KR100830843B1 - Process for treatment of halogenate volatile organic compounds using akaline molten salt - Google Patents

Process for treatment of halogenate volatile organic compounds using akaline molten salt Download PDF

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KR100830843B1
KR100830843B1 KR1020070005981A KR20070005981A KR100830843B1 KR 100830843 B1 KR100830843 B1 KR 100830843B1 KR 1020070005981 A KR1020070005981 A KR 1020070005981A KR 20070005981 A KR20070005981 A KR 20070005981A KR 100830843 B1 KR100830843 B1 KR 100830843B1
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molten salt
volatile organic
halogenated volatile
organic compound
mixed gas
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Korean (ko)
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양희철
조용준
은희철
김응호
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한국원자력연구원
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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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/68—Halogens or halogen compounds
    • B01D53/70—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s

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Abstract

A process for treatment of halogenated volatile organic compounds using an alkaline molten salt is provided to intercept fundamentally the production of dioxins, effectively decompose the halogenated volatile organic compounds, cut off generation of secondary waste, and omit an additional post-treatment process for treating the secondary waste by reacting the halogenated volatile organic compounds with the alkaline molten salt. A process for treatment of halogenated volatile organic compounds comprises the steps of: supplying a mixed gas of the halogenated volatile organic compounds and dry air into a mixed gas supply pipe in a molten salt oxidation reactor(1) containing an alkaline molten salt(15); and contacting the mixed gas that has been supplied into the mixed gas supply pipe with the alkaline molten salt in the molten salt oxidation reactor while maintaining the mixed gas to a temperature at which the halogenated volatile organic compounds are not subjected to an oxidation reaction by the dry air. The process further comprises the step of mixing oxygen with flue gas that has been exhausted from the molten salt oxidation reactor after the reaction with the alkaline molten salt, injecting the mixed gas into a second molten salt oxidation reactor containing an alkaline molten salt to contact the mixed gas with the alkaline molten salt.

Description

알칼리용융염을 이용한 할로겐화 휘발성 유기화합물의 처리방법{Process for treatment of halogenate volatile organic compounds using akaline molten salt}Process for treatment of halogenate volatile organic compounds using akaline molten salt}

도 1은 본 발명의 할로겐화 휘발성 유기화합물의 처리방법을 구현하기 위한 용융염 산화장치의 구성도이다.1 is a block diagram of a molten salt oxidation apparatus for implementing a method for treating a halogenated volatile organic compound of the present invention.

도 2는 도1에 도시된 용융염 산화장치의 혼합기체 공급관의 구조이다.FIG. 2 is a structure of a mixed gas supply pipe of the molten salt oxidizer shown in FIG. 1.

도 3은 본 발명의 할로겐화 휘발성 유기화합물의 처리방법을 구현하기 위한 장치의 또 다른 구성도이다.3 is another configuration diagram of an apparatus for implementing the method for treating a halogenated volatile organic compound of the present invention.

<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>

1 : 용융염 산화반응기 2 : 1차 용융염 산화반응기1: molten salt oxidation reactor 2: primary molten salt oxidation reactor

3 : 2차 용융염 산화반응기 11, 21 : 산소공급장치3: secondary molten salt oxidation reactor 11, 21: oxygen supply device

12,22 : 불활성 운반기체 공급장치 13,23 : 할로겐화 VOCs공급장치12,22: inert carrier gas supply device 13,23: halogenated VOCs supply device

14, 24 : 혼합기체 공급관 15, 25, 32 : 알칼리용융염14, 24: mixed gas supply pipe 15, 25, 32: molten alkali salt

16, 26, 33 : 배가스 배출구 141 : 단열층16, 26, 33: exhaust gas outlet 141: heat insulation layer

142 : 냉각공기유출입층 143 : 혼합기체 유입층142: cooling air inlet and outlet layer 143: mixed gas inlet layer

31 : 배가스 공급관 34 : 냉각기31: exhaust gas supply pipe 34: cooler

본 발명은 본 발명은 할로겐화 휘발성 유기화합물의 처리방법에 관한 것으로서, 상세하게는 할로겐화 휘발성 유기화합물과 건조공기가 혼합된 혼합기체를 알칼리용융염이 구비된 용융염 산화반응기 내의 혼합기체 공급관으로 공급하는 단계; 상기 혼합기체 공급관 내에 유입된 혼합기체를 할로겐화 휘발성 유기화합물이 건조공기에 의하여 산화반응이 일어나지 않는 온도로 유지하면서 용융염 산화반응기 내의 알칼리용융염과 접촉시키는 단계; 를 포함하는 것을 특징으로 한다.The present invention relates to a method for treating a halogenated volatile organic compound, and more particularly, to supply a mixed gas of a halogenated volatile organic compound and dry air to a mixed gas supply pipe in a molten salt oxidation reactor equipped with an alkali molten salt. step; Contacting the mixed gas introduced into the mixed gas supply pipe with an alkali molten salt in a molten salt oxidation reactor while maintaining the halogenated volatile organic compound at a temperature at which oxidation reaction does not occur by dry air; Characterized in that it comprises a.

종래에는 산업공정에서 폐기되는 할로겐화 휘발성 유기화합물(할로겐화 VOCs)의 처리기술로 활성탄 흡착층에 의한 흡착제거법, 촉매산화법 및 고온소각에 의해 처리하는 방법이 널리 사용되고 있다. 이중에서 흡착제거법은 제거효율이 95%이하로 높지 않을 뿐만 아니라 흡착층을 재생할 때 다시 발생되는 할로겐화 휘발성 유기화합물은 또 다시 다른 방법으로 처리해야 하기 때문에 부가적으로 경제적 문제점이 발생된다. 촉매 산화하는 방법이나 고온 소각하는 기술의 경우에는 일반적인 휘발성 유기화합물에 대해서는 비교적 처리효율이 높으나 할로겐화 휘발성 유기화합물에 대해서는 분해효율이 높지 않으며 산화 또는 소각 처리 후 산 가스가 발생되어 이러한 산 가스를 처리하기 위한 후처리공정이 필요할 뿐만 아니라 또 산 가스에 의한 부식을 방지하기 위해 후처리장치가 특별한 고가의 재질로 제작되어야 하기 때문에 이 또한 경제적인 부담으로 가중된다. 아울러 산 가스 처리를 위해 사 용되는 세정기에서 산성폐수와 같은 이차 폐기물이 발생함은 물론 후처리공정에서 발생된 다이옥신과 같은 독성가스가 배기가스와 함께 배출될 수 있어 이를 해결하기 위한 방안이 반드시 필요하다.Conventionally, as a treatment technique of halogenated volatile organic compounds (halogenated VOCs) which are discarded in an industrial process, adsorption removal by activated carbon adsorption layer, catalytic oxidation method and high temperature incineration are widely used. Among them, the adsorption removal method does not have a high removal efficiency of less than 95%, and additionally economical problems arise because the halogenated volatile organic compounds that are generated again when regenerating the adsorption layer have to be treated by another method. In the case of catalytic oxidation or high temperature incineration, the treatment efficiency is relatively high for general volatile organic compounds, but the decomposition efficiency is not high for halogenated volatile organic compounds, and acid gases are generated after oxidation or incineration treatment to treat such acid gases. This also adds to the economic burden because the post-treatment device has to be made of a special expensive material to prevent corrosion by acid gas as well as a post-treatment process. In addition, secondary scrubbers such as acidic wastewater are generated in the scrubber used for acid gas treatment, and toxic gases such as dioxins generated in the post-treatment process can be discharged together with the exhaust gas. Do.

본 발명은 상기의 문제점을 해소하기 위한 것으로, 본 발명의 목적은 할로겐화 휘발성 유기화합물을 알칼리용융염으로 처리하여 다이옥신과 같은 독성 물질 생성의 전구체인 할로겐원소가 알칼리용융염과 반응하여 포집되도록 함으로써 다이옥신류의 생성을 근원적으로 차단하기 위한 방법을 제공하는 것이며, 또 다른 목적으로는 할로겐화 휘발성 유기화합물을 기상으로 용융염 반응기내로 공급하여 역류 및 화염의 발생 없이 접촉이 원활히 이루어져 할로겐화 휘발성 유기화합물이 효과적으로 분해되도록 하는 할로겐화 휘발성 유기화합물의 처리방법을 제공하는 것이며, 또한 처리시 발생되는 산 가스를 용융염과 반응시켜 배출가스로 배출되지 않게 함으로써 기존의 휘발성 유기화합물 처리공정의 단점인 2차폐기물의 발생을 차단할 수 있고 2차폐기물의 처리를 위한 부가적인 후처리공정이 필요 없는 할로겐화 휘발성 유기화합물의 처리방법을 제공하는 것이다.The present invention is to solve the above problems, an object of the present invention is to treat the halogenated volatile organic compound with an alkali molten salt, so that the halogen element which is a precursor of the generation of toxic substances such as dioxins is collected by reacting with the alkali molten salt to dioxins The present invention provides a method for fundamentally blocking the formation of oils, and another object of the present invention is to supply halogenated volatile organic compounds into the molten salt reactor in a gaseous phase to facilitate contact without generating backflow and flames. The present invention provides a method for treating halogenated volatile organic compounds that decomposes, and also generates secondary waste, which is a disadvantage of the conventional volatile organic compounds treatment process, by reacting acid gas generated during treatment with molten salt so as not to be discharged as exhaust gas. Can block It is to provide a method for treating halogenated volatile organic compounds that does not require additional aftertreatment for the treatment of waste.

상기 기술적 과제를 달성하기 위한 것으로서, 본 발명에 따른 할로겐화 휘발성 유기화합물의 처리방법은 할로겐화 휘발성 유기화합물과 건조공기가 혼합된 혼 합기체를 알칼리용융염이 구비된 용융염 산화반응기 내의 혼합기체 공급관으로 공급하는 단계; 상기 혼합기체 공급관 내에 유입된 혼합기체를 할로겐화 휘발성 유기화합물이 건조공기에 의하여 산화반응이 일어나지 않는 온도 이하로 유지하면서 용융염 산화반응기 내의 알칼리용융염과 접촉시키는 단계; 를 포함하는 것을 특징으로 한다.In order to achieve the above technical problem, a treatment method of a halogenated volatile organic compound according to the present invention is a mixed gas supply pipe in a molten salt oxidation reactor equipped with an alkali molten salt mixed gas mixture of the halogenated volatile organic compound and dry air Supplying; Contacting the mixed gas introduced into the mixed gas supply pipe with an alkali molten salt in a molten salt oxidation reactor while maintaining the halogenated volatile organic compound below a temperature at which oxidation reaction does not occur by dry air; Characterized in that it comprises a.

본 발명에 따른 할로겐화 휘발성 유기화합물의 처리방법은 할로겐화 휘발성 유기화합물로서 트리클로로에탄 및 트리클로로플루오르메탄을 예시하여 설명한 하기의 화학반응식(1) 및 화학반응식(2)에서 기재한 바와 같이 할로겐화 휘발성 유기화합물은 함께 공급되는 산소와 함께 알칼리용융염과 반응하여 할로겐화알칼리염, 이산화탄소 및 물이 생성되는 방법으로서 휘발성 유기화합물을 분해함과 동시에 할로겐원소는 염화나트륨(NaC)l, 불화나트륨(NaF) 및 브롬화나트륨(NaBr)등의 유용한 무기염으로 전환되어 회수하여 공업용으로 재활용할 수 있는 장점이 있다.The method for treating a halogenated volatile organic compound according to the present invention is a halogenated volatile organic compound as described in the following Chemical Scheme (1) and Chemical Scheme (2), which exemplifies trichloroethane and trichlorofluoromethane as halogenated volatile organic compounds. The compound reacts with the alkali molten salt together with oxygen supplied to produce halogenated alkali salts, carbon dioxide and water, and decomposes volatile organic compounds, while the halogen elements are sodium chloride (NaC) l, sodium fluoride (NaF) and bromide. There is an advantage that can be recovered and converted to useful inorganic salts such as sodium (NaBr) and recycled for industrial use.

2C2HCl3(g)+3Na2CO3+3O2(g) -> 6NaCl+7CO2(g)+H2O(g) (1)2C 2 HCl 3 (g) + 3Na 2 CO 3 + 3O 2 (g)-> 6NaCl + 7CO 2 (g) + H 2 O (g) (1)

CCl3F(g)+2Na2CO3 -> 3NaCl+NaF+3CO2(g) (2)CCl 3 F (g) + 2Na 2 CO 3- > 3NaCl + NaF + 3CO 2 (g) (2)

상기의 혼합기체 공급관 내에 유입된 혼합기체를 할로겐화 휘발성 유기화합물가 건조공기에 의하여 산화반응이 일어나지 않는 온도로 유지하는 조건은 본 발명에 다른 방법에 있어서 가장 특징적인 구성으로서, 상기의 온도 조건을 채용함으 로써 800℃ 이상의 고온이 유지되는 용융염 산화반응기 내의 고온 분위기의 영향으로 혼합기체 공급관 내에 유입된 혼합기체인 할로겐화 휘발성 유기화합물과 건조공기가 알칼리용융염과 접촉 전에 연소반응 등의 산화반응을 방지하는 효과를 얻을 수 있으며, 또한 고온의 혼합기체가 알칼리용융염 내로 공급됨으로써 고온의 용융염내에서 갑작스런 기화에 의해 급격한 부피팽창이 일어나지 않게 하고, 할로겐화 휘발성 유기화합물의 혼합기체가 고온의 용융염 반응기내 액상 용융염의 하부에서부터 미세한 기체방울로 골고루 분산되도록 하는 역할을 하게 된다.The condition in which the mixed gas introduced into the mixed gas supply pipe is maintained at a temperature at which the halogenated volatile organic compound is not oxidized by dry air is the most characteristic configuration in another method according to the present invention. The effect of high temperature atmosphere in the molten salt oxidation reactor that maintains high temperature above 800 ℃ prevents oxidation reaction such as combustion reaction before the halogenated volatile organic compound which is the mixed gas introduced into the mixed gas supply pipe and dry air is contacted with alkali molten salt. In addition, a high temperature mixed gas is supplied into the molten alkali salt to prevent sudden volume expansion due to sudden vaporization in a high temperature molten salt, and a mixed gas of a halogenated volatile organic compound is melted in a high temperature molten salt reactor in a liquid phase. Fine groups from the bottom of the salt It is responsible for so evenly distributed as droplets.

상기 혼합기체 공급관 내에 유입된 혼합기체를 할로겐화 휘발성 유기화합물이 건조공기에 의하여 산화반응이 일어나지 않는 온도는 할로겐화 휘발성 유기화합물의 종류에 따라 달라질 수 있으나, 상기 온도는 일반적으로 언급되는 할로겐화 휘발성 유기화합물 기준으로 볼 때 200 내지 300℃인 것이 적절하다.The temperature at which the halogenated volatile organic compound does not oxidize the mixed gas introduced into the mixed gas supply pipe may vary depending on the type of halogenated volatile organic compound, but the temperature is based on the halogenated volatile organic compound generally mentioned. It is appropriate that it is 200 to 300 ℃.

한편 본 발명에서는 800℃ 이상의 고온이 유지되는 용융염 산화반응기 내의 고온 분위기의 영향을 받지 않고 상기의 혼합기체 공급관 내에 유입된 혼합기체를 할로겐화 휘발성 유기화합물이 건조공기에 의하여 산화반응이 일어나지 않는 온도를 유지하기 위해서 상기 혼합기체 공급관은 외부 온도에 영향을 적게 받는 단열공급관을 채용하는 것이 바람직하며, 특히 외부공기 등을 냉매로 사용하는 단열냉각관을 채용하는 것이 더욱 바람직하다.On the other hand, in the present invention, the mixed gas introduced into the mixed gas supply pipe is subjected to the temperature at which the halogenated volatile organic compound does not undergo oxidation reaction by dry air without being affected by the high temperature atmosphere in the molten salt oxidation reactor maintained at a high temperature of 800 ° C. or higher. In order to maintain the mixed gas supply pipe, it is preferable to employ an insulated supply pipe which is less influenced by the external temperature, and more preferably, an insulated cooling tube using external air as a refrigerant.

본 발명에서 채용되는 알칼리용융염은 탄산칼륨(K2CO3), 탄산나트륨(Na2CO3) 또는 그 혼합물을 포함하며, 용융염 산화반응기 내의 반응온도는 상기 알칼리용융 염을 용융염 상태로 유지할 수 있는 온도 이상이 필요하며, 상기 용융염 산화반응기 내의 반응온도는 800 내지 900℃가 바람직하다.The alkali molten salt employed in the present invention includes potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ) or a mixture thereof, and the reaction temperature in the molten salt oxidation reactor maintains the molten salt in the molten salt state. It can be more than the temperature that can be, the reaction temperature in the molten salt oxidation reactor is preferably 800 to 900 ℃.

할로겐화 휘발성 유기화합물과 혼합되는 건조공기는 실질적으로는 산소를 의미하는 것으로서, 할로겐화 휘발성 유기화합물과 혼합되는 건조공기의 양이 많아지면 할로겐화 휘발성 유기화합물의 알칼리용융염 내의 체류시간이 짧아져 알칼리용융염과의 반응효율이 떨어지는 단점이 있으므로 상기 건조공기의 공급량은 건조공기 내 산소기준으로 할로겐화 휘발성 유기화합물과의 반응당량비(할로겐화 휘발성 휘발성 유기화합물의 탄소 및 수소함량 기준 완전연소에 필요한 산소량의 당량비)로 1:0.6~0.8로 공급되는 것이 바람직하다.The dry air mixed with the halogenated volatile organic compound substantially means oxygen. When the amount of dry air mixed with the halogenated volatile organic compound increases, the residence time in the alkali molten salt of the halogenated volatile organic compound is shortened. Since the reaction efficiency is lower than that of the dry air, the supply amount of the dry air is equal to the reaction equivalent ratio of the halogenated volatile organic compound based on oxygen in the dry air (equivalent ratio of oxygen required for complete combustion based on carbon and hydrogen content of the halogenated volatile volatile organic compound). It is preferable to supply at 1: 0.6 to 0.8.

할로겐화 휘발성 유기화합물과 건조공기의 혼합방법은 제한되지 않으나, 할로겐화 휘발성 유기화합물을 질소, 아르곤 등의 불활성 운반기체에 의하여 공급되도록 하여 상기 건조공기와의 혼합할 수 있다.The method of mixing the halogenated volatile organic compound and dry air is not limited, but the halogenated volatile organic compound may be mixed with the dry air by supplying the halogenated volatile organic compound by an inert carrier such as nitrogen and argon.

한편 본 발명에 따른 할로겐화 휘발성 유기화합물의 처리방법은 앞서 언급한 용융염 산화반응기(1차 용융염 산화반응기) 내의 알칼리용융염과 접촉하는 단계 이후에 상기 알칼리용융염과의 반응 후에 용융염 산화반응기로부터 배출되는 배가스를 산소 또는 공기와 함께 혼합하여 2차 용융염 산화반응기에 투입하여 알칼리용융염과 접촉시키는 단계를 더 포함할 수 있다. 상기의 추가 단계는 용융염산화반응이 저산소분위기에서 운전하는 것에 기인되어 생성된 CO의 제거하는 역할을 하는 것으로 2차 용융염 산화반응기 내 용융염의 하부에서부터 미세한 기체방울로 고온의 액상 용융염내에 골고루 분산시켜 미반응 할로겐화 휘발성 유기화합물을 분해함과 동 시에 산화되지 않은 탄화수소가스와 CO를 CO2로 전환시키는 작용을 한다.Meanwhile, the method for treating a halogenated volatile organic compound according to the present invention is a molten salt oxidation reactor after the reaction with the alkali molten salt after the step of contacting with the alkali molten salt in the molten salt oxidation reactor (primary molten salt oxidation reactor) mentioned above. The exhaust gas discharged from the mixture may be further mixed with oxygen or air and introduced into a secondary molten salt oxidation reactor to contact the alkali molten salt. The additional step is to remove CO generated due to the operation of the molten chlorination reaction in the low oxygen atmosphere. Evenly in the high temperature liquid molten salt with fine gas bubbles from the bottom of the molten salt in the secondary molten salt oxidation reactor. It disperses and decomposes unreacted halogenated volatile organic compounds and simultaneously converts unoxidized hydrocarbon gas and CO into CO 2 .

상기의 추가 단계에서 2차 용융염 산화반응기에 공급되는 산소는 1차 용융염 산화반응기에 공급되는 산소의 양에 추가하여 과잉의 산소를 공급함으로서 1차 용융염 산화반응기 및 2차 용융염 산화반응기에 공급되는 총 공기량이 최초 할로겐화 휘발성 유기화합물 기준으로 완전 연소에 필요한 산소량의 1.2 배 이상, 바람직하게는 1.5 내지 2.5배가 되게 하여 산화반응이 완전히 일어나도록 하는 것이 바람직하다.In the additional step, the oxygen supplied to the secondary molten salt oxidation reactor is supplied to the primary molten salt oxidation reactor in addition to the amount of oxygen supplied to the primary molten salt oxidation reactor, thereby providing the primary molten salt oxidation reactor and the secondary molten salt oxidation reactor. It is preferable that the total amount of air supplied to is at least 1.2 times, preferably 1.5 to 2.5 times, the oxygen amount required for complete combustion on the basis of the first halogenated volatile organic compound so that the oxidation reaction occurs completely.

이하 첨부된 도면을 바탕으로 본 발명에 따른 할로겐화 휘발성 유기화합물의 처리방법을 설명하나, 본 발명은 이에 한정되지 않음은 물론이다.Hereinafter, a method for treating a halogenated volatile organic compound according to the present invention will be described with reference to the accompanying drawings, but the present invention is not limited thereto.

도 1은 본 발명의 할로겐화 휘발성 유기화합물의 처리방법을 구현하기 위한 용융염 산화장치의 구성도이며, 도 2는 도 1에 도시된 용융염 산화장치의 혼합기체 공급관의 구조이고, 도 3은 본 발명의 할로겐화 휘발성 유기화합물의 처리방법을 구현하기 위한 장치의 또 다른 구성도이다.1 is a block diagram of a molten salt oxidizer for implementing a method of treating a halogenated volatile organic compound of the present invention, Figure 2 is a structure of a mixed gas supply pipe of the molten salt oxidizer shown in Figure 1, Figure 3 Another configuration diagram of an apparatus for implementing the method for treating a halogenated volatile organic compound of the present invention.

도 1에 도시된 바와 같이 할로겐화 휘발성 유기화합물 공급탱크(13)에 저장된 할로겐화 휘발성 유기화합물은 불활성 운반기체 공급장치(12)로부터 공급된 불활성 운반기체에 의하여 공급되어 산소공급장치(11)로부터 공급된 산소와 혼합되며, 혼합된 할로겐화 휘발성 유기화합물과 건조공기의 혼합기체는 알칼리용융염(15)이 구비된 용융염 산화반응기(1) 내의 혼합기체 공급관(14)으로 공급된다. 상기 혼합기체 공급관은 고온이 유지되는 용융염 산화반응기 내의 고온 분위기의 영향을 받지 않고 상기의 혼합기체 공급관(14) 내에 유입된 혼합기체를 할로겐화 휘발성 유기화합물이 건조공기에 의하여 산화반응이 일어나지 않는 온도를 유지하기 위해서 상기 혼합기체 공급관(14)은 도 2에 도시된 바와 같이 외부공기를 냉매로 사용하는 냉각공기유출입층(142)을 채용한다. 할로겐화 휘발성 유기화합물이 건조공기에 의하여 산화반응이 일어나지 않는 온도 이하로 유지되는 혼합기체는 산기관을 통하여 용융염 산화반응기 내의 알칼리용융염(15)과 접촉시킴으로써 할로겐화 휘발성 유기화합물은 할로겐화알칼리염과 CO2 및 물로 전환된다.As shown in FIG. 1, the halogenated volatile organic compounds stored in the halogenated volatile organic compound supply tank 13 are supplied by the inert carrier gas supplied from the inert carrier gas supply device 12 and supplied from the oxygen supply device 11. The mixed gas of the mixed halogenated volatile organic compound and dry air with oxygen is supplied to the mixed gas supply pipe 14 in the molten salt oxidation reactor 1 provided with the alkali molten salt 15. The mixed gas supply pipe is a temperature at which the halogenated volatile organic compound is not oxidized by dry air to the mixed gas introduced into the mixed gas supply pipe 14 without being affected by the high temperature atmosphere in the molten salt oxidation reactor maintained at a high temperature. In order to maintain the mixed gas supply pipe 14, as shown in FIG. 2, a cooling air inlet and outlet layer 142 using external air as a refrigerant is employed. The mixed gas in which the halogenated volatile organic compound is kept below the temperature at which the oxidation reaction does not occur by dry air is brought into contact with the alkali molten salt (15) in the molten salt oxidation reactor through an acid pipe. 2 and water.

또한 도 3에 도시된 바와 같이 1차 용융염 산화반응기(2)에서 알칼리용융염과의 반응 후에 1차 용융염 산화반응기(2)로부터 배출되는 배가스는 산소공급장치(21)로부터 공급되는 과량의 산소와 함께 혼합되어 2차 용융염 산화반응기(3)에 투입하여 미반응 할로겐화 휘발성 유기화합물을 분해함과 동시에 탄화수소 및 CO를 CO2로 산화시킨다.3, the exhaust gas discharged from the primary molten salt oxidation reactor 2 after the reaction with the alkali molten salt in the primary molten salt oxidation reactor 2 is excessively supplied from the oxygen supply device 21. It is mixed with oxygen and introduced into the secondary molten salt oxidation reactor (3) to decompose the unreacted halogenated volatile organic compound and to oxidize hydrocarbon and CO to CO 2 .

이하 본 발명을 실시예를 들어 설명한다.Hereinafter, the present invention will be described with reference to Examples.

[실시예 1]Example 1

도 3과 같은 구성을 가지는 용융염산화공정장치에서 몰비 1:1로 혼합된 탄산칼륨(K2CO3) - 탄산나트륨(Na2CO3) 혼합용융염을 이용하여 850 oC와 900 oC의 온도 하에 염소계 유기용매 분해시험을 수행하였다. 분해대상물질로 산업공정에서 널리 활 용되어 폐기물로 배출되고 있는 트리클로로에틸렌(TCE; Trichloroethylene)을 선정하였으며, 트리클로로에틸렌을 시간당 약 1.5 kg과 2.0 kg의 처리속도로 용융염 산화반응기에 주입하였다. 이 때 1차 용융염 산화반응기에 이론공기량의 70%에 해당하는 산화용 공기를, 2차 용융염 산화반응기에는 추가로 이론산소량의 80%(1차 반응기에 투입되는 트리클로로에틸렌의 완전연소에 필요한 절대공기량의 80%)에 해당하는 산소를 공급하였다. 이상의 조건으로 수행된 분해시험에서 배출되는 배기가스는 테프론백에 포집한 후 GC-MSD/ECD를 이용하여 트리클로로에틸렌을, 대기오염공정시험법상의 오르토톨리딘 흡수분광법과 티오시안산 제 2수은법에 따라 시료를 채취하여 염소가스(Cl2)와 염화수소(HCl)를 분석하였다. 그 결과, 트리클로로에틸렌은 모두 검출한계(0.001ppm) 이하로 나타나 트리클로로에틸렌 분해효율이 모두 99.99999%를 초과하는 것으로 확인되었으며, 염화수소(HCl)과 염소가스(Cl2)의 농도는 모두 2.5ppm 이하로 검출되어 용융염내에서 99.999% 이상의 높은 염소포집효율 보였다.850 o C and 900 o C using a molten salt mixed with potassium carbonate (K 2 CO 3 )-sodium carbonate (Na 2 CO 3 ) mixed molten salt in a molten chlorination process apparatus having a configuration as shown in FIG. Chlorine-based organic solvent decomposition test was performed under temperature. Trichlorethylene (TCE; Trichlorethylene), which is widely used in industrial processes and discharged as waste, was selected as a decomposition material, and trichloroethylene was injected into a molten salt oxidation reactor at a processing rate of about 1.5 kg and 2.0 kg per hour. . At this time, the primary molten salt oxidation reactor is supplied with oxidizing air corresponding to 70% of the theoretical air volume, and the secondary molten salt oxidation reactor is further added to 80% of the theoretical oxygen amount (complete combustion of trichloroethylene injected into the primary reactor. Oxygen equivalent to 80% of the absolute air required). The exhaust gas discharged from the decomposition test carried out under the above conditions was collected in Teflon bag and trichloroethylene was collected using GC-MSD / ECD. Orthotolidine absorption spectroscopy and airborne mercury thiocyanate in the air pollution process test method Samples were collected and analyzed for chlorine gas (Cl 2 ) and hydrogen chloride (HCl). As a result, all of the trichloroethylene was detected below the detection limit (0.001 ppm), and the trichloroethylene decomposition efficiency was found to exceed 99.99999%, and the concentrations of hydrogen chloride (HCl) and chlorine gas (Cl 2 ) were both 2.5 ppm. It was detected as below and showed high chlorine capture efficiency of over 99.999% in molten salt.

Figure 112007005613882-pat00001
Figure 112007005613882-pat00001

이상과 같은 본 발명에 따른 할로겐화 휘발성 유기화합물의 처리방법은 다이옥신류의 생성을 근원적으로 차단 가능한 방법으로서 종래의 방법에 의한 할로겐화 휘발성 유기화합물의 처리 시에 발생되던 2차폐기물이 발생되지 않을 뿐만 아니라 산 가스가 발생되지 않기 때문에 분해처리장치 이후의 배기가스 후처리장치의 추가나 배관을 내부식성 재질로 구성할 필요가 없으며, 부산물로 생성되는 염화나트륨(NaC)l, 불화나트륨(NaF) 및 브롬화나트륨(NaBr)과 같은 무기염을 공업적으로 재활용할 수 있어 산업세정공정 등 할로겐화 휘발성 유기화합물 배출 산업공정의 운영비를 절감할 수 있는 장점이 있다.The treatment method of the halogenated volatile organic compounds according to the present invention as described above is a method capable of fundamentally blocking the production of dioxins, and does not generate secondary waste generated during the treatment of the halogenated volatile organic compounds by the conventional method. Since no acid gas is generated, there is no need to add exhaust gas aftertreatment after the decomposition treatment device or to construct the pipe with a corrosion resistant material. Sodium chloride (NaC) l, sodium fluoride (NaF), and sodium bromide (by Since inorganic salts such as NaBr) can be industrially recycled, there is an advantage of reducing the operating costs of halogenated volatile organic compound emission industrial processes such as industrial cleaning processes.

Claims (9)

할로겐화 휘발성 유기화합물과 건조공기가 혼합된 혼합기체를 알칼리용융염이 구비된 용융염 산화반응기 내의 혼합기체 공급관으로 공급하는 단계;Supplying a mixed gas of a halogenated volatile organic compound and dry air to a mixed gas supply pipe in a molten salt oxidation reactor equipped with an alkali molten salt; 상기 혼합기체 공급관 내에 유입된 혼합기체를 할로겐화 휘발성 유기화합물이 건조공기에 의하여 산화반응이 일어나지 않는 온도로 유지되면서 용융염 산화반응기 내의 알칼리용융염과 접촉시키는 단계;Contacting the mixed gas introduced into the mixed gas supply pipe with an alkali molten salt in a molten salt oxidation reactor while maintaining the temperature at which the halogenated volatile organic compound is not oxidized by dry air; 를 포함하는 할로겐화 휘발성 유기화합물의 처리방법.Method of treating a halogenated volatile organic compound comprising a. 제 1 항에 있어서,The method of claim 1, 상기 혼합기체 공급관은 외부공기의 순환에 의하여 냉각되는 단열냉각관이 구비되는 것을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.The mixed gas supply pipe is a method of treating a halogenated volatile organic compound, characterized in that the heat insulation cooling tube is cooled by the circulation of external air. 제 1 항에 있어서,The method of claim 1, 혼합기체 공급관 내의 산화반응이 일어나지 않는 온도는 200 내지 300℃인 것을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.Process for the treatment of halogenated volatile organic compounds, characterized in that the temperature at which the oxidation reaction does not occur in the mixed gas supply pipe. 제 1 항에 있어서,The method of claim 1, 상기 알칼리용융염은 탄산칼륨(K2CO3), 탄산나트륨(Na2CO3) 또는 이들의 혼합물인 것을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.The alkali molten salt is a method of treating a halogenated volatile organic compound, characterized in that potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ) or a mixture thereof. 제 1 항에 있어서,The method of claim 1, 상기 용융염 산화반응기 내의 반응온도는 800 내지 900℃인 것을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.The reaction temperature in the molten salt oxidation reactor is a method for treating halogenated volatile organic compounds, characterized in that 800 to 900 ℃. 제 1 항에 있어서,The method of claim 1, 할로겐화 휘발성 유기화합물과 혼합되는 건조공기는 상기 건조공기 중의 산소기준으로 할로겐화 휘발성 유기화합물의 완전연소에 필요한 산소량의 반응당량비로 1:0.6~0.8로 공급되는 것을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.The dry air mixed with the halogenated volatile organic compound is supplied in a ratio of 1: 0.6 to 0.8 in a reaction equivalent ratio of the amount of oxygen required for complete combustion of the halogenated volatile organic compound on the basis of oxygen in the dry air. . 제 6 항에 있어서,The method of claim 6, 상기 할로겐화 휘발성 유기화합물은 불활성 운반기체에 의하여 공급되는 것 을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.And the halogenated volatile organic compound is supplied by an inert carrier gas. 제 1 항에 있어서,The method of claim 1, 상기 알칼리용융염과의 반응 후에 용융염 산화반응기로부터 배출되는 배가스를 산소와 함께 혼합하여 2차 용융염 산화반응기에 투입하여 알칼리용융염과 접촉시키는 단계를 더 구비하는 것을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.The halogenated volatile organic compound further comprises the step of mixing the exhaust gas discharged from the molten salt oxidation reactor with oxygen after the reaction with the molten alkali salt and injecting the secondary molten salt oxidation reactor into contact with the alkali molten salt. Treatment method. 제 8 항에 있어서,The method of claim 8, 1차 용융염 반응기 및 2차 용융염 반응기에 공급되는 총산소량은 최초 할로겐화 휘발성 유기화합물 기준으로 완전 연소에 필요한 산소량의 1.5 내지 2.5배인 것을 특징으로 하는 할로겐화 휘발성 유기화합물의 처리방법.The total amount of oxygen supplied to the primary molten salt reactor and the secondary molten salt reactor is 1.5 to 2.5 times the amount of oxygen required for complete combustion on the basis of the first halogenated volatile organic compound treatment method of the halogenated volatile organic compound.
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