배기가스 정화용 폐 자동차 촉매를 이용한 휘발성 유기화합물의 제거

심왕근; 김상채; Wang Geun Shim; Sang Chai Kim

Journal of the Korean Industrial and Engineering Chemistry, Vol.19, No.5, 574-581, October, 2008

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배기가스 정화용 폐 자동차 촉매를 이용한 휘발성 유기화합물의 제거

Catalytic Oxidation of Volatile Organic Compounds Over Spent Three-Way Catalysts

심왕근, 김상채^{1, †}

전남대학교 응용화학공학과, 광주 500-757
¹목포대학교 환경교육학과, 무안 534-729

Wang Geun Shim, and Sang Chai Kim^{1, †}

School of Chemical Engineering, Chonnam National University, Gwangju 500-757, Korea
¹Department of Environmental Education, Mokpo National University, Muan 534-729, Korea

E-mail:

초록

폐 자동차 배기가스 정화용 촉매를 휘발성 유기화합물(VOCs) 처리 시스템에 재활용하기 위해 운전조건이 서로 다른 폐 자동차 촉매를 이용하여 촉매의 최적 재생 조건 및 VOCs 연소활성특성을 조사하였다. 폐 촉매의 최적 재생 조건을 찾기 위해 산세기가 서로 다른 5종류(질산(HNO3), 황산(H2SO4), 옥살산(C2H2O4), 구연산(C6H8O7), 인산(H3PO4))의 산을 이용하여 재생 처리하였으며, 질소 흡착등온선, XRD와 ICP를 이용하여 폐 촉매와 재생 처리한 촉매의 물리화학적 특성을 비교하였다. 폐 자동차 촉매의 피독물질과 백금족 금속(PGMs)의 상대적 함유율은 촉매의 위치에 따라 달랐으며, 주요 피독물질은 윤활유 오일첨가제와 엔진 및 배출가스 파이프에 함유된 물질이었다. 그리고 폐 자동차 촉매는 산수용액 전처리 후 백금족 금속의 상대적 함유율, BET 비표면적 및 평균기공크기가 폐 촉매에 비해 증가하였다. 폐 촉매와 재생 처리한 촉매의 VOCs 연소활성 실험 결과 폐 촉매가 VOCs 처리에 충분히 이용될 수 있다는 가능성을 보여 주었으며, HNO3와 C2H2O4 전처리를 한 촉매의 반응활성이 가장 우수하였다. 그리고 전처리한 촉매의 반응활성은 산처리로 인한 피독 오염물질의 제거율 및 조직 특성 변화 보다는 백금족 금속인 백금(Pt)의 함유율에 더 큰 영향을 받았다.

The optimum regeneration conditions for the regeneration of three way spent catalysts (TWCs), which were taken from automobiles with different driving conditions, were investigated to evaluate the suitability as alternative catalysts for removing VOCs. The spent catalysts were washed with five different acids (HNO3, H2SO4, C2H2O4, C6H8O7, and H3PO4) to remove contaminants and examine the optimum conditions for recovering the catalytic activity. The physicochemical properties of spent and its regenerated TWCs were evaluated by using nitrogen adsorption-desorption isotherms, XRD, and ICP. The relative atomic ratios of contaminants and platinum group metals (PGMs) of the spent TWCs were greatly dependent on the placed positions. The main contaminants formed were lubricant oil additives and metallic components. Also, the regeneration treatment increased the PGMs ratio, BET surface area, and average pore diameter of TWCs. The catalytic activity results indicated that the spent TWCs have the possibility for removing VOCs. Moreover, the employed acid treatments greatly enhanced the catalytic activity of the spent TWCs. Especially, nitric and oxalic acids provided the most improvement in the catalytic behavior. The catalytic activities of the regenerated TWCs were significantly influenced by the containing platinum ratios rather than the removal ratios of contaminants and the changes in the structural properties offered by the acid treatments.

Keywords:acid;catalytic oxidation;regeneration;spent three-way catalyst (TWCs);VOCs

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[1] Angelidis TN, Papadakis VG, Appl. Catal. B: Environ., 12(2-3), 193 (1997)

[2] Seo SG, Moon JS, J. Korean Soc. Environ. Eng., 22, 819 (2000)

[3] Kaspar J, Fornasiero P, Hickey N, Catal. Today, 77(4), 419 (2003)

[4] Birgersson H, Eriksson L, Boutonnet M, Jaras SG, Appl. Catal. B: Environ., 54(3), 193 (2004)

[5] Birgersson H, Boutonnet M, Jaras SG, Eriksson L, Topics in Catal., 30, 433 (2004)

[6] Christou SY, Brigersson H, Fierro JLG, Efstathiou AM, Environ. Sci. Technol., 40, 2030 (2006)

[7] Kim SC, Shim WG, J. Korean Ind. Eng. Chem., 18(4), 303 (2007)

[8] Lambrou PS, Christou SY, Fotopoulos AP, Foti FK, Angelidis TN, Efstathiou AM, Appl. Catal. B: Environ., 59(1-2), 1 (2005)

[9] Kim SW, Song YW, Lee JY, Prospect. Ind. Chem., 2(1), 6 (1999)

[10] Trimm DL, Appl. Catal. A: Gen., 212(1-2), 153 (2001)

[11] Angelidis TN, Skouraki E, Appl. Catal. A: Gen., 142(2), 387 (1996)

[12] Ruddy EN, Carroll LA, Chem. Eng. Prog., 89, 29 (1993)

[13] Cordi EM, Falconer JL, J. Catal., 162(1), 104 (1996)

[14] Everaert K, Baeyens J, J. Hazard. Mater., 109(1-3), 113 (2004)

[15] Kim SC, Seo SS, J. of KASE, 18, 205 (2002)

[16] Kim SC, Nahm SW, Shim WG, J. of KSAE, 22, 431 (2006)

[17] Barresi AA, Baldi G, Ind. Eng. Chem. Res., 33(12), 2964 (1994)

[18] Chu W, Windawi H, Chem. Eng. Prog., 92(3), 37 (1996)