스톡홀름협약은 2004년 발효되어 잔류성유기오염물질(POPs, Persistent Organic Pollutants)로 12종에 대한 생산 또는 사용에 대하여 금지하거나 제한하기 시작하였다. 2017년 현재 잔류성 유기오염물질로 관리되는 화합물은 총 28종으로 등재되어 있다. 브롬화난연제는 플라스틱, 텔레비전, 건축자재, 섬유 등 가연성 물질이나 재료에 첨가하여 발화방지 및 지연을 목적으로 사용하는 화합물이다. 본 연구 조사대상 시료는 5개 사업장에서 TV 후면하우징 플라스틱, 냉장고, 세탁기 혼합플라스틱, 자동차 실내등, 우레탄 폼 등 22건을 채취하였다. 채취한 시료를 절단/분쇄하여 분석용 시료로 사용하였다. 스크리닝 하기 위해 XRF(X-ray Fluorescence)로 측정하였다. 브롬화난연제 분석은 국제 전기표준기구 IEC 62321, 한국표준협회 KS M 1072, 일본 표준협회 JIS C 0950을 참고하여 분석하였다. 브롬화난연제 중 PBDEs, PBBs는 파쇄된 시료를 추출하여 GC/MS로 분석하였고, HBCD, TBBPA는 LC/MS로 분석하였다. 연구 결과 XRF 분석결과, 2000년 이전 TV 후면 하우징에서 Br 함량이 14.84~61.28%, 2000년 이후 것은 47.19~64.17%로 나타났고, 냉장고, 세탁기에서 Br 함량은 낮았다. PBDEs는 TV 후면하우징 플라스틱에서 주로 검출되었으며, 특히 deca-BDE가 높게 검출되었다. 자동차 카시트와 파쇄 잔재물에서는 주로 deca-BDE가 검출되었다. TBBPA는 TV 후면하우징 플라스틱에서 0.7 mg/kg~53.5 mg/kg, 세탁기와 냉장고 플라스틱에서 0.4mg/kg, 자동차 카시트에서 6.4 mg/kg, 706.5 mg/kg으로 검출되었다.

Persistent organic pollutants are highly toxic, stay in the environment for a long time, accumulate in the body according to the food chain, and cause damage not only to the area where they occur but also to other areas beyond the border. Parties to the Convention, as well as Korea, are obliged to carry out various efforts to control, reduce or eliminate sources of POPs in accordance with the national implementation plan. In addition, national efforts to limit the production, distribution and use of persistent organic pollutants and the current state of domestic pollution and emissions should be submitted every five years. A flame retardant is a polymeric material with a property that is easy to burn, and it lowers the ignition point by adding a compound having a large flame retarding effect such as halogen, phosphorus, and a nitrogen metal compound. Among them, chlorine-based flame retardants classified as halogen-based are used for suppressing ignition of combustible organic materials including plastics, furniture, textiles, clothing, and electronic products. It is also used as an alternative to brominated flame retardants, causing mutations in carcinogenic substances, hormone destruction, and nervous system damage. In the case of waste containing chlorine-based flame retardants in Korea, the methods and standards for disposal of waste are not specified. The highest SCCP values were 4,253.09 mg/kg for polyurethane foam, 628.29 mg/kg for mobile phone case and 341.91 mg/kg for flame retardant rubber sheet. In the case of car seats no SCCPs were detected, and TCEP was detected at 512. 66 mg/kg, exceeding the EU limit of 5 mg/kg. However, other chlorinated flame retardants TDCP and TDCPP were not detected in all samples.

국제 원자재 가격 상승 및 환경규제 강화 등으로 인해 폐자원의 재활용에 대한 관심이 높아지고 경제적 가치가 부각되고 있다. 그 중 일상적인 전자제품들은 편의성에 따라 널리 사용되며 폐기시 유해물질로 인한 각종 환경오염 문제를 일으킨다. 이에 정부는 폐전기・전자제품의 재활용 활성화를 위하여 EPR 제도를 도입하여 시행하고 있으며, 2014년 폐소형가전까지 확대 지정하여 EPR 대상품목에 포함하였다. 폐소형가전의 경우 해마다 새로운 제품들이 쏟아져 나오며 재활용 대상 폐가전제품의 발생량도 크게 증가할 것으로 예상된다. 가볍고, 성형이 쉬운 플라스틱을 가전제품에 사용할 경우에는 화재에 취약하다는 단점을 가지고 있다. 특히, 소형가전제품에는 화재예방을 위한 난연제, 제품의 상품성을 높이기 위한 착색제, 제품을 보호하기 위한 코팅제 및 대전방지제 등 각종 첨가제들을 여러 종류 사용하고 있다. 난연제의 경우 우수한 난연 성능 및 저렴한 가격으로 인하여 브롬화난연제(Brominated Flame Retardants, BFRs)를 가장 널리 사용하고 있으며, 대표적인 브롬화난연제는 PBDE(polybrominated diphenyl ether), TBBPA(Tetrabromobisphenol A), HBCD(Hexabromocyclododecane) 등이 있다. 가전제품으로부터 회수한 플라스틱의 효율적인 재활용을 위해서는 브롬화난연제가 함유된 플라스틱의 사전제거가 중요하다. 브롬화난연제를 함유한 플라스틱을 인식/식별하는 기술은 개발되었으나, 선별기술의 상용화사례는 전무한 실정이다. 따라서, 본 연구에서는 레이저 기반 기술을 이용하여 폐소형가전에서 회수한 플라스틱 중 브롬화난연제를 함유한 플라스틱의 특성을 파악하였다. 향후 폐소형가전으로부터 발생한 플라스틱의 효율적인 재활용을 위한 선별기술 개발 자료로 활용하고자 한다.

The use of electrical and electronic products made of low specific gravity and easy processing plastics has increased alongside industrial development. As these products were abandoned, environmental problems such as Dioxine and Furan began to rise. Accordingly, through long-time reviews and discussions, the EU has implemented the Restriction of Hazardous Substances (RoHS) and the Waste Electrical and Electronic Equipment (WEEE) regulations. In addition, the Stockholm Convention was adopted in April 2011 to regulate wastes containing brominated flame retardants. Therefore, the Basel Convention issued technical guidelines and environmentally friendly treatments for wastes containing brominated flame retardants. Proper management and treatment plans that are suitable to Korea’s circumstances are required for Korea to respond to both conventions and changing trends in international POPs management. In this regard, the study identified domestic and international trends in environmental regulations and usages, obtained fundamental data for the management of waste containing brominated flame retardants, and investigated the current status of waste generation in Korea. The results of analyses were used to make a lab-scale incineration reactor as the basis for setting incineration temperature ranges for experiments. After incineration, five general air pollutants (O2, CO, CO2, SOx, and NOx) and three components of BRFs in emission gases and flooring were analyzed to identify whether the PBDEs in waste can be destroyed in a stable and environmental manner during heat treatment. In the analysis, HRMS was used for PBDEs and GC/MS/MS for TBBPA and HBCD. PBDD/DFs was proportionally increased in facilities that had high concentrations of PCDD/DFs during incineration. In conclusion, wastes containing brominated flame retardants in Korea can be incinerated in an environmentally friendly manner.

Brominated flame retardants (BFRs) including PBDEs, TBBPA, and HBCD have been used in a variety of products such as automobiles, electronic products, building materials, and textiles. Because some of BFRs are known to be toxic, persistent, bioaccumulative in the environment, they have a great potential and possibility of human exposure and the environmental release through the use, treatment and disposal of products containing BFRs. Although there have been various efforts on laws and regulations of the restriction on the use of BFRs in many countries, only limited information regarding the levels, flow, treatment technology and regulations of products and wastes containing BFRs is available. In this study, the levels, current regulations and treatment guideline on products and wastes containing BFRs in electronics, automotives, construction materials, and textiles have been examined and summarized. Relative high levels of BFRs in TVs, construction materials and end-of-life vehicles were found, while textiles contained less amounts of BFRs. According to the study, more strengthened regulations are currently underway around the world. Thus, more limited use of BFRs such as deca-BDE in products and wastes is expected. Other chemicals such as TBBPA and HBCD are being evaluated for toxicity and risk assessment. Specific regulatory guideline of BFRs containing products after use (e.g. collection, separation, treatment) should be developed to prevent the widespread dispersion in the environment and human exposure of such chemicals as a result of improper disposal such as incineration and landfilling.

Elemental analysis, calorific value, etc. were measured to obtain basic information such as decomposition temperature and required oxygen amount for thermal treatment of waste containing chlorine-based flame retardant. Moisture, flammability and ash content of polyurethane foam were high in water, flammable rubber sheet in case of ash and flame retardant rubber sheet in case of ash. As a result of thermogravimetric analysis, the weight change in the range of 300 ~ 600 ℃ was large. The content of chlorinated flame retardant agent was analyzed to be higher than that of polyurethane foam (4,253.09 mg/kg), cell phone case (cloth, leather) 628.29 mg/kg and flame retardant rubber sheet 341.91 mg/kg. Chlorinated flame retardant materials, TDCP and TDCPP, were not detected in all samples. As a result of the decomposition tests for chlorine-based flame retardants at 850 ℃ and 1,100 ℃, chlorine-based flame retardant components were not detected in exhaust gas at all at 1,100 ℃ as well as at 850 ℃ in all samples including mobile phone cases, flame retardant rubber sheets and car seats. As a result of calculating the conversion rate for total chlorine value, it showed more than 99% even at 850 ℃ as well as at 1,100 ℃. Considering the decomposition rate in laboratory experiments of chlorine-based flame retardant-containing wastes, it is considered possible to incinerate at a scale of 2 ton/hour or more, which is the existing incineration facility. It is judged that it is not necessary to set separate operating conditions or preventive facility standards since the material is decomposed sufficiently at 850 ℃ or more. However, considering the possibility of dioxin or unintentional persistent organic pollutants, it is considered appropriate to operate at above 1,100 ℃.

PBDEs, TBBPA 및 HBCD를 포함한 브롬계 난연제(BFRs)는 자동차, 전자 제품, 건축 자재 및 직물과 같은 다양한 제품에 사용되고 있다. 일부 브롬화 난연제는 환경적으로 독성, 지속성, 생체 축적성이 있는 것으로 알려져 있어 브롬화 난연제를 함유한 제품의 사용, 처리 및 처분을 통한 인체 노출 및 환경 배출 가능성이 있다. 많은 국가에서 브롬화 난연제 사용에 대한 규제에 관한 법률 및 규정이 다양하게 시행되고 있지만 BFR을 포함하는 제품 및 폐기물의 수준, 흐름, 처리 기술 및 규정에 관한 정보는 제한적으로 이용 가능한 실정이다. 본 연구의 연구 방법은 먼저 국내 브롬화 난연제 적용 현황 및 함유 제품 및 폐기물 내 브롬화 난연제 함량을 파악하였다. 또한 국내외 브롬화 난연제 함유 제품 및 폐기물에 대한 규제현황 및 처리현황을 파악하고 국내에서 적용 가능한 브롬화 난연제 함유 폐기물에 대한 관리기준 및 처리 방안울 제시하고자 하였다. 국내 브롬화 난연제 적용 현황, 함유 제품 및 폐기물 내 브롬화 난연제 함량 검토, 브롬화 난연제 함유 제품 및 폐기물의 규제현황 및 처리현황은 관련 연구보고서 및 논문검토 등 문헌조사 및 통계자료 조사를 통하여 실시하였다. 연구 결과, 1) 국내 유통되는 브롬화 난연제의 사용량은 전기･전자/자동차제품에 범용으로 적용되는 경우가 가장 많았으며(11,077톤), 전기전자, 건축자재, 운송수단의 순이었다. 2) 브롬화난연제 함유 폐기물 내 함량은 폐전기전자제품의 경우 TV가, 건축자재에서는 보온단열재 및 재활용 원료에서 높게 나타났다. 3) 국내외 브롬화 난연제 함유 제품 및 폐기물의 규제현황을 검토한 결과, 전 세계적으로 브롬화 난연제를 규제대상물질로 설정하여 제품 및 폐기물 내 함유 농도로 관리하고 있으나, 국내의 경우 폐기물에 대한 정의 및 관리기준이 수립되어 있지 않았다. 4) 국외 BFRs 함유 폐기물 처리 기술에 대한 조사 결과 재활용, 매립, 물리화학적 처리, 에너지회수 및 소각처리를 하고 있으며 EU 등 일부 국가에서는 브롬화 난연제 함유 물질의 매립을 금지하고 스톡홀름협약에서 제시한 최적가용조건으로 소각처리를 하고 있으나, 국내의 경우 아직까지 브롬화 난연제 함유 폐기물에 대한 처리지침이 수립되어 있지 않다. 본 연구는 브롬화 난연제 함유 폐기물 처리 및 적정 관리 방안 마련을 위한 자료로 활용이 가능하며, 항후 브롬화 난연제를 포함한 잔류성 유기 오염물 관리에 대한 정책 기초자료로 활용할 수 있다.

With industrial development, the use of electrical and electronic products made of low-specific-gravity and easyprocessing plastics has increased. As these products have been abandoned, environmental problems, such as Dioxine and Furan, have begun to arise. Accordingly, through long-time reviews and discussions, the EU has implemented the Restriction of Hazardous Substances (RoHS) and Waste Electrical and Electronic Equipment (WEEE) regulations. Additionally, the Stockholm Convention was adopted in April 2011 for wastes containing brominated flame retardants. Therefore, the Basel Convention issued technical guidelines on environment-friendly treatment for wastes containing brominated flame retardants. For Korea to respond to both the conventions and changing trends in international persistent organic pollutant (POP) management, proper management and treatment plans suitable to Korean circumstances are required. In this regard, the study identified domestic and international trends in environmental regulations and usages, obtained fundamental data for the management of wastes containing brominated flame retardants, and investigated the current status of waste generation in Korea. Based on the results, six target samples were selected and evaluated to see if they were heat-treatable through content analysis, three-component analysis, element analysis, calorific value analysis, and thermogravimetric (TGA) analysis. The results of the analyses were used to make a lab-scale incineration reactor, and the results of the TGA analysis became the basis for setting the incineration temperature ranges for experiments. After incineration, five general air pollutants (O2, CO, CO2, SOx, and NOx) and three components of BRFs in the emission gas and flooring were analyzed to identify if the PBDEs in wastes can be destroyed in a stable and environmental manner during heat treatment.

In this study, the silicone-based flame retardant compound is combined in case of fire, the fire-resistance board structure stability and durability, performance, such as the possibility of secure confirmation. For this purpose, a silicon compound ATH, MDH, MC, a flame retardant of ocher made by the weight ratio, the thermal properties of the specimen analysis tests were carried out.

In this study, conducted an experiment for fire-resistance of silicone/inorganic flame retardant composites as fire resistant materials. Thermal characteristic analysis were performed by TGA(Thermogravimetric analysis) and Fire-resistance analysis performed by flame test. Through this study, we realized that the silicone/inorganic flame retardant composites have fire resistance and potential as Fire resistant materials.