KR101038295B1 - Apparatus for decomposition of PFCs gas using gliding arc discharge - Google Patents

Apparatus for decomposition of PFCs gas using gliding arc discharge Download PDF

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KR101038295B1
KR101038295B1 KR1020080082805A KR20080082805A KR101038295B1 KR 101038295 B1 KR101038295 B1 KR 101038295B1 KR 1020080082805 A KR1020080082805 A KR 1020080082805A KR 20080082805 A KR20080082805 A KR 20080082805A KR 101038295 B1 KR101038295 B1 KR 101038295B1
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gas
perfluorinated compound
compound gas
reactor
decomposition
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KR1020080082805A
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KR20100024108A (en
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박동화
신백균
이종문
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인하대학교 산학협력단
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    • 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]

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  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
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Abstract

The present invention relates to a perfluorinated compound gas cracking apparatus using a gliding arc discharge, specifically, a cylindrical reactor having an exhaust port thereon; An electrode unit mounted in the shape of two blades inside the reactor; A power source installed outside the reactor to induce a gliding arc by applying electricity to the electrode unit; A mixer for mixing and supplying a perfluorinated compound gas, which is a raw material gas, and a diluting gas between the electrode units in the reactor; The present invention relates to a perfluorinated compound gas decomposition device using a gliding arc including a perfluorinated compound gas storage device and a diluent gas storage device supplied to the mixer, and a perfluorinated compound gas decomposition method using the same. The gliding arc used in the perfluorinated compound gas cracker according to the present invention generates a large number of chemically active species such as ions or radicals, thereby effectively decomposing the perfluorinated compound gas which is stable and difficult to decompose. In addition, it is possible to process a large amount of fluid per unit time, and the simple structure has the advantage that can be more efficiently treated perfluorinated compound gas if applied to the semiconductor and display process.

PFCs, gliding arc, decomposition, greenhouse effect

Description

Apparatus for decomposition of PFCs gas using gliding arc discharge}

The present invention relates to a perfluorinated compound gas cracker using a gliding arc discharge.

Recently, there is a growing concern and concern about global warming. Accordingly, there is a great need for a technology that suppresses the emission of global radiant heat and suppresses the generation of a material that causes global warming and an efficient technology for treating the generated material.

These materials, called perfluoro carbons or perfluoro compounds, are PFCs, which contain a number of fluorine-containing gases such as CF 4 , C 3 F 8 , and C 2 F 6. Inorganic gases such as NF 3 and SF 6 can be classified.

PFCs account for a large portion of the etching and deposition (CVD) processes of the exhaust gases from display material manufacturing processes such as semiconductors and LCDs, and are becoming environmental problems due to high stability and global warming index. The PFCs are relatively safe and non-toxic, but since they decompose on Earth for more than 1,000 to 10,000 years, they remain on Earth for a long time and prevent global radiation from radiating, causing global warming. Therefore, research on recovery and development of alternative materials, including decomposition techniques for PFCs, is needed.

Currently, PFCs decomposition technology has a high temperature incineration method using hydrogen or a thermochemical treatment method using a catalyst. However, the high temperature incineration method is expensive to mass process, and the thermochemical treatment method using a catalyst or the like has a problem that the volume of the substrate is limited.

Accordingly, the present inventors developed a perfluorinated compound gas decomposing apparatus using a gliding arc method to efficiently disperse the perfluorinated compound gas at a high flow rate while studying to decompose hardly decomposable perfluorinated compound gas. It was confirmed that it can be decomposed, and the present invention was completed.

An object of the present invention is to provide a perfluorinated compound gas cracking apparatus using a gliding arc method.

Another object of the present invention to provide a method for decomposing a perfluorinated compound gas using the perfluorinated compound gas decomposition device.

In order to achieve the above object, the present invention provides a cylindrical inner space and a reactor having an exhaust port thereon; An electrode unit mounted in the shape of two blades inside the reactor; A power source installed outside the reactor to induce a gliding arc by applying electricity to the electrode unit; A mixer for mixing and supplying a perfluorinated compound gas, which is a raw material gas, and a diluting gas into the reactor; Provided is a perfluorinated compound gas decomposition device using a gliding arc including a perfluorinated compound gas storage device and a diluent gas storage device supplied to the mixer.

The present invention also provides a method for decomposing a perfluorinated compound gas using the perfluorinated compound gas decomposition device.

The perfluorinated compound gas decomposition device according to the present invention uses a gliding arc discharge, and since the gliding arc has both an equilibrium state and an unbalance state, it is in the category of low temperature plasma and has a tendency of thermal plasma. Since it generates a lot of chemically active species such as radicals, it is possible to effectively decompose stable and difficult to decompose perfluorinated gas. In addition, it is possible to process a large amount of fluid per unit time, and the simple structure has the advantage that can be more efficiently treated perfluorinated compound gas if applied to the semiconductor and display process.

Hereinafter, the present invention will be described in detail.

The present invention is a cylindrical reactor having an exhaust port at the top; An electrode unit mounted in the shape of two blades inside the reactor; A power source installed outside the reactor to induce a gliding arc by applying electricity to the electrode unit; A mixer for mixing and supplying a perfluorinated compound gas, which is a raw material gas, and a diluting gas between the electrode units in the reactor; Provided is a perfluorinated compound gas decomposition device using a gliding arc including a perfluorinated compound gas storage device and a diluent gas storage device supplied to the mixer.

In the perfluorinated compound gas cracking apparatus according to the present invention, the apparatus may further include an analyzer provided at the end of the exhaust port for qualitative and quantitative analysis of the gas discharged after the perfluorinated compound gas is decomposed in the reactor.

Hereinafter, one embodiment according to the present invention will be described in more detail with reference to FIG. 1 .

The perfluorinated compound gas decomposing device according to the present invention includes a reactor (1) providing a cylindrical internal space having a predetermined diameter, an electrode portion (3) mounted inside the reactor, and applying electricity to the electrode portion to form a gliding arc. An inducing power source 4; And a mixer 5 for mixing and supplying a perfluorinated compound gas, which is a raw material gas, and a diluent gas, into the reactor.

First, the reactor (1) takes the form of a cylinder, the inner wall surface provides a cylindrical inner space having a certain diameter. The electrode portion 3 is vertically positioned in the inner space, and a plasma region is formed by an arc discharge in a space between the inner circumferential surface of the inner wall surface and the outer circumferential surface of the electrode portion.

The upper part of the reactor is provided with an exhaust port (2). The exhaust port 2 is a passage through which the exhaust gas is discharged after the perfluorinated compound gas supplied to the reactor is decomposed by the arc discharge in the reactor. In order to qualitatively and quantitatively analyze the exhaust gas, an analyzer such as FT-IR may be provided at the end of the exhaust port.

Next, the electrode unit 3 is located vertically in the reactor, and consists of two electrodes having a blade shape. An arc discharge occurs between the blade-shaped electrodes. At this time, the spacing between the two electrodes is preferably 2-3mm for effective arc discharge. In addition, the electrode is preferably made of stainless steel alloy (SUS). This is because the SUS reacts with fluorine generated when the perfluorinated compound gas is decomposed to form FeF 3 , thereby performing a catalytic role of inhibiting recombination and decomposition reaction of the perfluorinated compound (see FIG. 8 ).

Next, the power source 4 serves to induce a gliding arc by applying electricity to the electrode portion. In this case, it is preferable to use a pulsed AC power as the power source. The pulsed AC power source can generate and maintain an arc more efficiently than conventional AC and DC discharges.

Next, the mixer 5 serves to mix the perfluorinated compound gas, which is the raw material gas, and the diluent gas, and to supply the inside of the reactor. In this case, the concentration of the perfluorinated compound may be variously adjusted by mixing the high purity perfluorinated compound gas and the diluent gas through the mixer.

In the apparatus according to the present invention, the perfluorinated compound gas used may be CF 4 , NF 3 , SF 6, etc., and the concentration-adjusted perfluorinated compound gas is fed to the reactor through a 1/8 inch nozzle. Supplied.

In the apparatus according to the invention, the flow rate of the perfluorinated compound gas supplied to the reactor was adjusted to 3 ~ 10 L / min. If the flow rate of the perfluorinated compound gas is too small, there is a problem in that the arc cannot be pushed up to generate a plasma region, and if the flow rate of the perfluorinated compound gas is too large, the residence time in the reactor is reduced, so that the reaction does not occur sufficiently, so that the decomposition rate is decreased. There is a decreasing problem.

The method of decomposing the perfluorinated compound gas using the perfluorinated compound gas decomposition device according to the present embodiment configured as described above includes the following steps:

Introducing a subject perfluorinated compound gas into the reactor through a 1/8 inch nozzle (step 1);

The perfluorinated compound gas introduced in step 1 is decomposed by arc discharge generated between the electrodes while passing between two blade-shaped electrodes (step 2);

Discharging the gas decomposed in the step 2 through the exhaust port (step 3).

Specifically, step 1 is a step of introducing the perfluorinated compound gas to be treated into the reactor through a 1/8 inch nozzle. In this step, a perfluorinated compound gas, such as CF 4 , NF 3 , SF 6, etc., is mixed with the diluent gas through a mixer and introduced into the reactor, using a 1/8 inch nozzle for introducing a certain amount. desirable.

In addition, the flow rate of the perfluorinated compound gas supplied to the reactor was adjusted to 3 ~ 10 L / min. If the flow rate of the perfluorinated compound gas is too small, there is a problem in that the arc cannot be pushed up to generate a plasma region, and if the flow rate of the perfluorinated compound gas is too large, the residence time in the reactor is reduced, so that the reaction does not occur sufficiently, so that the decomposition rate is decreased. There is a decreasing problem.

Step 2 is a step of decomposing the perfluorinated compound gas introduced in Step 1 through an arc discharge. In this step, the arc discharge is generated between two blade-shaped electrodes in the reactor, and the perfluorinated compound gas introduced into the reactor reacts with the arc generated while passing between the electrodes, thereby forming a plasma region. The perfluorinated compound gas is decomposed. At this time, the spacing between the two electrodes is preferably 2-3mm for effective arc discharge. In addition, the electrode is preferably made of stainless steel alloy (SUS). This is because the SUS reacts with fluorine generated when the perfluorinated compound gas is decomposed to form FeF 3 , thereby performing a catalytic role of inhibiting recombination and decomposition reaction of the perfluorinated compound.

Next, step 3 is a step of discharging the gas decomposed in step 2. The gas decomposed in step 2 is discharged through the exhaust port. Decomposition gas can be passed through an analyzer such as FT-IR to determine the rate of decomposition.

Since the gliding arc used in the present invention has both equilibrium and non-equilibrium characteristics, it is in the category of low-temperature plasma and has a tendency of thermal plasma, and because it generates many chemically active species such as ions and radicals, it is perfluorinated. It is possible to efficiently decompose stable and difficult to decompose harmful gases such as compound gas. In addition, it is possible to process a large amount of fluid per unit time, and the simple structure has the advantage that can be more efficiently treated perfluorinated compound gas if applied to the semiconductor and display process.

Hereinafter, the present invention will be described in more detail through experimental examples.

However, the following experimental examples are only illustrative of the present invention, and the content of the present invention is not limited to the following experimental examples.

< Experimental Example  1> according to gas flow rate Perfluoridation  Decomposition rate measurement of compound gas

CF 4 , NF 3 , one of PFCs gas, which is considered as an egg cracking gas in the perfluorinated compound gas cracking apparatus of FIG. 1. Alternatively, SF 6 was used to measure the decomposition rate according to the gas flow rate.

(One) Perfluoridation  Compound gas cracker

As the reaction tube, a Pyrex tube having an inner diameter of 95 mm and a length of 300 mm was used. The top and bottom of the reaction tube were sealed with bakelite plates. The electrode in the reaction tube used a blade-shaped electrode having a length of 150 mm, a material of SUS-304, and a maximum spacing of 20 mm. The electrode installed in the reaction tube had a minimum proximity interval of 2.5 mm and the reaction gas was directly injected through a tube having an inner diameter of 2 mm between the positive electrodes. At this time, the distance between the tube and the electrode was set to 5 mm. Plasma generating power generated arc discharge using an ultra short pulse power generating device (EN TECHNOLOGIES, IHP-1002). The output frequency of the power generator was fixed at 40 kHz and on time at 5 μsec. In the experiment, the voltage applied to the gliding arc plasma discharge tube was fixed at 10 kV, which shows the best decomposition rate. The flow rate of the gas introduced into the reaction tube was controlled by using a mass flow meter (SiFC) and a ball-flow meter. The gas decomposed by the arc discharge plasma in the reaction tube was collected by FT-IR by the tube connected to the discharge tube to observe the decomposition rate of the gas after decomposition and the components remaining in the gas after decomposition were analyzed.

(2) Decomposition rate measurement

CF 4 , NF 3 with high purity air Alternatively, SF 6 was introduced into a mixer by adjusting a ball-flow meter and a mass flow controller (MFC), respectively, and then a flow rate of each gas sufficiently mixed with air flows into the reactor was adjusted as shown in Table 1 below. The concentration of introduced gas was fixed at 5000 ppm to analyze the decomposition rate of the decomposed gas. The measurement results are shown in FIGS. 2 to 4 and Table 2.

gas Gas flow rate (sccm) CF 4 4130 6130 8130 10130 NF 3 7050 8060 9065 10060 SF 6 7080 8095 9110 10125

CF 4 NF 3 SF 6 Gas flow rate
(sccm) Decomposition
(%) Gas flow rate
(sccm) Decomposition
(%) Gas flow rate
(sccm) Decomposition
(%) 4130 82.7 7050 98.8 7080 98.9 6130 71.7 8060 96.7 8095 92.7 8130 59.2 9065 84 9110 88.7 10130 54.6 10060 79.6 10125 86.9

2 shows the decomposition rate of CF 4 according to the gas flow rate, FIG. 3 shows the decomposition rate of NF 3 , and FIG. 4 shows the decomposition rate of SF 6 .

As shown in Figures 2 to 4 and Table 2, the most stable material CF 4 was decomposed up to 82% at 4L / min, NF 3 , SF 6 was decomposed about 99% at 7L / min. In addition, it can be seen that as the flow rate increases, the residence time in the reactor decreases, so that the reaction does not occur sufficiently and the decomposition rate decreases.

< Experimental Example  2> Qualitative analysis of exhaust gas

CF 4 , NF 3 in Experiment 1 Alternatively, after decomposing SF 6 , the exhaust gas is qualitatively analyzed through FT-IR, and the results are shown in FIGS. 5 to 7 , respectively.

As shown in FIGS . 5 to 7 , when air is used as a diluent gas, NO, NO 2 and HF are commonly generated as exhaust gases, and in the case of CF 4 and SF 6 , CO 2 and SO 2 F 2 are produced as by-products. Generated.

< Experimental Example  3> Analysis of powder deposited on the inner wall of the reactor

After decomposing the perfluorinated compound gas in Experimental Example 1, the powder deposited on the inner wall of the reactor was analyzed by XRD, and the results are shown in FIG. 8 .

As shown in FIG . 8 , the deposited powder was found to be FeF 3 , and due to the synthesis of the powder, the effect of reducing the amount of fluorine gas generated during decomposition of the perfluorinated compound gas was significantly reduced, and the recombination reaction was also suppressed. It can be seen that the component acted as a catalyst in the reaction.

1 is a perspective view showing a perfluorinated compound gas decomposition apparatus using a gliding arc discharge according to an embodiment of the present invention.

2 is a graph showing the decomposition rate of CF 4 according to the gas flow rate according to an embodiment of the present invention.

3 is a graph showing the decomposition rate of NF 3 according to the gas flow rate according to an embodiment of the present invention.

4 is a graph showing the decomposition rate of SF 6 according to the gas flow rate according to an embodiment of the present invention.

5 is a spectrum of qualitative analysis of the exhaust gas after decomposition of CF 4 according to an embodiment of the present invention through FT-IR.

6 is a spectrum of qualitative analysis of the exhaust gas after decomposition of NF 3 according to an embodiment of the present invention through FT-IR.

7 is a spectrum obtained by qualitative analysis of the exhaust gas after decomposition of SF 6 according to an embodiment of the present invention through FT-IR.

8 is a graph showing the results of analyzing the powder deposited on the inner wall of the reactor according to an embodiment of the present invention by XRD method.

<Short description of drawing symbols>

1: reactor 2: exhaust

3: electrode part 4: power supply

5: Mixer 6: Perfluorinated Compounds (PFCs) Gas Storage

7: Dilution Gas Storage 8: Analyzer (FT-IR)

Claims (4)

A cylindrical reactor having an exhaust port at the top; An electrode unit in which two blade-shaped electrodes of two stainless steel alloys (SUS) are mounted at intervals of 2 to 3 mm in the reactor; A pulsed AC power source which is installed outside the reactor and induces a gliding arc by applying electricity to the electrode unit; A mixer for supplying a mixture of CF 4 , NF 3, or SF 6 gas, which is a perfluorinated compound gas, and a dilution gas, as a raw material gas between electrode portions of the reactor; Perfluorinated compound gas decomposition device using a gliding arc comprising a perfluorinated compound gas storage device and a dilution gas storage device is supplied to the mixer at a rate of 3 ~ 10 L / min. According to claim 1, Perfluorinated compound gas decomposition apparatus using a gliding arc further comprises an analyzer provided at the end of the exhaust for qualitative, quantitative analysis of the gas discharged after the perfluorinated compound gas in the reactor. delete Introducing a perfluorinated compound gas into the reactor through a 1/8 inch nozzle (step 1); The perfluorinated compound gas introduced in step 1 is decomposed by arc discharge generated between the electrodes while passing between two blade-shaped electrodes (step 2); Method for decomposing the perfluorinated compound gas using the decomposition device of claim 1 comprising the step (step 3) of discharging the gas decomposed in the step 2 through the exhaust port.
KR1020080082805A 2008-08-25 2008-08-25 Apparatus for decomposition of PFCs gas using gliding arc discharge KR101038295B1 (en)

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CN115646155B (en) * 2022-10-14 2024-07-16 国家电网有限公司 Oil-cooled sulfur hexafluoride degradation device and degradation method based on sliding arc discharge
CN115624849A (en) * 2022-10-21 2023-01-20 国家电网有限公司 Optimizing device based on dielectric barrier discharge degradation sulfur hexafluoride

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002085939A (en) * 2000-09-14 2002-03-26 Air Water Inc Decomposition treatment process of fluorine-based waste gas
JP2006007219A (en) * 2005-07-19 2006-01-12 Dowa Mining Co Ltd Decomposition equipment of carbon fluorides
KR20060026424A (en) * 2003-06-17 2006-03-23 닛테쯔 고우교 가부시키가이샤 Gas processing method and gas processing apparatus utilizing oxidation catalyst and low-temperature plasma
KR100596511B1 (en) * 2004-06-30 2006-07-03 플라즈마에너지자원 주식회사 Air cleaner

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002085939A (en) * 2000-09-14 2002-03-26 Air Water Inc Decomposition treatment process of fluorine-based waste gas
KR20060026424A (en) * 2003-06-17 2006-03-23 닛테쯔 고우교 가부시키가이샤 Gas processing method and gas processing apparatus utilizing oxidation catalyst and low-temperature plasma
KR100596511B1 (en) * 2004-06-30 2006-07-03 플라즈마에너지자원 주식회사 Air cleaner
JP2006007219A (en) * 2005-07-19 2006-01-12 Dowa Mining Co Ltd Decomposition equipment of carbon fluorides

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