KR20060036261A - Method for removing polychlorinated biphenyls by catalyst - Google Patents
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Abstract
본 발명은 변압기 절연유 중 함유된 폴리클로리네이티드 바이페닐(PCBs) 을 팔라듐 촉매와 암모늄포메이트 또는 나트륨포메이트와 반응시켜 PCBs 를 완전히 분해하는 방법을 제공하기 위한 것이다. 본 발명의 방법은 극소량의 촉매 및 포메이트류를 사용함으로써 경제성 및 안전성 측면에서 우수할 뿐만 아니라 반응조건이 상대적으로 온화하여 어떠한 장소에서도 용이하게 적용할 수 있는 장점이 있다.The present invention is to provide a method for completely decomposing PCBs by reacting polychlorinated biphenyls (PCBs) contained in transformer insulating oil with a palladium catalyst and ammonium formate or sodium formate. The method of the present invention is advantageous in terms of economics and safety by using a very small amount of catalysts and formates, and also has an advantage that the reaction conditions are relatively gentle and can be easily applied at any place.
변압기, 절연유, 폴리클로리네이티드 바이페닐, 팔라듐 촉매, 암모늄포메이트, 나트륨포메이트Transformer, Insulating Oil, Polychlorinated Biphenyl, Palladium Catalyst, Ammonium Formate, Sodium Formate
Description
본 발명은 촉매를 이용한 폴리클로리네이트 바이페닐의 제거방법에 관한 것이다. 더욱 상세하게, 본 발명은 난분해성인 유기 염소화합물 특히, 제조 및 사용이 금지되어 있는 폴리클로리네이티드 바이페닐 (Polychlorinated biphenyls, 이하 PCBs라 칭함)을 극소량의 촉매를 사용하여 제거하는 방법으로서, 변압기 절연유 중 함유되어 있는 PCBs의 농도를 저감하거나, 사용완료 후 변압기를 폐기처분할 때 변압기 내부의 절연유 중에 함유되어 있는 PCBs의 무해화처리를 목적으로 하는 방법에 관한 것이다. The present invention relates to a method for removing polychlorate biphenyl using a catalyst. More specifically, the present invention relates to a method for removing a polychlorinated biphenyls (hereinafter referred to as PCBs), which are difficult to manufacture and use, for example, difficult to decompose organic chlorine compounds. The present invention relates to a method for reducing the concentration of PCBs contained in insulating oil or detoxifying the PCBs contained in insulating oil in the transformer when the transformer is disposed of after use.
PCBs는 2001년 스톡홀름 협약에 의하여 제조, 판매, 사용이 금지된 잔류성 유기오염물질로서, 1980년대 이전 PCBs의 뛰어난 절연성과 내열성으로 인하여 변압기 절연유로 주로 사용되어 왔다. PCBs는 화학적으로 안정한 물질로 난분해성을 가지고 있어 인체 및 자연환경조건에서 그 수명이 상당기간 지속되는 경향이 있다. 따라서, 선진국을 중심으로 PCBs 제거를 위한 다양한 연구가 수행되어 용융나트륨분해법, 화학추출분해법, 수열산화법 등이 상업화 또는 실증 단계에 이르고 있는 실정이다. 하지만, 기존의 방법에서는 화학물질의 과다사용, 안전성, 에너지 과소비, 장치의 부식 등과 같은 단점을 가지고 있어 보다 효율적이고 안전한 PCBs 제거법의 개발은 큰 의미가 있다고 할 수 있다.PCBs are persistent organic pollutants that were not manufactured, sold, or used under the 2001 Stockholm Convention, and have been used primarily as transformer insulating oils because of the excellent insulation and heat resistance of PCBs prior to the 1980s. PCBs are chemically stable materials that are difficult to decompose and therefore tend to last a long time in human and natural conditions. Therefore, various studies have been conducted to remove PCBs, especially in developed countries, such that molten sodium decomposition, chemical extraction and hydrothermal oxidation have been commercialized or demonstrated. However, the conventional methods have disadvantages such as overuse of chemicals, safety, energy consumption, and corrosion of devices. Therefore, the development of more efficient and safe PCBs removal method is significant.
PCBs를 제거하는 방법으로 가장 오래된 소각법은 대기중으로 배기가스가 방출되므로 미연소 PCBs 또는 연소부생성물인 다이옥신의 발생이 우려되어 현재로서는 적용이 활발하지 않은 추세이다. As the oldest incineration method to remove PCBs, the exhaust gas is released into the atmosphere, so there is a concern that the generation of unburned PCBs or dioxin, a combustion byproduct, is not applicable.
한편, 일본공개특허공보 제2004-121954호에는 처리액과 산소와의 혼합을 빨리 일으켜 유기할로겐액의 분해반응을 촉진하는 수열분해방법에 관한 것이 소개되어 있고, 일본공개특허공보 제2003-310791호에는 초임계상태 조건에서 물, 과산화수소, 탄산나트륨 또는 탄산칼륨을 이용하여 PCBs를 분해하는 수열산화 분해법에 대해 게재되어 있다. 하지만, 상기와 같은 일본공개특허공보 제2004-121954호와 제2003-310791호에서는 PCBs를 분해하기 위하여 고온, 고압(370℃, 220기압 이상)의 반응조건이 필요하므로 에너지 소비가 많고, 설비의 안전성에 대한 우려가 있어 설비가 설치된 지역주민과의 갈등의 소지가 있을 뿐만 아니라, 격렬한 반응조건으로 인하여 장치의 부식이 발생할 수 있는 문제점이 있다. On the other hand, Japanese Laid-Open Patent Publication No. 2004-121954 discloses a method for hydrothermal decomposition that accelerates the decomposition reaction of an organic halogen solution by causing a rapid mixing of a treatment liquid and oxygen, and Japanese Laid-Open Patent Publication No. 2003-310791 Describes hydrothermal oxidative degradation of PCBs using water, hydrogen peroxide, sodium carbonate or potassium carbonate under supercritical conditions. However, Japanese Patent Laid-Open Publication Nos. 2004-121954 and 2003-310791 as described above require high temperature and high pressure (370 ° C. and 220 atm or higher) reaction conditions in order to decompose PCBs. There is a concern about safety and there is a possibility of conflict with the local people who have installed the equipment, and there is a problem that the corrosion of the device may occur due to the intense reaction conditions.
한편, 독일의 Bilger Umweltconsulting GmbH, 캐나다의 Ontario Hydro, Manitoba Hydro, Powertech, 일본의 Shinko Pantec 등에서는 나트륨의 사용을 기본으로 하는 탈염소화기술을 보유하고 있지만, 금속나트륨(Na)이나 수산화나트륨(NaOH)을 PCBs 기준 당량이상을 사용하여야 하는 단점이 있다. Meanwhile, Bilger Umweltconsulting GmbH in Germany, Ontario Hydro in Canada, Manitoba Hydro, Powertech and Shinko Pantec in Japan have dechlorination techniques based on the use of sodium, but metal sodium (Na) or sodium hydroxide (NaOH) The disadvantage of using more than equivalent PCBs standard.
또한, 일본의 관서테크와 관서전력에서는 Pd/C와 수소를 사용하여 PCBs를 제 거하는 기술을 보유하고 있지만, Pd/C 는 수분에 민감하여 취급이 까다로우며, 수소의 사용도 안전이 우려되는 단점이 있다. In addition, while Japan's Kwanseo Tech and Kwansai Electric Power have the technology to remove PCBs using Pd / C and hydrogen, Pd / C is sensitive to moisture, which makes it difficult to handle and the safety of hydrogen is also a concern. There is a disadvantage.
이에 본 발명에서는 상기와 같은 문제점을 해결하고자 지금까지 알려지지 않은 새로운 방법을 통해 PCBs를 제거하기 위한 것으로, 팔라듐을 촉매로, 포메이트류를 수소원으로 사용하되 극소량의 촉매와 포메이트류를 사용함으로써 경제성 및 안전성 측면에서 우수할 뿐 아니라 반응조건이 상대적으로 온화하여 어떠한 장소에서도 적용이 용이한 PCBs의 제거방법을 제공하는데 그 목적이 있는 것이다. Therefore, the present invention is to remove the PCBs through a new method not known so far to solve the above problems, by using palladium as a catalyst, formates as a hydrogen source by using a very small amount of catalyst and formates The aim is to provide a method of removing PCBs that is not only excellent in terms of economics and safety, but also relatively gentle in reaction conditions, so that it can be easily applied in any place.
상기와 같은 목적을 달성하기 위한 본 발명의 제조방법은 하기 구조식(I)의 PCBs와 수소공여체로서 다음 구조식(II)의 포메이트를 비교적 비극성용매내에서 팔라듐촉매와 반응시켜 하기 구조식(III)의 바이페닐을 제조하는 것으로 이루어진다. The production method of the present invention for achieving the above object is a PCBs of the following formula (I) and a hydrogen donor of the following formula (II) for reacting with the palladium catalyst in a relatively non-polar solvent of the formula (III) Consisting of preparing biphenyls.
여기서 R 은 NH4 또는 Na를 포함하는 금속성분을 의미하며, 비극성용매로는 1-메틸-2-피롤리디논, 1,3-디메틸-3,4,5,6-테트라히이드로-2(1H)-피리미디논, 1,3-디메틸-2-이미다졸리디논 중에서 적어도 하나를 선택하여 사용할 수 있다.Where R is a metal component containing NH 4 or Na, and as the non-polar solvent, 1-methyl-2-pyrrolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H ) -Pyrimidinone and 1,3-dimethyl-2-imidazolidinone can be selected and used.
이하 본 발명을 좀 더 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명의 방법은 상기 구조식(I)의 PCBs를 질소 분위기 하에서 용매에 팔라듐 촉매와 포스핀 리간드와 함께 극소량 넣고, 수소공여체로서 상기 구조식(II)의 1.1당량의 포메이트류, 예를들면 암모늄포메이트 또는 나트륨포메이트를 실온에서 가한 후, 고온, 예를 들면 100 ~ 200 oC에서 2 ~ 10시간 반응시켜 탈염소화하여 상기 구조식(III)의 바이페닐을 제조하는 것으로 이루어진다. In the method of the present invention, the PCBs of the formula (I) are added with a palladium catalyst and a phosphine ligand in a solvent in a nitrogen atmosphere in a small amount, and 1.1 equivalents of formate of the formula (II), for example, ammonium foam, as a hydrogen donor The mate or sodium formate is added at room temperature, followed by reaction for 2 to 10 hours at high temperature, for example, 100 to 200 ° C. to dechlorination to prepare biphenyl of the above formula (III).
본 발명에서 사용하는 포메이트류는 팔라듐 촉매 존재하에서 분해되어 이산화탄소와 수소가 발생하게 되며, 발생되는 수소를 이용할 경우 PCBs의 영소(Cl)를 제거할 수 있게 된다. The formates used in the present invention are decomposed in the presence of a palladium catalyst to generate carbon dioxide and hydrogen, and when the generated hydrogen is used, urea (Cl) of PCBs can be removed.
본 발명에서 사용되는 팔라듐 촉매는 저급 용매나 공기와 접촉할 경우 서서히 파괴되지만 본 발명의 반응이 비교적 신속히 진행되므로 무수용매가 아니더라도 수득율에는 큰 차이는 없다.The palladium catalyst used in the present invention is gradually destroyed when contacted with a lower solvent or air, but the reaction of the present invention proceeds relatively quickly, so there is no significant difference in yield even if it is not an anhydrous solvent.
본 발명에서 사용하는 팔라듐 촉매의 예로는 팔라듐아세테이트, 팔라듐테트라키스, 트리페닐포스핀 중에서 적어도 하나를 선택하여 사용하는 것이 좋고, 이들 촉매의 사용량은 0.01당량 ~ 0.1당량이 바람직하다.As an example of the palladium catalyst used in this invention, it is good to select and use at least 1 among palladium acetate, palladium tetrakis, and triphenyl phosphine, and the usage-amount of these catalysts is preferably 0.01 equivalent-0.1 equivalent.
그리고, 사용되는 리간드의 예로는 모노 또는 바이텐테이트 포스핀리간드가 가장 바람직하고 그 사용량은 상기 팔라듐의 2당량이 바람직하다. As examples of the ligand to be used, mono or bitentate phosphine ligand is most preferred, and its amount is preferably 2 equivalents of the palladium.
본 발명의 방법은 극소량의 촉매 및 포메이트류를 사용함으로써 경제성 및 안전성 측면에서 우수할 뿐만 아니라 반응조건이 상대적으로 온화하여 어떠한 장소에서도 용이하게 적용할 수 있는 장점이 있다.
The method of the present invention is advantageous in terms of economics and safety by using a very small amount of catalysts and formates, and also has an advantage that the reaction conditions are relatively gentle and can be easily applied at any place.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100740919B1 (en) * | 2006-07-31 | 2007-07-20 | 한국해양연구원 | Method for reproducting of insulating oil by removing polychlorinated biphenyl and insulating oil using the same |
| KR100927799B1 (en) * | 2009-03-04 | 2009-11-20 | 주식회사엠제이 | A simultaneously removal method of residual pcbs and electrical insulation oil immersed transformer |
| KR100953506B1 (en) * | 2009-08-26 | 2010-04-16 | 주식회사엠제이 | A removal apparatus of residual pcbs by chemical cleaning and vacuum treatment of oil immersed transformer |
| KR20190093822A (en) | 2018-02-01 | 2019-08-12 | 이성기 | A method for treating PCBs using a microorganism |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5013424A (en) * | 1990-07-30 | 1991-05-07 | Uop | Process for the simultaneous hydrogenation of a first feedstock comprising hydrocarbonaceous compounds and having a non-distillable component and a second feedstock comprising halogenated organic compounds |
| JP2810978B2 (en) * | 1995-09-12 | 1998-10-15 | 工業技術院長 | Dechlorination of aromatic chlorides with formate using palladium and phase transfer catalyst. |
| KR100462705B1 (en) * | 2002-04-09 | 2004-12-20 | 한국해양연구원 | Method of reducing a toxicity of PCB with Pd-Al2O3 and Ultrasonic |
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- 2004-10-25 KR KR1020040085349A patent/KR100749898B1/en active IP Right Grant
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100740919B1 (en) * | 2006-07-31 | 2007-07-20 | 한국해양연구원 | Method for reproducting of insulating oil by removing polychlorinated biphenyl and insulating oil using the same |
| KR100927799B1 (en) * | 2009-03-04 | 2009-11-20 | 주식회사엠제이 | A simultaneously removal method of residual pcbs and electrical insulation oil immersed transformer |
| KR100953506B1 (en) * | 2009-08-26 | 2010-04-16 | 주식회사엠제이 | A removal apparatus of residual pcbs by chemical cleaning and vacuum treatment of oil immersed transformer |
| KR20190093822A (en) | 2018-02-01 | 2019-08-12 | 이성기 | A method for treating PCBs using a microorganism |
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| KR100749898B1 (en) | 2007-08-21 |
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