KR970011328B1 - Tert-butyalcohol decomposing method using gamma rays and ozone - Google Patents
Tert-butyalcohol decomposing method using gamma rays and ozone Download PDFInfo
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- KR970011328B1 KR970011328B1 KR1019940024298A KR19940024298A KR970011328B1 KR 970011328 B1 KR970011328 B1 KR 970011328B1 KR 1019940024298 A KR1019940024298 A KR 1019940024298A KR 19940024298 A KR19940024298 A KR 19940024298A KR 970011328 B1 KR970011328 B1 KR 970011328B1
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Abstract
Description
제1도는 여러 가지 실험조건에서의 감마선 조사시간에 따른 터트-부틸알코올의 총 유기탄소농도감소 변화량.1 is a change in the total organic carbon concentration decrease of tert- butyl alcohol with gamma irradiation time under various experimental conditions.
제2도는 오존·방사선 병행조건에서 감마선 조사시간에 따른 터트-부틸알코올의 감소 및 분해부산물의 생성 변화량.2 is a decrease in the tert-butyl alcohol and the generation of decomposition by-products with the gamma irradiation time under ozone-radiation conditions.
본 발명은 오존만으로는 분해가 곤란한 물질인 터트(tert)-부틸알코올 용액을 오존과 감마선조사를 병용함으로써 분해하는 것에 관한 것이다.The present invention relates to the decomposition of a tert-butyl alcohol solution, which is a substance which is difficult to decompose only by using ozone, in combination with ozone and gamma irradiation.
터트-부틸알코올은 석유와 천연가스의 주성분으로써 산업적으로 매우 중요한 물질이다.Tert-butyl alcohol is an important industrial component as a main component of petroleum and natural gas.
이들은 주로 고분자물질을 합성하기 위한 원료물질로써 이용되어 왔지만 최근에는 페인트산업 등을 포함하는 용제로써도 많이 사용되어 있어 자연환경으로의 유출 가능성이 매우 높아지고 있으며 일부는 이미 유출된 경우도 있다.They have been mainly used as raw materials for synthesizing polymer materials, but lately they are also used as solvents, including paint industry, and the possibility of outflow into the natural environment is very high, and some have already leaked.
이것이 자연환경으로 유출될 경우에는 터트-부틸알코올이 지니고 있는 강한 독성(쥐에 대한 50% 치사율 : 933mg/kg)때문에 환경을 오염시키는 오염물질로 될 뿐만 아니라 매우 위험하다.If it is released into the natural environment, it is not only a pollutant that pollutes the environment because of the strong toxicity of tert-butyl alcohol (50% mortality in rats: 933 mg / kg).
그러나 이들을 처리하기 위하여 기존의 처리방법인 생물학적 처리방법을 적용할 경우, 미생물에 대한 독성 때문에 처리능력을 상실하게되며, 기존의 물리·화학적 방법을 적용할 경우에도 다량의 이차적 오염물질의 발생으로 인하여 완전한 처리는 불가능하다.However, when the biological treatment method, which is a conventional treatment method, is used to treat them, the treatment capacity is lost due to the toxicity to microorganisms, and even when the existing physical and chemical methods are applied, a large amount of secondary pollutants are generated. Complete processing is impossible.
최근에는 오존을 이용한 탄화수소 분해방법을 이용하여 이들의 문제점을 해결하려 하지만 오존의 선택적 반응성(즉, 불포화탄화수소 물질과는 쉽게 반응하지만 포화탄화수소 물질과는 반응하지 않음)때문에 이 방법 역시 완전한 해결방안으로는 될 수 없는 실정이다.In recent years, ozone-based hydrocarbon decomposition has been used to solve these problems, but due to the selective reactivity of ozone (that is, it reacts easily with unsaturated hydrocarbons but not with saturated hydrocarbons), this method is also a complete solution. Cannot be.
대부분의 포화탄화수소 물질이 오존과 반응시 분해되지 않는 이유는 포화탄화수소 물질의 산화에 관여하는 하이드록실 라디칼(OH-)이 반응 중 모두 자체에서 소모되고, 오존에 의한 연쇄반응을 유도하는 수퍼옥사이드 라디칼(O2-)역시 생성되지 않음으로써 연쇄반응이 중단되기 때문인 것으로 알려져 있다.The reason that most saturated hydrocarbons do not decompose upon reaction with ozone is that the hydroxyl radicals (OH-) that are involved in the oxidation of saturated hydrocarbons are all consumed in the reaction itself, and superoxide radicals that induce chain reaction by ozone. It is known that the chain reaction is stopped by not forming (O 2- ).
따라서 본 발명은 오존이 지니고 있는 단점을 보완함과 아울러 포화탄화수소 물질의 분해효과를 높이기 위하여 방사선의 독특한 특성을 착안하여 감마선 이용기법을 도입하였다.Therefore, the present invention introduces a gamma ray utilization technique by paying attention to the unique characteristics of radiation in order to compensate for the disadvantages of ozone and to enhance the decomposition effect of saturated hydrocarbon materials.
오존이 공급되는 물에 방사선을 조사하면 물이 분해되어 OH 라디칼과, 전자(eaq-)를 발생시킨다.Irradiation of water to which ozone is supplied causes water to decompose to generate OH radicals and electrons (e aq- ).
이때 발생되는 OH 라디칼은 유기물을 산화시키는 역할을 하며, 전자(eaq-)는 오존을 분해하여 수퍼옥사이드 라디칼(O2-)을 생성함으로써 오존만에 의한 포화탄화수소 물질의 분해반응의 진행을 지속시킬 수 있다.The OH radical generated at this time plays a role of oxidizing organic matter, and the electron (e aq- ) decomposes ozone to generate superoxide radical (O 2- ), thereby continuing the decomposition reaction of saturated hydrocarbon material by ozone only. You can.
또한 연쇄반응시에 생성되는 분해생성물질들은 미생물에 대한 독성이 거의 없는 유기산이 대부분으로, 생물학적으로 분해가 가능하도록 하는것에 그 목적이 있다.In addition, the degradation products generated during the chain reaction are mostly organic acids with little toxicity to microorganisms, the purpose of which is to enable biological degradation.
본 발명의 다른 목적은 기존의 물리·화학적 처리방식이 처리 후 다량의 슬럿지 발생으로 인한 이차공해물질의 발생이라는 문제점이 항상 내포되어 있는데 반하여, 본 발명에 의한 방법은 유기물질을 완전히 분해하여 이산화탄소와 물로 전환시킬 수 있음으로 인하여 이차 공해물질의 발생을 방지할 수 있도록 하는 것에 있다.Another object of the present invention is that the conventional physical and chemical treatment method is always a problem of the generation of secondary pollutants due to the generation of a large amount of sludge after treatment, the method according to the present invention is completely decomposed organic matter and carbon dioxide and It can be converted to water to prevent the generation of secondary pollutants.
이하 첨부된 도면에 연계하여 상세하 설명하면 다음과 같다.Hereinafter will be described in detail with reference to the accompanying drawings.
본 발명은 오존만으로는 분해가 안되는 대표적인 것으로 알려진 터트-부틸알코올용액을 분해대상물질로 선정하였다.In the present invention, a tert-butyl alcohol solution, which is known to be not decomposed only by ozone, was selected as a decomposition target material.
방사선원은 코발트를 이용한 감마선을 이용하였으며, 방사선량을 4.1kGy/hr 이었다.The radiation source was gamma-ray using cobalt and the radiation dose was 4.1 kGy / hr.
오존은 순산소를 이용하여 발생시켰으며, 농도는 1.3w%이었다.Ozone was generated using pure oxygen and the concentration was 1.3w%.
실시예Example
터트-부틸알코올 및 포화탄화수소물질을 분해함에 있어서, 오존에 의한 처리시 방사선을 동시에 조사시키되 감마선 조사조건은 실온에서 1kGy/hr이상의 선량률로써 총 1-100kGy/hr의 흡수선량으로 하고 포화탄화수소 물질의 총 유기탄소 농도는 200mg/L이하이며, 터트-부틸알코올의 총 유깅탄소농도 역시 200mg/L이하로 하며 오존의 농도는 순산소를 이용한 오존 발생시 공급산소의 3.0w%이하로 였다.In decomposing tert-butyl alcohol and saturated hydrocarbon materials, the radiation is simultaneously irradiated upon treatment with ozone, but the gamma-irradiation conditions are absorbed doses of 1-100 kGy / hr at a dose rate of 1 kGy / hr or more at room temperature. The total organic carbon concentration was 200 mg / L or less, the total yugging carbon concentration of tert-butyl alcohol was also 200 mg / L or less, and the concentration of ozone was 3.0 w% or less of the supply oxygen when ozone generation using pure oxygen was generated.
상기의 실시예의 본 발명의 효과를 입증키 위하여 실험방법은 일정농도를 갖는 터트-부틸알코올을 반응용기에 넣은후 오존을 반응기에 하부에 설치된 산기관을 통하여 공급하면서 동시에 방사선을 정해진 시간동안 조사하는 것이다.In order to prove the effect of the present invention of the above embodiment, the experimental method is to put a tert- butyl alcohol having a certain concentration in the reaction vessel and supply ozone through an acid pipe installed at the bottom of the reactor while irradiating radiation for a predetermined time. will be.
제1도는 총 유기탄소농도(TOC) 36mg/L인 터트-부틸알코올용액을 방사선 단독, 오존 단독, 방사선과 오존을 병행한 조건하에서 반응시간에 따른 총 유기탄소 농도의 감소경향을 나타낸 결과이다.FIG. 1 shows the result of decreasing the total organic carbon concentration according to reaction time of tert-butyl alcohol solution having a total organic carbon concentration (TOC) of 36 mg / L under radiation alone, ozone alone, and radiation and ozone.
방사선과 오존을 각각 단독으로 반응시켰을 경우 총 유기탄소농도는 거의 감소되지 않았다.When the radiation and ozone reacted alone, the total organic carbon concentration hardly decreased.
그러나 방사선과 오존을 병용시켜 반응하였을 경우에는 반응시간 1시간 경과후에 총 유기탄소농도가 16mg/L 50%로 감소되었으며, 반응시간을 연장할 경우 나머지 총 유기탄소도 모두 분해될 수 있음을 보여주었다.However, the reaction with radiation and ozone reduced the total organic carbon concentration to 16 mg / L 50% after 1 hour of reaction time, and it was shown that the total organic carbon could be decomposed if the reaction time was extended.
제2도는 방사선과 오존을 병용한 실험에서 반응시간에 따른 분해생성물의 생성양상을 보여주는 결과이다.2 is a result showing the formation of decomposition products according to the reaction time in the experiment using a combination of radiation and ozone.
터트-부틸알코올이 분해되면서 1차 분해생성물질인 아세톤이 생성되고 반응시간이 증가되면서 개미산, 초사, 유산, 피루빅산 등의 생성 역시 증가되고 있음을 보여주었다.As the tert-butyl alcohol was decomposed, the first decomposition product, acetone, was produced and the reaction time was increased, indicating that the production of formic acid, super sand, lactic acid, and pyruvic acid also increased.
따라서 본 반응에서 생성된 개미산을 포함한 모든 유기산은 방사선에 의하여 발생되는 OH라디칼에 의하여 쉽게 분해될 수 있어 방사선과 오존을 병용한 실험에서 총 유기탄소농도가 쉽게 감소될 수 있음을 뒷받침할 뿐만 아니라, 오존만으로는 전혀 분해가 이루어지지 않는 터트-부틸알코올도 방사선의 도움에 의하여 충분히 분해될 수 있음을 알 수 있다.Therefore, all organic acids, including formic acid produced in this reaction, can be easily decomposed by OH radicals generated by radiation, which not only supports that the total organic carbon concentration can be easily reduced in the experiment with radiation and ozone. It can be seen that tert-butyl alcohol, which is not decomposed at all, can be sufficiently decomposed with the aid of radiation.
또한 이들 유기산은 생물학적으로 쉽게 분해될 수 있어 생물학적 처리를 병용할 수도 있다.In addition, these organic acids can be easily decomposed biologically, so that a combination of biological treatments can be used.
반면 오존 또는 방사선 단독으로 터트-부틸알코올과 반응시켰을 경우에는 표 1에 나타난 바와같이 반응시간이 1시간 경과후에도 분해반응은 거의 진행되지 않아 부산물이 생성되어 않았음을 알 수 있다.On the other hand, when reacted with tert-butyl alcohol by ozone or radiation alone, as shown in Table 1, even after 1 hour, the decomposition reaction hardly proceeded, indicating that by-products were not produced.
따라서 방사선과 오존은 병용하는 처리방법은 오존만에 의해서는 분해가 되지 않는 터트-부틸알코올을 쉽게 분해할 수 있음을 보여주었으며, 오존의 선택적 반응에 따른 단점도 보완할 수 있어 포화탄화수소 물질의 분해에 대해서도 적용 가능함을 보여주고 있다.Therefore, the combination method of radiation and ozone showed that tert-butyl alcohol, which is not decomposed by ozone alone, can be easily decomposed, and the disadvantages caused by the selective reaction of ozone can be compensated for. It is also shown to be applicable.
이와같이 본 발명은 기존의 환경오염 방지기술이 갖고 있는 단점 즉, 이차오염물 발생들을 피하면서도 완벽하게 오염물질을 제거할 수 있음으로, 본 발명은 상수·폐수 처리장에 적용할 경우 많은 잇점이 있는 것이다.As described above, the present invention can completely remove the contaminants while avoiding the generation of secondary pollutants, that is, the present invention has many advantages when applied to water and wastewater treatment plants.
[표 1]TABLE 1
여러 가지 실험조건에서 분해생성물 농도(반응시간 60분)Decomposition product concentration under various experimental conditions (reaction time 60 minutes)
* tert-부틸알코올의 초기농도는 2.5m mol/L임* The initial concentration of tert-butyl alcohol is 2.5m mol / L
**tert-부틸알코올의 농도는 반응후 남아 있는 농도를 말함** Concentration of tert-butyl alcohol refers to the concentration remaining after the reaction
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