas inlet 22 for introducing a primary process gas from the primary process gas outlet 16 of the first column 10 and a chlorine remover layer. (24) and the secondary process gas outlet 26 which flows out the gas after the secondary process which passed the chlorine remover layer 24 are provided. A primary process gas line L is provided between the primary process gas outlet 16 of the first column 10 and the primary process gas inlet 22 of the second column 20, thereby providing a first column ( In step 10), the primary processing gas in which the fluorine atom is adsorbed and removed is introduced into the second column 20.

The exhaust gas from the exhaust gas generating source is introduced into the first column 10 from the exhaust gas outlet 12 via L _IN and passes through the chlorine trifluoride decomposition layer 14 in an upward flow. While passing through the chlorine trifluoride decomposer layer 24, the fluorine atoms in the exhaust gas are fixed to the chlorine trifluoride decomposer layer 24 to be removed from the exhaust gas, thereby forming a primary processing gas from which the fluorine atoms are removed. . The primary processing gas which has passed through the chlorine trifluoride decomposition layer 24 is the primary processing gas inlet of the second column 20 from the primary processing gas outlet 16 through the primary processing gas line L. Is introduced into the second column 20 via 22). In the second column 20, the primary processing gas passes through the chlorine remover layer 24 in an upward flow, and chlorine atoms are adsorbed and removed from the chlorine remover to form a secondary processing gas from which chlorine atoms are removed. Subsequently, the secondary processing gas is discharged to the outside via the L _OUT through the secondary processing gas outlet 26.

2 shows a second embodiment of the treatment apparatus of the present invention. In FIG. 2, two packed beds are arranged inside one packed column. That is, the waste gas processing apparatus 100 shown in FIG. 2 is a column which has an waste gas processing inlet and a process gas outlet, and the 1st process part which fills the chlorine trifluoride decomposition agent in the exhaust gas processing inlet side in the column. (110) and a second processing unit (120) formed by filling a chlorine remover on the processing gas outlet side, and a heat insulating unit (130) formed by filling a heat insulating material between the first processing unit (110) and the second processing unit (120). ) Is installed.                     

The exhaust gas from the exhaust gas generating source is introduced into the column 100 via L _IN , passes through the first processing unit 110, the heat insulating unit 130, and the second processing unit 120 in an upflow direction, and L _OUT. It is discharged to the outside via. The fluorine atoms in the exhaust gas are fixed by the chlorine trifluoride decomposition agent and removed in the first processing unit 110. The primary processing gas from which the fluorine atom is removed is introduced into the second processing unit 120 through the heat insulation unit 130, where the chlorine atoms are adsorbed and removed.

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.

Example 1

260 mL of synthetic zeolite (Mizukashib's 13X-1420B: made by Mizusawa Kagaku, particle diameter 14-20 mesh) was prepared so that two 42mm diameter SUS minicolumns were prepared and the layer height was 190 mm in one column. It filled and the 1st process part was prepared. Sulfur-based reducing agent (ECL-3: zude chemical catalyst, particle diameter 1.6 mmφ pellets), composition: basic zinc zinc 25%, sodium thiosulfate 17%, alumina 56%, clay 2 260 mL of%) was charged to prepare a second treatment part. Two columns were assembled in the processing apparatus of the structure shown in FIG. Treatment experiments were carried out using ClF ₃ diluted with N ₂ mimicking the exhaust gas.

In the processing apparatus shown in FIG. 1, ClF ₃ diluted with N ₂ was vented at an inlet concentration of 1.0% and a gas flow rate of 667 mL / min, and the secondary processing gas from the second processing unit was analyzed. Analysis of ClF ₃ and Cl ₂ is performed by mass spectrometry (Questor GP, ABB Extrel), and analysis of HCl and HF is performed by ion chromatograph (AI-450, Dionex), and analysis of SO ₂ F ₂ . Silver gas chromatograph mass spectrometer (QP-5050A by Shimadzu Corporation) was performed. The results are shown in Table 1.

Elapsed time after venting ~ 46.5 hours 47 hours Allowable concentration ClF ₃ <0.1 ppm <0.1 ppm 0.1 ppm Cl ₂ <0.2 ppm 0.6 ppm 0.5 ppm HCl <1 ppm <1 ppm 5 ppm HF <1 ppm <1 ppm 3 ppm SO ₂ F ₂ <1 ppm <1 ppm 5 ppm

Until 46.5 hours after the start of aeration, all kinds of ClF ₃ , Cl ₂ , HC1, HF, and SO ₂ F ₂ were always treated below the detection limit. After 47 time was still the vent because it starts to leak in excess of Cl ₂ (O.5 ppm as Cl ₂₎ permitted the concentration 0.6 ppm.

According to the present treatment method using the present treatment device according to the present embodiment, it can be seen that for a long time of 46.5 hours after the start of aeration, any component can be satisfactorily treated below the allowable concentration.

Comparative Example 1

As a first treatment unit, instead of a synthetic zeolite as a chlorine trifluoride decomposing agent, a sulfur-based reducing agent (ECL-3: zudecheme catalyst, a particle diameter of 1.6 mmφ pellet, composition: basic carbon zinc 25%, sodium thiosulfate 17%) as a chlorine remover , 56% alumina, 2% clay) was prepared in the same manner as in Example 1 except that the performance of the synthetic zeolite as a chlorine trifluoride decomposition agent was evaluated under the same aeration conditions. The results are shown in Table 2.

Elapsed time after venting ~ 47 hours 47.5 hours Allowable concentration ClF ₃ <0.1 ppm 2.1 ppm 0.1 ppm Cl ₂ <0.2 ppm 40 ppm 0.5 ppm HCl <1 ppm <1 ppm 5 ppm HF <1 ppm <1 ppm 3 ppm SO ₂ F ₂ 100-400 ppm 380 ppm 5 ppm

Up to 47 hours after the start of aeration, ClF ₃ , Cl ₂ , HC1 and HF could be treated below the detection limit, but SO ₂ F ₂ was found to leak at a very high concentration of 100 to 400 ppm. After 47.5 hours, ClF ₃ and Cl ₂ leaked beyond the allowable concentration.

When synthetic zeolite was not used as the first treatment part according to Comparative Example 1, it can be seen that harmful ₂ SO ₂ F ₂ was produced in excess of the allowable concentration as a byproduct.

Comparative Example 2

A second treatment part was prepared in the same manner as in Example 1 except that 260 mL of an anion exchange resin (20-50 mesh) manufactured by DOWEX was used instead of the sulfur-based reducing agent. The performance was evaluated. The results are shown in Table 3.

Elapsed time after venting ~ 41 hours 41.5 hours Allowable concentration ClF ₃ <0.1 ppm <0.1 ppm 0.1 ppm Cl ₂ <0.2 ppm 0.5 ppm 0.5 ppm HCl <1 ppm <1 ppm 5 ppm HF <1 ppm <1 ppm 3 ppm SO ₂ F ₂ <1 ppm <1 ppm 5 ppm

Up to 41 hours after the start of aeration, all kinds of ClF ₃ , Cl ₂ , HC1, HF, and SO ₂ F ₂ were always treated below the detection limit. After 41.5 hours has elapsed, Cl ₂ has been stopped because the air passage starts to leak in excess of the (O.5 ppm as Cl ₂₎ permitted the concentration 0.5 ppm.

In the case of using an anion exchange resin instead of the sulfur-based reducing agent according to Comparative Example 2, there is no generation of by-products, and all kinds of ClF ₃ , Cl ₂ , HCl, HF, and SO ₂ F ₂ can be treated well. It can be seen that the duration as the treatment agent is 41.5 hours, which is about 6 hours shorter than that of the combination of the synthetic zeolite and the sulfur-based reducing agent.

According to the treatment method of the present invention, even in an inorganic halogenated gas-containing exhaust gas containing a large amount of chlorine trifluoride and other acidic gases, ClF ₃ , Cl ₂ , HCl, HF, and SO ₂ F ₂ can be satisfactorily treated. .

Therefore, the treatment method of the present invention has a long cleaning time in the semiconductor manufacturing process, and a large amount of inorganic halogenated gas is generated to produce not only chlorine trifluoride (ClF ₃ ) but also silicon tetrafluoride (SiF ₄ ) and silicon tetrachloride. (SiCl ₄ ), boron trifluoride (BF ₃ ), boron trichloride (BCl ₃ ), phosphorus trifluoride (PF ₃ ), phosphorus trichloride (PCl ₃ ), fluorine gas (F ₂ ) and chlorine gas (Cl ₂ ) At least one acid gas selected from the group can also be applied to the treatment of exhaust gas containing a large amount, thereby obtaining sufficient treatment effect.

Moreover, according to this invention, the processing agent of the inorganic halogenated gas containing waste gas containing chlorine trifluoride which has a large processing capacity and has a long life is provided.

According to the present invention, there is provided an apparatus for treating inorganic halogenated gas, which is capable of sufficiently treating the inorganic halogenated gas-containing exhaust gas containing chlorine trifluoride even after long-term treatment.

Claims (9)

3 chlorine trifluoride (ClF ₃₎ an inorganic halide gas-containing exhaust gas containing is contacted with 3 chlorine trifluoride (ClF ₃₎ disintegrants, then containing from 3 chlorine trifluoride (ClF _3), comprising a step of contacting the chlorine scavenger In the method of treating the inorganic halogenated gas-containing exhaust gas, The chlorine trifluoride (ClF ₃ ) decomposition agent is a synthetic zeolite, and the chlorine removing agent is a sulfur-based reducing agent containing a thiosulfate. delete The method of claim 1, The exhaust gas is silicon tetrafluoride (SiF ₄ ), silicon tetrachloride (SiCl ₄ ), boron trifluoride (BF ₃ ), boron trichloride (BCl ₃ ), phosphorus trifluoride (PF ₃ ), phosphorus trichloride (PCl ₃₎ ), Fluorine gas (F ₂ ), and chlorine gas (Cl ₂ ). In the treatment agent for inorganic halogenated gas containing chlorine trifluoride (ClF ₃ ) containing a combination of a chlorine trifluoride (ClF ₃ ) decomposition agent and a chlorine remover, The chlorine trifluoride (ClF ₃ ) decomposition agent is a synthetic zeolite, the chlorine remover is a sulfur-based reducing agent containing thiosulfate, The chlorine trifluoride (ClF ₃ ) decomposition agent: chlorine remover ratio of the inorganic halogenated gas-containing exhaust gas, characterized in that in the range of 1: 1 to 1: 0.6. delete A chlorine trifluoride (ClF ₃ ) comprising a first treatment portion filled with a decomposition agent and a second treatment portion filled with a chlorine remover, wherein the first treatment portion is disposed upstream of the second treatment portion. An apparatus for treating inorganic halogenated gas-containing exhaust gas containing (ClF ₃ ), The chlorine trifluoride (ClF ₃ ) decomposition agent is a synthetic zeolite, and the chlorine remover is a sulfur-based reducing agent containing a thiosulfate treatment device of the inorganic halogenated gas containing exhaust gas. delete The method according to claim 6, And a heat insulation unit is further provided between the first processing unit and the second processing unit. A columnar shape having an exhaust gas treatment inlet and a process gas outlet, provided in the column at the exhaust gas treatment inlet side and filled with a chlorine trifluoride (ClF ₃ ) decomposition agent, and at the process gas outlet side; And an inorganic halogenated gas containing chlorine trifluoride (ClF ₃ ) comprising a _second treatment portion filled with a chlorine remover, and an insulation portion provided between the first treatment portion and the second treatment portion and filled with a heat insulating material. In the treatment apparatus of containing exhaust gas, The chlorine trifluoride (ClF ₃ ) decomposition agent is a synthetic zeolite, and the chlorine remover is a sulfur-based reducing agent containing a thiosulfate treatment device of the inorganic halogenated gas containing exhaust gas.

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