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1 w y wz 9«( 1y) 34~40, 2006 J. f the Krean Sciety fr Envirnmental Analysis V/ w y Áy yá váy * w» ( )», *» w y œw Simultaneus Remval f Dixin and Nitrgen Oxide n V/ Catalyst Jun-Yub Lee, Sung-H Hng, Sung-Pill Ch, and Sung-Chang Hng* Pwer Engineering Research Institute, Krea Pwer Engineering Cmpany, INC., Yngin-si , Krea *Department f Envirnment Engineering, Kynggi University, Suwn-si , Krea The study f remving dixin using V/ de-nox catalyst fr simultaneus remval f NOx and dixin was perfrmed, and the simultaneus remval f NOx and dixin was studied. The varius catalysts with different supprt ne anther were used fr testing thse effect The xidatin f dixin and the remval f NOx were carried ut at different active sites. The misture in flue gas and W dping culd nt affect the xidatin f dixin. Thus they culd nt affect each ther. Frm the results, it was cnfirmed that V/ de-nox catalyst can xidize the dixin. Key wrds : dixin, NOx, V/ catalyst 1. ƒ,, k y l y (NOx), z (N 2 O), w ( 30%), ww Ÿyw (, PAN ) j». NOx y ³ y š NOx w œ wd y y ³ w» w y ey š, xk šz NOx l w ƒ š. s» š (Dixin) w ü ƒ š. ys» ƒœ ù s» w x ƒ w w. x ¾ ƒ j ƒ. p ù w 700 C w ü e w,,»x,,,» ƒ ƒ w 1,2). w vw w ùk ý» w v ƒ. NOx w k y (Selective Catalytic Reductin, SCR) ƒ š. SCR NOxƒ k w ww N 2 H 2 O y œ. 4NO + 4NH 3 + O 2 4N 2 + 6H 2 O (1) NO + NO 2 + 2NH 3 2N 2 + 3H 2 O (2) SCR U.S. Petrleum œ ƒ w» w 3) 1970 l y w ƒ w,» w w T whm crrespndence shuld be addressed.

2 V/ w y 35» (Pt, Pd, Rh) V, W, Fe y y š w y w SOx w üv w x x œ w. NOx w f» w ù» NOx jš. x V 2 / k ƒ ƒ z, SO 2 ü w» w WO 3 ƒw» w. w w w x ƒ ü w» w w y k w 4) y k s» w q. ù w ƒ» ƒ w»» œ zvwš y NOx ³ w» w w œ w» w. ƒ w»ü d g CO 2, H 2 O, HCl ww» ƒ z ùkü š wì ƒ w š 5,6). p NOx V 2 /WO 3 /ƒ w y w y NOx w ù w ƒ š. Hagenmaier 7) NOx SCR V, W, M yw w w 250~350 C pilt x x mw w y, BASF KWH px» w w wš. Kawasaki œ 70~95% (, ZrO 2, SiO 2 ) 1~20% V 2, WO ~3% (Pt, Pd, Ru, Rh) w w ƒ œ w NOx w e šw. w, Mutsui Mn, Cr, C y Alumina g w» yw w š, NKK» SCR ƒw NOx w px w. ƒ w 2,4,7,8-TCDD (Tetrachlrdibenzdixin) w 1,2-DCB (Dichlrbenzene) w yp w w, k SCR y y y e w w ù g w w w š, y p w wš w, w y sƒw» w 1,2-DCB (Dichlrbenzene) w. 2. V 2 t ƒ ƒ y w w. y 6 w. ƒƒ Table 1 ùkü, w t» (A), (B), (C), (D), (E), (F) w. w we w. w ù w w wš, j Ammnium vanadate [NH 4 VO 3 ; Aldrich Chemical C.] 60 C ƒ. ƒ yww. slurry k yw 1 w z rtary vaccum evapratr(eyela C. N-N series) w 70 C k. jš ù ƒ w 110 C dry ven 24 k z 10 C/min tubular furnace w k z Table 1. Physical prperties f varius supprts and catalysts emplyed in this wrk BET area Pre vlume Average pre (m 2 /g) (cm 3 /g) diameter (ç) (A) (B) (C) (D) (E) (F)

3 36 Áy yá váy 4 air» w w. k, yp y y x š d». x e j ƒ,», š ƒ w.» œ ƒ NO, N 2, O 2, NH 3, SO 2 ƒ l MFC (Mass Flw Cntrller, MKS C.) w w. w, 1,2-DCB œ N 2ƒ bubbler mw 1,2-DCB w w» w œ w w» w jacket xk bubbler circulatr w y g. ƒ œ l w NO NH 3ƒ w» NH 4 -NO 3, NH 4 - NO 2 wš ƒ» w heating band 150 C w w.» x š d e ü 8 mm, 60 cm w d š w» w quartz wl w.» š d w K-type w PID» w ƒ d w» w d w xk ew d Áz d w. d w» w NO ƒ»(uras 10E, Hartman & Braun C.) yw Ÿ»(42C HL, Therm Ins.) w NO 2 ƒ 5ppm (9L, Gas Tec. C.), w» yw Ÿ» w. SO 2 w yw Ÿ»(43C HL, Therm Ins.) (5L, Gas Tec. C.) w. (3M, 3La, 3L, Gas Tec. C.) w, 1,2-DCB THC(Ttal Hydr- Carbn analyzer, 55C HL, Therm Ins.) w. 3. š 3.1. V/ p w yw w y w HCl Cl 2 w y v w. NOx y 6 V/ w 1,2-DCB y w x w. x 200 C, 1,2-DCB 300 ppm, O 2 1 3%, œ (Space Velcity, S.V) 10,000 hr w xw. Fig. 1, y w z j ƒ 6 50 x w y w.» x 1,2-DCB w w HCl Cl 2 w y y x w q. z XRD w y w vanadium xychlrideƒ d, ICP 450~550 ppm Cl. Cl w x q. V/ ƒ y w. w Krishnamrthy 8) Amiridis w V 2 / t w 7600 ppm Cl y w e š ew V 2 /Al 2 O 3 w 1,2-DCB y w x 500 C 6 w z w vanadium chlride aluminium chlrideƒ w d w, CuCl 2 -based plychlrinated biphenyls(c 12 HCl 9 ) x šw., w k V/ Fig. 1. The lngevity f a variety f V[2]/ catalysts fr the decmpsitin reactin f 1,2-DCB at 200 C, 1,2-DCB 300 ppm; O 2 3vl.%; S.V 10,000 hr 1.

4 V/ w y 37 Fig. 2. The effect f temperature n 1,2-DCB cnversin efficiency ver V[2]/varius supprts in ptimal calcinatin temperature, 1,2-DCB 300 ppm; O 2 3vl.%; S.V 10,000 hr 1. y p w p sww q. V/ 1,2- DCB y w z Fig. 2 ùkü. x y w z V/ (C), V/ (D), V/ (F) w ùkþ, V/ (A) > V/ (B) > V/ (E) y w. w 1,2-DCB y w z NOx y. z w ù V/ y V/ (A) > V/ (B) > V/ (C) > V/ (D) > V/ (E) > V/ (F). ù y ew. SCR w y yƒ w y š w. ù y x w wš yw w k. w 1,2-DCB y y w Krishnamrthy 9) V/ w 1,2-DCB y w x ù w ƒ SCR y ƒw 1,2-DCB yy w wš y y V-O-Ti w, V/ yy w ƒ w (V-O : 121, V-Cl : 121, Ti- O : 289, Ti-Cl : 213, C-O : 159, C-Cl : 117, Cr-Cl : 167 kj/ml) š w. k V/ 1,2-DCB y y V-O-Ti. Fig. 3. The effect f calcinatin temperature n 1,2-DCB cnversin efficiency ver V[2]/varius at 200 C, 1,2-DCB 300 ppm; O 2 3vl.%; S.V 10,000 hr 1. V/ y. Fig. 3 V/ w y 1,2-DCB yy ùk ü. V/ (A) V/ (C) w 400 C y y, V/ (F) w 500 C y š z ƒ y w. w NOx k w., NOx 1,2-DCB y y ù, w y y k w, y ù y t y k ƒ y š w y NOx. ƒ w. SCR» wš NOx k. n w w w v ƒ. 1,2-DCB y SCR w w w g y w š w» w Fig. 4 SCR NOx z 1,2-DCB y NOx z w ùkü, Fig. 5 1,2-DCB y y SCR ww

5 38 Áy yá váy Fig. 4. The cmparisn n NOx cnversin efficiency between SCR reactin and 1,2-DCB xidatin + SCR ver V[2]/varius supprts in ptimal calcinatin temperature, NH 3 /NOx 1.0; NO 760 ppm; NO 2 50 ppm; 1,2-DCB 300 ppm; O 2 3vl.%; S.V 10,000 hr 1. Fig. 5. The cmparisn n 1,2-DCB cnversin efficiency between 1,2-DCB xidatin and 1,2-DCB xidatin + SCR ver V[2]/varius supprts in ptimal calcinatin temperature, NH 3 /NOx 1.0; NO 760 ppm; NO 2 50 ppm; 1,2-DCB 300 ppm; O 2 3vl.%; S.V 10,000 hr 1. yy w ùkü., SCR 1,2-DCB n w NOx z w w x 170~300 C y» w., SCR V=O V-OH site w 1,2- DCB y V-O-Ti p w y w q. w 1,2-DCB NH 3 NOx ƒw 1,2-DCB y z x 200 C¾ Fig. 6. The effect f NOx and NH 3 n 1,2-DCB cnversin efficiency ver V[2]/ (C5) at 200 C, 1,2-DCB 300 ppm; O 2 3vl.%; NOx 830 ppm; NH ppm; S.V 10,000 hr 1. V/ (C), V/ (D), V/ w, 170 C (F) w y w. 170 C» SCR NOxƒ k w NH 3 NOxƒ 1,2-DCB y z e w w» w SCR NOx V/ (A) w 1,2-DCB y NOx w y y y Fig. 6 ùkü. x 1,2-DCB y NOx n yy w ù, n yy w j n w» y z w., sx w 1,2-DCB ww y w w w y š, n» y y z w n 1,2-DCB, w y y q ƒ w Fig. 7 l l ƒ w w w, y y w w wì w. V/ (A) l l w V/W/ (A). x w

6 V/ w y 39 Fig. 7. The effect f H 2 O and WO3 n 1,2-DCB cnversin efficiency ver V[2]/ (C5) and V[2]/ W[6]/ (C5), 1,2-DCB 300 ppm; O 2 3vl.%; NH 3 /NOx 1.0; NO 760 ppm; NO 2 50 ppm; S.V 10,000 hr 1. y y x ùkû, l l w V/W/ (A) y. w SCR y w. w y y» Fig. 7 y w q, l l ƒ w y y w l l y w y j xk ù y w w, l l ƒ y ƒw y y j yƒ w. V/ k l l ƒ ƒ y j w e š w. s» ƒ ƒ ü yy 0.3~31 ppm t x ù sulfite(v-so 3 )» SO 2 sx kƒ 1,2-DCB y ƒ w q. Fig. 8 l l w V/W/ yy 50 ppm n üy ùkü.» y V/W/ (C) V/W/ (D) w SO 2 Ák sx w w 1,2-DCB z w ù, V/W/ (A)» y û ù SO 2 Ák sx w t x Fig. 8. The effect f SO 2 n 1,2-DCB cnvertin efficiency ver a variety f V[2]/W[6]/, 1,2-DCB 300 ppm; O 2 3vl.%; SO 2 50 ppm; H 2 O 6vl.%; S.V 10,000 hr 1. ù sulfite(v-so 3 ) w w w z., V/ W/ (A) yy ƒ û SO 2 y sx w, k SCR w SCR y w y w SCR ƒ w. 4. SCR k V/ w w w k w k. k y y y». NOxƒ w y k z ƒ. ù SCR y ƒ n yy w, w y z.. w l l ƒ y ƒw l l ƒ w y y q.» sƒ Á

7 40 Áy yá váy šy x œ l ( y : )». š x 1. ½ «, Á x s» ƒ», w y Á z (y ), w, 1999, I. Y. Kashiwabara, K. Okada, S. Mri, and T. Hara, Chemsphere, 1996, 32, H. L. Hill, "SCR Prcess Cuts NOx Emissin", 1981, 141, Hydrcarbn Prcessing, U.S.A. 4. K. Miura and K. Hashimt, J. f Chem. Eng. Japan, 1977, 10, ½ «, s» ƒ w, 1999, w Ph. D. Thesis, w. 6. D. van de Kleut and B. van den Akker, Dixin'98, 1998, 36, H. Hagenmaier et al., U. S. Patent , S. Krishnamrthy and M. D. Amiridis, Catal. Tday, 1999, 51, S. Krishnamrthy, J. P. Paker and M. D. Amiridis, Catal. tday, 1998, 40, 39.