국내 자동차 폐촉매의 발생 및 재활용 현황

권영식,이재천,신도연,이승훈,김형진,최윤근,Kwon, Young-Shik,Lee, Jae-Chun,Shin, Do Yun,Yi, Seung-Hoon,Kim, Hyung-Jin,Choi, Yoon-Geun 한국자원리싸이클링학회 2014 資源 리싸이클링 Vol.23 No.1

백금족 귀금속이 함유된 자동차 폐촉매는 경제적 가치 및 귀금속 확보 측면에서 재활용의 중요성이 매우 높은 순환자원 이다. 본 연구에서는 국내에서 발생하고 있는 자동차 폐촉매의 재활용과 관련된 정책수립 및 기술개발의 효율적 추진을 위하여 자동차 폐촉매 발생량, 유통현황, 재활용 기술 및 재활용 산업 현황을 조사하였다. 자동차 폐촉매 발생량은 자동차 등록 및 폐차 통계와 신차(新車)에 대한 촉매 장착 이력 등을 분석하여 추정하였다. 재활용 기술 및 산업 현황은 국내 최대 자동차 폐촉매 재활용 기업인 (주)희성피엠텍의 재활용 공정 및 현황을 중심으로 조사하였다. 더불어 자동차 폐촉매 재활용 산업의 활성화를 위한 제도적 개선 방안도 제시하였다. Recycling of spent autocatalyst that includes the platinum group metals (PGMs), namely palladium, platinum and rhodium, is a very profitable endeavor. In order to ensure an efficient promotion of an appropriate policy-making and the technical development of the recycling process of spent autocatalyst in Korea, the generated amount, trading conditions, and recycling technology for spent autocatalyst were surveyed. The generated amount of spent autocatalyst was estimated by analyzing the domestic statistical data of registration & disuse of automobiles and the records of autocatalyst installation to new cars. The review of the recycling technology was carried out by surveying the recycling processes of 'Heesung PMTech Ltd.', which is the largest company in the recycling industry for spent autocatalyst in Korea. In addition to the above, some policy suggestions for the improvement of recycling industries for spent autocatalyst were offered.

산처리된 자동차 폐촉매의 VOCs 연소 성능평가

서성규 ( Seo Seong-gyu ),문정선 ( Moon Joung-sun ),조성용 ( Cho Sung-yong ) 한국환경기술학회 2000 한국환경기술학회지 Vol.1 No.2

본 연구는 자동차 폐촉매의 재활용 가능성을 검토하기 위하여 산처리에 따른 촉매의 VOCs 연소활성에 관하여 조사하였다. 자동차 폐촉매의 물리화학적 특성을 조사하기 위하여 EA(Elemental analyzer) 및 ICP-AES(Inductively coupled plasma-atomic emission spec-trophotometer) 분석을 실시하였다. Pt, Pd 및 Rh 중 Pt가 가장 많이 함유되어 있었으며, 귀금속 함유량은 주행거리가 길수록 감소하는 경향을 보였다. 침적 carbon의 제거를 위하여 공기를 이용한 전처리 영향을 조사한 결과, 400℃에서 1hr동안 전처리 했을 때 가장 우수한 활성을 보였다. 또한, 자동차 폐촉매에 함유되어 있는 피독 물질 제거 및 재생에 의한 촉매활성을 증가시키기 위하여 0.1N의 순으로 활성이 나타났다. 0.1N-HNO₃ 산처리 촉매에 대한 접촉시간(W/F) 영향은 접촉시간이 증가할수록 acetaldehyde의 연소활성이 증가하였다. acetaldehyde에 대한 LEL(Lower Explosive Limit : 4%)의 25%에 해당하는 1 mole% 이하에서 반응물 농도에 따른 mol% 이하, 반응온도 280℃ 이상, 접촉시간(W/F)이 1.56 g-cat.hr/g-mol 이상일 때 국내 법규상 VOCs 처리시설의 처리효율 기준인 90% 이상의 전화율을 보였다. 산처리한 자동차 폐촉매를 이용한 VOCs 연소활성은 매우 우수하였으며, 향후 소규모 VOCs 배출원 제어용 기술로서의 적용가능성을 보였다. On the study, the waste automotive catalyst was treated by acid, and the effects of the Acid treatment on VOCs combustion activities were evaluated The physic-chemical Characteristics of waste automotive catalyst were examined by EA(Elemental analyzer) and ICP-AES(Inductively coupled plasma-atomic emission spectrophotometer) analysis. Compared to the Pd and Rh contents in the waste automotive catalysts, the Pt was contained in the highest level, and the content levels of precious metals decreased with increasing mileage. The air was introduced to the waste catalyst with heating to remove the deposited carbon On the catalyst surface, and the result of this pretreatment showed the highest catalytic activity in using 400℃ for 1 hour. In addition, the waste catalyst was treated with the various types of acid(0.1N) to eliminated poison materials besides to increase the catalytic activity. The effects of acid types on the catalytic activity were improved by the order of HNO₃ >HCI >H₂SO₄ >H₃PO₄. The combustion activity of acetaldehyde also enhanced With increasing the contact time(W/F). The destruction efficiency of acetaldehyde was Evaluated with the variation of reaction temperature and its concentration. The tested Acetaldehyde concentration was below 1 mole %, which was 25% of the LEL(Low Explosive Limits). According the results of the experiments, the VOCs destruction efficiency was higher than 90%), and be utilized to control the VOCs from small size industries.

자동차(自動車) 폐촉매(廢觸媒)의 침출액(浸出液)으로부터 백금족(白金族) 금속(金屬)의 용매추출(溶媒抽出)

김미애,이재천,김치권,김민석,김병수,유경권,Kim, Mi-Ae,Lee, Jae-Chun,Kim, Chi-Kwon,Kim, Min-Seuk,Kim, Byung-Su,Yoo, Kyoung-Keun 한국자원리싸이클링학회 2006 資源 리싸이클링 Vol.15 No.5

자동차 폐촉매의 침출액으로부터 백금족 금속의 분리를 위하여 용매추출에 대한 기초연구가 수행되었다. 추출제로 tri-n-butyl phosphate (TBP), tri-n-octylamine (TOA) 그리고 di-n-hexyl sulfide (DHS)를 등유에 희석하여 사용하였다. 추출제의 종류 및 농도가 백금, 팔라듐 그리고 로듐의 추출거동에 미치는 영향을 조사하였다. 또한 세륨, 납, 철, 마그네슘 그리고 알루미늄 등 침출액에 존재하는 주요 금속불순물의 추출거동도 함께 조사하였다. TBP는 백금과 팔라듐, 그리고 TOA는 백금, 팔라듐, 로듐을 동시에 추출하였다. DHS 추출제인 SFI-6에 의한 용매추출 시 백금이 팔라듐과 함께 유기상으로 추출되었으나, SFI-6R은 팔라듐만 선택적으로 추출하였다. SFI-6R은 SFI-6에 비하여 팔라듐에 대한 선택성이 우수하였으나 추출속도가 느렸다. 추출제의 종류에 따라 백금족 금속과 함께 추출되는 금속불순물들이 달라지며 세정 또는 탈거공정에서 이들을 제거하여야 한다. 자동차 폐촉매의 침출액으로부터 백금, 팔라듐 그리고 로듐을 분리하기 위하여 먼저 DHS 추출제인 SFI-6R를 사용하여 팔라듐을 분리한 다음 TBP 또는 TOA으로 백금을 추출하여 로듐과 분리하는 공정이 적절한 것으로 나타났다. The solvent extraction for the separation of platinum group metals from the leach liquor of spent automotive catalysts has been studied. Tri-n-butyl phosphate (TBP), tri-n-octylamine (TOA) and di-n-hexyl sulfide (DHS) were used as extractants and kerosene as a diluent. The extraction behavior of platinum, palladium and rhodium has been investigated as functions of different kinds of extractants and their concentrations. In addition, the extraction behavior of the major metal impurities such as cerium, lead, iron, magnesium and aluminum has been investigated. Platinum and palladium were extracted with TBP. And platinum, palladium and rhodium were extracted with TOA. Platinum was co-extracted with palladium into the organic phase by solvent extraction using SFI-6 of DHS extractant, but only palladium was selectively extracted with SFI-6R. The selective extraction of palladium with SFI-6R was found better than that with SFI-6, but the kinetics of extraction with SFI-6R was found poor in comparison to SFI-6. The metal impurities extracted simultaneously during the extraction of platinum group metals should be removed in scrubbing and stripping processes. A suitable process has been proposed for the separation of platinum group metals from the leach liquor of spent automotive catalysts. Initially palladium was extracted with SFI-6R, followed by the separation of platinum with TBP or TOA leaving rhodium in the raffinate.

자동차(自動車) 폐촉매(廢觸媒)의 침출액(浸出液)으로부터 시멘테이션에 의한 백금족(白金族) 금속(金屬)의 회수(回收)

김민석,김병수,김은영,김수경,류재욱,이재천,Kim, Min-Seuk,Kim, Byung-Su,Kim, Eun-Young,Kim, Soo-Kyung,Ryu, Jae-Wook,Lee, Jae-Chun 한국자원리싸이클링학회 2011 資源 리싸이클링 Vol.20 No.4

금속분말을 환원제로 사용하는 시멘테이션에 의하여 자동차 폐촉매의 침출액과 침출잔사의 세척액으로부터 백금족 금속을 환원 석출시켜 회수하는 연구를 수행하였다. 환원제로 사용한 알루미늄, 마그네슘 그리고 아연이 백금족 금속의 시멘테이션에 미치는 영향을 조사하였으며 알루미늄을 최적 환원제로 선정하였다. 침출액에 19.3 당량의 알루미늄을 첨가하고 $50{\sim}60^{\circ}C$에서 10분간 시멘테이션을 행하였을 때 백금, 팔라듐, 로듐의 환원석출율은 각각 99.3%, 99.4%, 90.2% 정도 이었다. 또한 세척액에 알루미늄을 45 당량 투입한 후 시멘터이션 반응을 통해 백금, 팔라륨, 로듐을 각각 97%, 97%, 90% 회수할 수 있었다. 그리고 회수한 환원석출물의 금속불순물들을 질산침출로 제거함으로써 백금족 금속의 품위를 약 10% 정도 향상시킬 수 있었다. The recovery of platinum group metals (PGMs) from the leach solution of spent auto-catalyst and the wash solution of the leach residue was investigated in the laboratory scale experiments by the cementation process using metal powders as the reductant. In this study, the effect of Al, Mg and Zn powders on the cementation process was particularly examined. Aluminum powder was selected as the most suitable reductant for the cementation of PGMs. At the cementation time of 10 minute under the aluminium stoichimetric amount of 19.3 and the reaction temperature of $50{\sim}60^{\circ}C$, the recovery of platinum group metals from the leach solution of the spent auto-catalyst was found to be 99.3%, 99.4%, 90.2% for Pt, Pd and Rh, respectively. Under the same conditions with the aluminium stoichimetric amount of 45, the recovery of platinum group metals from the wash solution of the leach residue of spent catalyst was observed to be 97%, 97% and 90% for Pt, Pd and Rh, respectively. In addition, it was possible to upgrade the platinum group metals in the precipitates obtained from the cementation process by about 10% through the removal of metal impurities by the nitric acid leaching at ambient temperature.

자동차 폐촉매를 이용한 휘발성유기화합물(VOC)의 제어기술

서성규,문정선 여수대학교 1999 論文集 Vol.14 No.2

The characteristics and the combustion activities of a waste automotive catalyst were carried out in this study. Methanol was selected as a model VOC(Volatile Organic Compound) and the combustion activity was examined in a fixed bed reactor. The characteristics of waste automotive catalyst was investigated by EA(Elemental Analysis). ICP-AES(Inductively Coupled Plasma-Atomic Emission Spectrophotometer) and BET(Brunauer-Emmett-Teller) analysis. Carbon deposit amount was decreased with increasing pretreatment temperature and air. Conversion of methanol at the reaction temperature of 100℃ was above 90% on the regenerated catalyst with air,60cc/min,400℃.1hr. The selectivities of HCHO and HCOOCH₃were decreased with increasing reaction temperatures. And combustion activity of a waste automotive catalyst was decreased with mileage. Catalytic activity of a waste automotive catalyst for methanol combustion was increased with acid treatment, and the order of acid effect was summarized as follows : HNO₃>HCL>H₂SO₄>CH₃COOH. Finally, we might say that the regenerated waste automotive catalyst by regeneration method has a excellent catalytic activity for VOC combustion.