KR930005292B1 - Treating method of nitrogen oxide exhausting gas - Google Patents

Treating method of nitrogen oxide exhausting gas Download PDF

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KR930005292B1
KR930005292B1 KR1019900015715A KR900015715A KR930005292B1 KR 930005292 B1 KR930005292 B1 KR 930005292B1 KR 1019900015715 A KR1019900015715 A KR 1019900015715A KR 900015715 A KR900015715 A KR 900015715A KR 930005292 B1 KR930005292 B1 KR 930005292B1
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nitrogen oxide
gas
exhaust gas
treatment
generated
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KR920006020A (en
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김창환
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주식회사 임호엔지니어링
임호섭
김창환
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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
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes

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  • Environmental & Geological Engineering (AREA)
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Abstract

This invention relates to simplifying the treatment of NOx and maximizing the efficiency of exhaust gas by pretreatment in the NOX generator. In the treatment introgen oxides, especially NO and NO2 gas, which is generated from furnaces, car engine, chemical industry plants, et al, is oxidized to NO2 by preheated steam and air. Oxidized NO2 is treated by caustic soda (NaOH) in a neuralizing and rinsing scrubber. Thereafter colorless exhaust gas is discharged.

Description

질소산화물(NOx)배기가스의 처리방법Nitrogen oxide (NOx) exhaust gas treatment method

첨부된 도면은 본 발명에 따른 질소산화물 배기가스 처리공정도이다.The accompanying drawings are nitrogen oxide exhaust gas treatment process diagram according to the present invention.

본 발명은 주로 산업현장등의 발생원에서 발생 배출되어 환경오염에 지대한 영향을 끼칠 수 있는 질소산화물(NOx)배기가스의 발생처리방법을 간단화하고 또한 처리된 배기가스의 효율을 극대화할 수 있도록 한 질소산화물 배기가스의 처리방법에 관한 것이다.The present invention mainly simplifies the method of generating and discharging nitrogen oxide (NO x ) exhaust gas that can be generated and discharged from a source such as an industrial site and have a great influence on environmental pollution, and also to maximize the efficiency of the treated exhaust gas. A method for treating nitrogen oxide exhaust gas.

일반적으로 질소산화물(NOx)배기가스 즉, 산화질소(NO), 이산화질소(NO2), 산화질소(N2O), 오산화질소(N2O5) 등의 여러 산화물은 주로 발생원인 가열로(연소로), 자동차배기, 질소화학공장, 황산공장, 금속표면처리 공장, 무ㆍ유기화학처리 공장 등에서 발생하게 되는데 특히, 상기의 발생원에서 배출되는 가스의 형태를 보면, 고온상태(약 1000℃ 이상)로 연소될때의 질소산화물은 공기중의 질소와 산소가 반응하여 비교적 처리가 용이한 농도로 발생하지만 상온 및 저온상태(약 100℃ 이하)에서의 화학반응에 의한 질소산화물은 처리가 매우 곤란한 농도로 발생 배출되었던 것이다.In general, various oxides such as nitrogen oxide (NO x ) exhaust gases, such as nitrogen oxides (NO), nitrogen dioxide (NO 2 ), nitrogen oxides (N 2 O), and nitrogen pentoxide (N 2 O 5 ), are mainly generated by heating furnaces. (Combustion furnace), automobile exhaust, nitrogen chemical plant, sulfuric acid plant, metal surface treatment plant, organic / organic chemical treatment plant, etc., especially in the form of gas discharged from the above-mentioned sources, Nitrogen oxide when burned in the above) is generated at a relatively easy concentration due to the reaction of nitrogen and oxygen in air, but it is very difficult to process nitrogen oxide by chemical reaction at room temperature and low temperature (about 100 ℃ or less). It was generated and discharged at a concentration.

한편, 질소산화물 배기가스층의 NO가스(산화질소)는 그냥 외부로 배출될 경우에는 환경의 오염에 막대한 영향을 주는 것은 물론이며, 그 처리가 매우 어려운 질소산화물 배기가스인 것이다.On the other hand, the NO gas (nitrogen oxide) of the nitrogen oxide exhaust gas layer is a nitrogen oxide exhaust gas that is very difficult to process, as well as having a great influence on the pollution of the environment when just discharged to the outside.

따라서, 상기의 질소산화물 배기가스를 처리하기 위하여 종래에는 전자의 방법으로서 배출된 질소산화물을 중화세정 스크라버(세정집진장치)의 세정액에 처리하는 것으로서 고온상태에서 발생된 질소산화물은 처리가 가능하지만, 상온 및 저온상태에서 발생된 질소산화물은 그 처리 상태가 극히 불량하며 특히, 질소산화물 중에서 환경오염에 영향이 많은 NO가스가 처리가 되지 않은 상태에서 그대로 배출됨으로써 백연(하얀 안개)이 외관상 확실하게 나타나게 되고 배출된 NO가스는 간접적으로는 2차 오염물질을 발생시키게 되며 또한 광화학 반응에 따른 O3를 생성함은 물론 유기연무질(有機煙霧質)이라는 스모그(SMOG)현상으로 까지 나타나게 되어 복잡한 자연환경의 변화 및 오염을 일으키는 원인의 하나가 되는 문제점이 있는 것이다.Therefore, in order to process the nitrogen oxide exhaust gas, conventionally, the nitrogen oxide discharged by the former method is treated in the cleaning liquid of the neutralization scrubber (cleaning dust collector). , Nitrogen oxides generated at room temperature and low temperature are extremely poor in their treatment status. Especially, NO gas, which has a large impact on environmental pollution, is discharged as it is without treatment. The emitted NO gas indirectly generates secondary pollutants, and also generates O 3 from photochemical reactions, as well as SMOG phenomenon called organic fumes. There is a problem that becomes one of the causes of change and pollution.

따라서, 환경오염의 원인이 되는 질소산화물은 종래의 중화세정 스크라버 시설장치로 처리할때는 상기에서와 같이 처리가 매우 어려웠던 것으로서, 이를 감안하여 약 30∼40개의 중화세정 스크라버 시설을 설치 이용하여 본바, 양호한 세정 효율을 얻을 수는 있었으나, 이 또한 많은 량의 중화세정 스크라버 시설을 설치하여야 하기 때문에, 그에 따른 막대한 설치비용과 설치면적이 소요됨은 물론 작업관리상의 어려움 등으로 인한 경제적 손실 등의 여러 가지 문제점이 있었다.Therefore, the nitrogen oxide that causes the environmental pollution was very difficult to process as described above when treated with a conventional neutralization scrubber facility apparatus, and in view of this, about 30 to 40 neutralization scrubber facilities were installed and used. In addition, it was possible to obtain good cleaning efficiency, but this also requires the installation of a large amount of neutralized scrubber facilities, which entails enormous installation costs and installation area as well as economic losses due to difficulties in work management. There were three problems.

따라서, 본 발명의 목적은 상기한 바와같은 제반 문제점을 해결하기 위한 것으로서, 발생원에서 발생 배출된 질소산화물 배기가스를 일차적으로 수증기 및 예열공기를 주입시켜주는 전처리 수단으로 전처리하고 전처리된 질소산화물을 최종적으로 기존의 시설인 1∼2개 정도의 중화세정 스크라버 수단으로 이차 처리하여 줌으로써 세정 효율의 상승은 물론 외부로 배출시 백연의 발생을 방지할 수 있으며, 또한 간단한 처리 장치의 설치에 따른 부대비용을 절감할 수 있도록 한 질소 산화물 배기가스의 처리방법을 제공함에 있다.Accordingly, an object of the present invention is to solve the above-mentioned problems, and pretreatment by pretreatment means for injecting the nitrogen oxide exhaust gas generated from the source and injecting steam and preheating air, and finally the pretreated nitrogen oxide Secondary treatment with one or two neutral cleaning scrubber means that the existing facilities can increase the cleaning efficiency and prevent the generation of white smoke when discharged to the outside. It is to provide a method for treating nitrogen oxide exhaust gas to reduce the cost.

이하, 본발명에 따른 실시예를 첨부된 도면에 개략적으로 도시된 배기가스의 처리 공정도를 참조하면서 상세히 설명하면 다음과 같다.Hereinafter, an embodiment according to the present invention will be described in detail with reference to a process chart of the exhaust gas schematically illustrated in the accompanying drawings.

즉, 발생원에서 발생 배출되는 질소산화물(NOx)배기가스를 효과적으로 처리하기 위한 전처리 수단을 발생원에 연결 설치하여 발생된 질소산화물 배기가스에 일차적으로 가열수단에 따른 수증기 발생과 도시되지 않은 예열공기 주입방법으로 공기를 주입시켜 처리가능한 비율로 동시에 발생시키게 되면 배출되던 질소산화물 배기가스의 대부분은 양호하게 처리됨은 물론 특히, 처리가 불가능했던 NO가스 역시 상기의 수증기 및 더운공기의 주입에 의하여 산화 처리되어 환경상 처리가 용이한 NO2가스로 산화 처리되면서 이차 처리장치인 중화세정 스크라버의 장치로 유입된다.That is, the preliminary air generation and the not shown preheating air injection by the heating means primarily to the nitrogen oxide exhaust gas generated by installing a pre-treatment means for effectively treating the nitrogen oxide (NO x ) exhaust gas generated from the generation source to the generation source When the air is injected at the same time and generated at a treatable rate, most of the emitted nitrogen oxide exhaust gas is well treated, and in particular, the NO gas, which cannot be treated, is oxidized by the injection of steam and hot air. It is oxidized to NO 2 gas, which is easy to treat in the environment, and is introduced into the apparatus of the neutralization scrubber, which is a secondary treatment device.

이때 일차적으로 NO2가스로 산화 처리된 배기가스는 중화세정 스크라버로 유입 반응되면서 양호한 효율로 NO2가스는 재차 처리가 되고, 제거 처리된 NO2가스는 맑은 공기상태로 되어 외부로 배출하게 되는데 이때의 배기되는 가스의 상태 즉, 백연의 발생은 발견할 수 없을 정도인 무색의 배기가스 상태로 배출하게 되어 환경의 오염에 지장을 주지 않게됨과 아울러, 외관상으로도 문제가 되지 않는 것이다.At this time, the exhaust gas oxidized with NO 2 gas is introduced into the neutralization scrubber and reacted with good efficiency, and the NO 2 gas is treated again, and the removed NO 2 gas is discharged to the outside due to the clean air. At this time, the state of the exhaust gas, that is, the generation of white smoke, is discharged in a colorless exhaust gas state which cannot be detected, so that it does not interfere with the environment and is not a problem in appearance.

한편, 상기의 전처리 수단인 수증기 및 더운공기 주입방법은 본 발명에서는 구체적으로 언급하지는 않았지만 필요에 따라서 여러 가지의 장치로 이루어질 수 있는 것이며, 또한, 이차 처리 수단인 중화세정 스크라버에 담겨있는 세정액은 일차처리된 질소산화물의 배기가스가 극히 양호한 상태로 제거 처리시킬 수 있는 화학성분(주로 가성소다)을 적절히 사용할 수 있는 것이다.On the other hand, the steam and hot air injection method as the pretreatment means is not specifically mentioned in the present invention, but may be composed of a variety of devices as needed, and the cleaning liquid contained in the neutralization scrubber as a secondary treatment means It is possible to suitably use a chemical component (mainly caustic soda) capable of removing the primary treated nitrogen oxide exhaust gas in an extremely good state.

따라서, 상기와 같은 전처리 수단은 간단한 구성으로 마련하여 발생원에 설치 사용함으로써 종래의 처리방법으로 처리가 불가능했던 NO가스를 간단한 방법으로 방출 가능한 상태로 용이하게 처리함에 따라, 배출되더라도 환경상 오염의 문제가 되지 않는 가스로 제거 처리할 수 있는 것이다.Therefore, the pretreatment means as described above has a simple configuration and is installed and used in a generation source so that the NO gas, which cannot be treated by the conventional treatment method, is easily treated in a state capable of being discharged by a simple method, so that even if discharged, there is a problem of environmental contamination It can be removed and treated with gas that does not exist.

이의 처리 수단을 보다 구체적으로 설명하기 위한 화학식을 보면(주로 질소산화물 배기가스는 NO, NO2가스가 많이 발생됨),Looking at the formula for explaining the treatment means in more detail (mainly NO, NO 2 gas is generated a lot of nitrogen oxide exhaust gas),

첫째로, 전처리 수단에 따른 NO 및 NO2가스의 화학반응식에서는,First, in the chemical reaction of NO and NO 2 gas according to the pretreatment means,

2NO+O2―→ 2NO2 2NO + O 2 ― → 2NO 2

2NO2+H2O ―→ HNO3+HNO2 2NO 2 + H 2 O ― → HNO 3 + HNO 2

3NO2+H2O ―→ 2HNO3+NO3NO 2 + H 2 O ― → 2HNO 3 + NO

NO+NO2+H2O ―→ 2HNO2로 반응되며,NO + NO 2 + H 2 O ― → reacts with 2HNO 2 ,

즉, 2NO+4NO2+O2+3H2O ―→ 3HNO3+3HNO2로 되며,That is, 2NO + 4NO 2 + O 2 + 3H 2 O ― → 3HNO 3 + 3HNO 2 ,

둘째로, 일차 처리된 NO, NO2가스가 중화세정 스크라버에서 가성소다(NaOH)를 이용한 경우의 처리 화학 반응식은,Secondly, the treatment chemical equation when the primary treated NO and NO 2 gas uses sodium hydroxide (NaOH) in a neutralization scrubber is,

HNO2+NaOH ―→ NaNO3+H2OHNO 2 + NaOH ― → NaNO 3 + H 2 O

HNO2+NaOH ―→ NaNO2+H2OHNO 2 + NaOH ― → NaNO 2 + H 2 O

2NO2+2NaOH ―→ 2NaNO3+H2O2NO 2 +2 NaOH-→ 2NaNO 3 + H 2 O

NO+NO2+2NaOH ―→ 2NaNO2+H2O로 중화 반응되어 염이 생겨 제거된다.NO + NO 2 + 2 NaOH-→ 2 NaNO 2 + H 2 O neutralization reaction to form a salt is removed.

즉, 발생원에서 발생 배출된 NO가스는 전처리 수단에서는 화학반응하여 처리가능한 NO2가스로 변화되며, 이차 처리의 중화세정 스크라버에서는 소정의 세정액인 가성소다용액(NaOH)에 의해 양호한 효율로 처리됨을 확실하게 알 수 있는 것이다.That is, the NO gas generated from the source is converted into NO 2 gas which can be chemically reacted in the pretreatment means, and in the neutralization scrubber of the secondary treatment, it is treated with good efficiency by the caustic soda solution (NaOH), which is a predetermined cleaning solution. I can know for sure.

이상과 같은 본 발명에 따른 처리 수단을 알미늄 표면처리 공장에서 사용한 실시예를 서술하여 본다.The Example which used the processing means which concerns on this invention as mentioned above in an aluminum surface treatment plant is described.

즉, 강산성 화학 연마액(이산액 85%, 질산액 60%, 황산액 98%)을 100℃의 온도에서 알미늄 제품을 표면 처리하기 위해 약 10초 전후로 침적한 후 물에 세척하는 작업시 발생되는 가스의 화학 반응식을 보면,That is, a strong acid chemical polishing liquid (85% of diacid, 60% of nitric acid, 98% of sulfuric acid) is deposited at about 100 seconds to immerse the aluminum product at a temperature of 100 ° C and then washed in water. If you look at the chemical reaction of the gas,

1) 100℃의 온도로 작업할 때,1) When working at a temperature of 100 ℃,

7Al+7H3POt+5HNO3―→ 7AlPO4+N2↑+NO2↑+BH2O7Al + 7H 3 PO t + 5HNO 3 ― → 7AlPO 4 + N 2 ↑ + NO 2 ↑ + BH 2 O

2Al+6HNO3―→ Al2O3+6NO↑+3H2O로 반응되어 N2, NO2및 NO황갈색 가스가 발생되며,2Al + 6HNO 3 ― → Al 2 O 3 + 6NO ↑ + 3H 2 O to react with N 2 , NO 2 and NO tan gas,

2) 100℃의 온도에서 작업이 없을 때,2) When there is no work at a temperature of 100 ℃,

2HNO3―→ H2O+2NO↑+30(묽은 질산)으로서 질산은 비점은 86℃임으로 자체의 황갈색 가스와 NO가스가 발생되어 외부에 백연의 상태로 배출됨을 알 수 있다.2HNO 3 ― → H 2 O + 2NO ↑ + 30 (dilute nitric acid), the nitric acid has a boiling point of 86 ℃ and its own yellowish brown gas and NO gas are generated and discharged as white lead on the outside.

하지만, 발생된 황갈색(NO2)가스 등은 기존 시설인 중화세정 스크라버에서 처리가 가능하지만, NO가스는 처리가 되지 않아 백연이 나타나는 상태로 배출되었다. 하지만, 이에 전처리 수단을 설치하고 수증기 및 공기를 주입하여 준 다음 중화세정 스크라버로 처리하여 줌으로써 상기와 같은 배기가스가 제거처리됨은 물론 외부로 배출되어 나타나던 백연은 발견할 수 없었다.However, the generated yellowish brown (NO 2 ) gas, etc. can be treated in an existing facility neutralization scrubber, but the NO gas was not treated, so it was discharged with white lead. However, by installing the pretreatment means, injecting water vapor and air, and then treating with a neutralization scrubber, the exhaust gas was removed and the white smoke appeared to be discharged to the outside.

따라서, 본 발명에 따른 처리방법을 이용한 환경오염 및 효율을 측정한 결과 표 1과 같은 효과를 얻었다.Therefore, as a result of measuring environmental pollution and efficiency using the treatment method according to the present invention, the effects shown in Table 1 were obtained.

[표 1]TABLE 1

상기와 같이 특히 질소산화물(NOx)배기가스는 상당히 높은 효율을 얻음은 물론 허용기준 보다 양호한 값을 얻을 수 있음을 알 수 있다.As described above, in particular, the nitrogen oxide (NO x ) exhaust gas can obtain a significantly higher efficiency as well as a better value than the limit.

한편, 이상과 같은 실시예의 본원 발명을 여러 방법을 이용하여 백연의 발생 상태를 대비 관찰하여 본바 아래의 표 2와 같은 시험 데이타의 결과를 얻을 수 있었다.On the other hand, the present invention of the embodiment as described above by using a variety of methods to observe the occurrence state of white lead was obtained the results of the test data as shown in Table 2 below.

[표 2]TABLE 2

즉, 상기 대비표에서와 같이 본원 발명에 따른 처리 방법인 전처리수단의 수증기 및 공기를 발생원에서 발생된 NO가스에 예열 주입처리하고 이에 NaOH(가성소다용액)으로 후처리 수단인 중화세정 스크라버에서 처리하여 줌으로써 백연의 발생이 없음을 알 수 있으나, 다른 처리방법에서는 백연이 발생되고 있는 것임을 알 수 있다. 한편 중화세정 스크라버에 진한 황산액과 NaOH 용액으로 처리하여 주어도 백연의 발생은 없었으나, 이는 진한 황산액 사용에 따른 작업의 위험성 및 황산 소모에 대한 교환 위험과 부식 등의 여러가지 결점으로 인하여 사용하기에는 어려운 점이 있는 것이다.That is, as shown in the comparison table, the steam and air of the pretreatment means, which is the treatment method according to the present invention, are preheated and injected into the NO gas generated from the source, and in the neutralization scrubber, which is a post treatment means with NaOH (caustic soda solution). It can be seen that there is no occurrence of white smoke by the treatment, but it can be seen that white smoke is generated in another treatment method. On the other hand, the treatment of neutralized scrubber with concentrated sulfuric acid solution and NaOH solution did not produce white lead, but it was not possible to use due to various defects such as the risk of work due to the use of concentrated sulfuric acid solution and the risk of exchange and sulfuric acid consumption. There is a difficulty.

이상과 같이 본원발명은 환경오염물질을 가진 질소산화물 배기가스의 제거처리를 수증기 및 공기를 주입하는 전처리 수단으로 일차 처리하고 이에 NaOH(가성소다)으로 후처리 수단인 중화세정 스크라버에서 이차 처리하여 줌으로써, 질소산화물 배기가스를 간단한 방법을 백연의 발생이 없으며, 양호한 배기가스 처리 효율을 얻을 수 있어 배출되더라도 환경에 전혀 영향을 주지 아니함은 물론, 종래 처리수단에 비해 설치가 간단하고 작업이 용이하며, 설치비용이 절감되어 경제적 손실을 막을 수 있는 매우 유용한 효과를 갖는 발명인 것이다.As described above, the present invention primarily treats the removal of nitrogen oxide exhaust gas with environmental pollutants by pretreatment means for injecting water vapor and air, and then secondary treatment in neutralization scrubber, which is a post-treatment means with NaOH (caustic soda). By providing nitrogen oxide exhaust gas with a simple method, no white smoke is generated, and good exhaust gas treatment efficiency can be obtained, which does not affect the environment even when discharged, and is simpler to install and easier to work with than conventional treatment means. Therefore, the invention is an invention having a very useful effect that can reduce the installation cost and prevent economic losses.

Claims (1)

발생원에서 발생 배출되는 질소산화물(NOx)의 백연발생및 환경오염물질을 처리함에 있어서, 발생원에서 발생되는 질소산화물 중 특히, 환경에 영향을 주는 산화질소(NO) 및 이산화질소(NO2)를 전처리 수단의 수증기 및 공기를 예열 주입하여 일차적으로 처리가 용이한 이산화질소(NO2) 가스로 산화처리하고 이를 후처리 수단인 중화세정 스크라버에 처리가능한 가성소다(NaOH)용액으로 최종처리하여 백연의 발생을 방지할 수 있도록 한 질소산화물(NOx)배기가스의 처리방법.In treating the white smoke generation and environmental pollutants of nitrogen oxide (NO x ) generated from the source, the pretreatment of nitrogen oxide (NO) and nitrogen dioxide (NO 2 ) that affect the environment, among the nitrogen oxides generated from the source, By preheating and injecting steam and air from Sudan, it is oxidized with nitrogen dioxide (NO 2 ) gas, which is easy to process, and finally treated with a caustic soda (NaOH) solution which is treated in a neutralizing scrubber, which is a post-treatment means, to generate white lead. Method of treating nitrogen oxide (NO x ) exhaust gas to prevent the gas.
KR1019900015715A 1990-09-29 1990-09-29 Treating method of nitrogen oxide exhausting gas KR930005292B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100694492B1 (en) * 2006-09-18 2007-03-14 문형우 Device for preventing white plume phenomenon with self heating

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100694492B1 (en) * 2006-09-18 2007-03-14 문형우 Device for preventing white plume phenomenon with self heating

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