44(2)-15.fm

Transcription

1 Krean Chem. Eng. Res., Vl. 44, N. 2, April, 2006, pp i s Cu-Mn { m Š s Ç kçmy *, * e e 1000 ( p r, p }ˆ) Activity and Characteristics f Cu-Mn Oxide Catalysts Supprted n Hye-jin Kim, Sung-W Chi and Chang-Sep Lee* Department f Envirnmental Science, * Department f Chemistry, Keimyung University, 1000, Shindang-dng, Dalse-gu, Daegu , Krea (Received 29 September 2005; accepted 27 March 2006) k l v Cu-Mn l Š l mr pp 160~280 Cp m l r p s m. BET, SEM, TPR, TPO, XPS XRD pn l p m. Š lp mr pp 280 C p l p lrp, rr Cu-Mn v p 15.0 wtícu-10.0 wtímnp p ˆ. TPR/TPO XPS, 15 Cu-10 Mn p n p m p mp l v p p p m. XRD, Mn CuO p pq p l p n n p, p p p p p ˆl p p. h Abstract The catalytic xidatin f tluene ver -Al 2 supprted cpper-manganese xide catalysts in the temperature range f C was investigated by emplying a fixed bed flw reactr. The catalysts were characterized by BET, scanning electrn micrscpy (SEM), temperature-prgrammed reductin(tpr), temperature-prgrammed xidatin(tpo), X-ray phtelectrn spectrscpy (XPS) and X-ray diffractin(xrd) techniques. Catalytic xidatin f tluene was achieved at the belw 280 C, and the ptimal cntent f cpper and manganese in the catalyst was fund t be 15.0 wtícu-10.0 wtímn. Frm the TPR/TPO and XPS results, the redx peak f 15 Cu-10 Mn catalyst shifted t the lwer temperature, and the binding energy was shifted t the higher binding energy. Furthermre, It is cnsidered that is superir t Mn xides and CuO in the rle as active factr f catalysts frm the XRD results and als catalytic activities are dependent n the redx ability and high xidatin state f catalysts. Key wrds: Tluene, Cpper, Manganese,, Catalytic Oxidatin 1. (vlatile rganic cmpunds, VOC)p p n nr, r r, p l n v me (pht chemical xidants)p p v k r m. l pq vp p vp ep v VOC lr rr l p. VOC p nr tep r l p p 72Í v p s l lr r} p v p [1]. VOC rl l,, p, l, p p, p tl l p r, p p d } l r p k r pp rml nm T whm crrespndence shuld be addressed. hjkim6529@kmu.ac.kr pl, l v pp p rl ep p [2]. p rp VOC } m r p p. v Pt, Pd pp p p pm l p p ˆ k dl m vl p l lnp p n p [3, 4]. p p rp rs np p l p p p. l r p p p rp p rs l ep k v p. p rp tl l l v p, t Cum Mnp VOC r p l, ep p p. Li [5]p reverse micremulsin l p rs p n, 220~280 C l 98Íp Š l r p 193

2 194 vë nëp} p ll mp, Mazzcchiam Kadduri[6] n pn l lžk p p mr pp e, 200 C l lžk p mr r p m., Terribile [7]p Ce-Zr l Cu m Mnp ~ l p rs pn l ˆ p mr pp ee, Cum Mnp pp p vv lpp p. l l p pn l v Cu Mn rs m. rs pn l Š lp mr p p ee l p l pl Cu/Mn pp l m p s m., rs p ˆ, ˆ p p p mp, XRD XPS p p r ˆl l s m { m v Cu-Mn (Aldrich, 155 m 2 /g) ~l Cu(N ) 3 6H 2 O(Aldrich, 99.99Í)m Mn(N ) 2 xh 2 O(Aldrich, 99.99Í) r ~ n l l p rs m. r v l p r vp n e l v e p, v v r v l p p r 120 C s l 12e s, l 500 Cp m 4e k m. l v p p Cu 5, 10, 15, 20 wtí, Mn 10 wtí mp, m l 5ÍCum 10ÍMnp v p n 5 Cu-10 Mnp ep m { m l l n e q k r p rp q Fig. 1l ˆ l. 10 mmp U-type m l 0.1 gp m vv l p m. p d Š l 200 ppm/n 2 balance rs Š l dm O 2, N 2 n m. v rl (MFC, BROOKS 5850E SERIES) n l Š l 30, 75, 150 ppm, O 2 21 vlí, N vlí sr mp p 50 ml/min pr v l 160~280 C m l p e p ee m. p d p d p FID q d Š (Hewlett Packard mdel 6890 Series II) pn m. Š l r p p p el p mp inlet Š l m l v v k e n mp utlet Š l v m l p n m. Inlet tluene Inlet tluene Outlet tluene Cnversin = 100 Š l p e p r p l p Š l r pl m p l ml 3e k Š lp m l Š l pp s m. p p m 160~280 C l 20 C p dme p, m l 1e k kr eˆ p p Š l l r m. p Š l mr l m p s l k Fig. 1. Schematic diagram f the micr reactr. A. Mass flw meter D. Temperature cntrller B. Micr syringe E. Catalyst reactr C. Heater F. GC-FID 1Íp H 2 O Fig. 1p micr syringe pn l tp mp, p tp r 110 Cp m l e p dm p p e p m { m p p s l TCD q TPR/TPO q (Autchem 2910, Micrmeritics Inc.)p n l dm e p ee m. e p 0.1 gp p l 500 Cl 1e k O 2 r } p 10Í H 2 /Ar d 20 ml/minp p t 2.5 C/minp dm ml 500 C v H 2p p r m. e p p mp eˆ, 2Í O 2 /He d 20 ml/ minp p t 3 C/minp dm ml 500 C v O 2p p r m. rs p rp BET(Micrmeritics, ASAP 2400)p p n m p ˆ SEM(Hitachi, S-4200)p pn l r m. p r s X-ray diffractin(xrd, Panalytical X'pert PRO MRD analyzer) pn m, s p Cu Kα (λ= nm)p n l dƒ (2θ) 20~80 l j m. p ˆ s l XPS(X-ray phtelectrn spectrscpy) spectrmeter(v.g. Scientific, Escalab 250) n l Al K-alpha(CAE=50 ev) s l XPS p mp, } C1s p l v p 285 ev t l chemical shift p r m { m ~ Cu-Mn l p Š l mr pp s l Fig. 2l ˆ l. Š l 30 ppmp n, k 260 C l Š lp mr p k pp Cu v p v l p p v kk. pl, Š lp 75 ppmp nl 10 Cu-10 Mn 15 Cu-10 Mn l p Š lp mr pp 260 Cl ˆ p, 15 Cu- 10 Mn p Š l pp q n mp p 15 Cu-10 Mn>20 Cu-10 Mn>10 Cu-10 Mn>5 Cu-10 Mnp

3 l v Cu-Mn p 195 Fig. 2. Catalytic xidatin f tluene ver Cu-Mn xide catalysts as functins f reactin temperature and cncentratin. pp k pl. 150 ppmp l p l vp pl 75 ppm p m mp, 15 Cu-10 Mn 260 Cl Š lp mr pp ˆ p 5 Cu-10 Mn 280 Cl Š lp mr l. pm p, Š lp d l Š l m r p lvp k plp, p p Kim[8]p l ˆ. Kimp Š l v p p ˆ VOC pl p r p ˆ p m. Fig. 2l ˆ pn l 50Í, 90Íp Š l r pp ˆ m T 50 T 90 p e l Table 1l ˆ l. Š lp 30 ppmp r r l e, Cup v m T 50 p 190 C l, T 90 p 235 C l p pp ˆ l., 75 ppm l 15 Cu-10 Mn p T 50 p 202 C T 90 p 236 Cpp k pp 150 ppm l 15 Cu-10 Mn p T 50 p 238 C T 90 p 256 Cp rm mll Š l Table 1. Catalytic xidatin f tluene ver Cu-Mn xide catalysts Catalyst Cncentratin T 50 ( C) T 90 ( C) 5 Cu-10 Mn 130 ppm ppm ppm Cu-10 Mn 130 ppm ppm ppm Cu-10 Mn 130 ppm ppm ppm Cu-10 Mn 130 ppm ppm ppm Fig. 3. The influence f reactin time n reactivity f catalytic xidatin f tluene ver Cu-Mn xide catalystsg (A:G tluene cncentratin =150 ppm, temperature=220 C; B:G tluene cncentratin=30, 75 ppm, temperature=220 C at 15 Cu-10 Mn catalyst). p mr v p p pl. p Cu v p l Š lp mr m p ˆ p, 15 Cu-10 Mn q rml Š lp mr pp ˆ p k pl., 15ÍCu-10ÍMn p Cu-Mn rs p f Š lp mr p p p pp p m. Š l mr p d eq m p 220 C l e l Š l r pp r m. Fig. 3(a)l p 15 Cu-10 Mn p p rp n p p pp, r pp 2e p p 31Íp 8e e 25Í r pp kvp mp 14e p l 29Í p pr v p p pl., p p Cup v p l l. Š l r pp n 15 Cu-10 Mn l p 30, 75 ppm q d Fig. 3(b)l ˆ m p 30 ppm l 30Í p r pp p 45Í p p r pp ˆ lp, 75 ppm l 30Í l 25Í pp Š l r pp ˆ p pl. 220 Cl p p p r pp n 15 Cu-10 Mn p p l p p pl { m Ž Š Cup v p e rs p rp r Table 2l ˆ l. l Mn Cu v Cu-Mn p rp 155 m 2 /gp p r n mpp k pp, Cu p v l rp p ˆ l. pr l p l 10Í Krean Chem. Eng. Res., Vl. 44, N. 2, April, 2006

4 196 vë nëp} Table 2. The BET surface area f Cu-Mn xide catalysts Catalyst Surface Area (m 2 /g) 5 Cu-10 Mn Cu-10 Mn Cu-10 Mn Cu-10 Mn 96.5 Fig. 5. X-ray diffractin patterns f Cu-Mn xide catalysts. Fig. 4. SEM images f Cu-Mn xide catalysts (1:5 Cu-10 Mn, 2:10 Cu- 10 Mn, 3:15 Cu-10 Mn, 4:20 Cu-10 Mn). Mn v e p n p rp m /g m 2 p Cup p p rp m /gp n 2 lpp k pp, Cu p v l p rp n mpp k pl. Cu-Mn p ˆ s SEM rp Fig. 4l p p 5 Cu-10 Mn, 10 Cu-10 Mn p l t 300 nm p p qp pq p l. p vp Cum Mnp ~ l l p p ˆ t p. 15 Cu-10 Mn l pq p vp rp l, Cu p q p 20 Cu-10 Mn pq vp ƒ r p t l. r r SEM Š l mr m l e l, p r l m p v k p k pl. p Kim[8] p ee l p v l VOC pl l l lv p k, l l p Š lp mr p l tqp l t p. Cu v l Cu-Mn p r s s l XRD p mp, Fig. 5l ˆ l. l p 5 Cu-10 Mn l 2θ = 30.43, 35.88, 43.74, 57.73, l p d sl p r l n ˆ lp, 10 Cu-10 Mn p rl k l. Papavasiliu [9]p l e l rs m l p d s r lpp pl. 15 Cu-10 Mn l pnl CuOl 2θ = 35.45, 38.69, l l p Cu v p v l v m., Mnp p Cu p 5 Cu-10 Mn l Mn l v k p k Mnp Cum n~ l d sp ˆ sq r ˆ sq p. Chen [10] p Mnp 5Í p v n r p Mn p p m, Papavasiliu [9]p n k l rs Cu-Mn l p d sm Mn 2 p p m. pl Alns [11]p CuOm MnO 2 rp l rs l l l XRD patternp m. Tang [12]p MnO-CeOxp XRD Ž p Mn Cep l ps m. Mn/(Mn+Ce) 0.75 pp Mn 2 p rp ˆ Mn/(Mn+Ce) 0.5 p Mn 2 m CeO 2 pl n~ Mn 2 p l ˆ v kp CeO 2 p r ˆ m. Mnp n~ np p l l Mnp rp Mn/(Cu+Mn) p l ps p lv. Mn/(Cu+Mn) p p, 5 Cu-10 Mn:0.7, 10 Cu-10 Mn:0.54, 15 Cu-10 Mn:0.44, 20 Cu-10 Mn:0.37p Mnp p p 5 Cu-10 Mnm 10 Cu-10 Mn l Mnp p Mn r ˆ v kp Cum Mn pl n~ Mn l ˆ v k p. p l p rs p l Mn p l lpp p. Table 3l XRD l llv r m CuOp pp ˆ l. 5 Cu-10 Mn 10 Cu-10 Mn r p sq p lp, 15 Cu-10 Mn 20 Cu-10 Mn m CuOp rp el sq

5 Table 3. The crystallite ratis f Cu-Mn xide catalysts XRD phases( ) Catalyst CuO 5Cu-10Mn Cu-10Mn Cu-10Mn Cu-10Mn Cup p v l CuOp p kv p k pl. v 5 Cu-10 Mn 10 Cu-10 Mn l t p tn r s l. pl, Cup v p 15Í p p Cu-Mn p nl p nl CuO r s lp CuO rp pp Cup v p v v p k pl. p, l l rs Cu-Mn rp l rmmll n p p r p sq p p rp Cup v p v 15 Cu-10 Mn p p q n mp Mn CuO rp pq l p n p Ž., 15 Cu-10 Mn p p 20 Cu-10 Mn n ˆ p CuOp p p vv p k CuO tn pq k p r. Mn CuOp l p n CuO r p pq p l p n n p. Š l pl p m CuOp p l l l l v n p pp p Ž. p p r l H 2 -TPR e p mp r Fig. 6l ˆ l. p H 2 -TPR, 5 Cu-10 Mn l v Cu-Mn p 197 p ~ w n 172 Cl w n 278 Cl lp, 10 Cu-10 Mn 160 Cm 246 Cl, 20 Cu-10 Mn 154 Cm 227 Cl ~ w w n ˆ l., 15 Cu-10 Mn p ˆ p, 154 Cm 182 C, 226 Cl p p pl., Cup v p v l p m rmp p mp 15, 20Í p Cu v p n ~ w m p m., 15 Cu-10 Mn 20 Cu-10 Mn p ~ w p H 2 r signal 15 Cu-10 Mn p H 2 p pp p pl. e s p q p s l O 2 -TPO e p m Fig. 7l ˆ l. p p 5 Cu-10 Mn Cup v p v rml p p kv p p plp, ~ w n v O 2 p rml q p p 15 Cu-10 Mn p p ˆ., mmll p eq l p m l ~ v p k p. p p pp Kim Lee[13] rl pq p p pl pqp v q rl pq p e p v l m p Ž m. p p e s, 15 Cu-10 Mn p p q n p p pp, p m l p p ˆ p Cu-Mn l p p p p r p Ž. p l pp Š l e p m. pp p p r l p pp p. l p t Langmuir-Hinshelwd Fig. 6. TPR curves f Cu-Mn xide catalysts. Fig. 7. TPO curves f Cu-Mn xide catalysts. Krean Chem. Eng. Res., Vl. 44, N. 2, April, 2006

6 198 vë nëp} p rl p p l ˆl pl l p rr p p Mars-van Krevelen p l pp p q l p v qm q p p v kp q d lr qm p l p q q l p e }r rp q l pp p p [14]. l l n Cu-Mn Š l mr p e p pl p ppv k Š l l p ppv p l Š l ˆ e p m. r e p 0.1 gp 110 Cl O 2 1e r} ml v v eˆ 200 ppm Š lp 50 ml/minp tp Š l p GC-FID m. tp 200 ppmp Š l t l p v v k Š l p kp 2 min p m. Š lp kp blank e m p kp Š l p s p e l Š l p p lv p r Š lp tp rp l m. tp Š l kp l p r rp l p m., Š l p mml/gpl. pl p p lv l rp Š lp r l ml v ~ v eˆ, 2 C/min p m d m l Š l ˆ e p m l ˆ lv m. Cu-Mn p Š l mr pp ƒ vl p p k vl p p pl p rp lp p mr pp n v p. Table 4 p ˆl r l XPS p. p rp CuO 933.4~933.9 ev, Cu 2 O 932.1~932.5 ev, MnO ev, Mn ~641.4 ev, MnO ~642.4 ev mlp l v [15]. l l ˆ Cum Mnp kk, Cu 2p 3/2p l v ~ evp ˆ p Cu 2+ Cu 1+ ~Cu sq p p pp, Mn 2p 3/2p l v ~ ev Mn 2+ ~Mn ˆpp p 4+ p. p ˆm p r p } l n p q n 15 Cu-10 Mn p q p p ˆ p p Š lp mr l m p p. p rp ˆ v l v v eˆ mp [16] l vp v pp p., p ˆ Table 4. The binding energies(ev) f Cu(2p) and Mn(2p) levels fr Cu-Mn xide catalysts Binding energies (ev) Catalyst Cu 2p 3/2 Mn 2p 3/2 5Cu-10Mn ev ev 10Cu-10Mn ev ev 15Cu-10Mn ev ev 20Cu-10Mn ev ev k Fig. 8. Influence f water n reactivity f catalytic xidatin f tluene ver 15 Cu-10 Mn catalystg(water cncentratin=1, tluene cncentratin=100 ppm, reactin temperature=260 C). qrq k p eˆ pp pl p m [14]. l l n p ˆ Š l pp n p p. Fig. 8l rs p er r rn p r l p qn p m p s m. r 260 C m l 20e k Š l mr pp ˆ v s m. e 99.9Íp Š l r pp v p p plp, 1Í tp l 260 Cl Š l pp m p l p pp p ˆ v kk. l Cu p v l p m p s Wang[17]p l l 20Í p p m Wangp p l p k. l l rs Cu-Mn p v k p s lp p rl rnp p. 4. Cu-Mn pn Š l mr pl pp p s l p p p ll. rr p pp l Cu 15Í, Mn 10Í v p ˆ p, Š lp kvl r pp mp 260 C l mr p k rm p n p k pl. rs p r p ˆ l m p v kpp k pl. p l Š lp mr l p p ˆ p k pl. p r sm ˆ p Mn CuOp l p n CuO r p pq p l p n n p Š l mr pl pl p l rp p p r p npp qn p Ž. e r p p r

7 l v Cu-Mn p 199 qe l m p m p s, e p l l p Š lp r p p ˆ v kk. Cu-Mn d s l rm p l k l k r p n mp, p ƒ vp p. l lq l e vlr l l p k l l p p. l v t l q l. y 1. Sichir, S., J. Env. Hi-Tech., 9, 15-19(2004). 2. Cper, C. D., Alley, F. C., Air Pllutin Cntrl, 2nd ed., Waveland Press, 337(1994). 3. Ihm, S. K., Jun, Y. D., Kim, D. C. and Jeng, K. E., Lw-temperature Deactivatin and Oxidatin State f Pd/-Al 2 Catalysts fr Ttal Oxidatin f n-hexane, Catal. Tday, 93(95), (2004). 4. Centen, M. A., Paulis, M., Mntes, M. and Odrizla, J. A., Catalytic Cmbustin f Vlatile Organic Cmpunds n Au/ CeO 2 /Al 2 and Au/Al 2 Catalysts, Appl. Catal. A:Gen., 234, 65-78(2002). 5. Li, W. B., Chu, W. B., Zhuang, M. and Hua, J., Catalytic Oxidatin f Tluene n Mn-Cntaining Mixed Oxides Prepared in Reverse Micremulsins, Catal. Tday, 93(95), (2004). 6. Mazzcchia, C. and Kadduri, A., On the Activity f Cpper Chrmite Catalysts in Ethyl Acetate Cmbustin in the Presence and Absence f Oxygen, J. Ml. Catal. A:Chem., 204(205), (2003). 7. Terribile, D., Trvarelli, A., Leitenburg, C. D., Primavera, A. and Dlcetti, G., Catalytic Cmbustin f Hydrcarbns with Mn and Cu-dped Ceria-zircnia Slid Slutins, Catal. Tday, 47, (1999). 8. Kim, S. C., The Catalytic Oxidatin f Armatic Hydrcarbns ver Supprted Metal Oxide, J. Haz. Mat., B91, (2002). 9. Papavasiliu, J., Avgurpuls, G. and Iannides, T., Steam Refrming Over Cpper-manganese Spinel Oxide Catalysts, Catal. Cm., 6, (2005). 10. Chen, T. J., Kim, H. J. and Chi, S. W., Tluene Catalytic Oxidatin by Manganese Oxide: (1) Activity and Characterizatin, J. Krean. Sc. Atms. Env., 21(2), (2005). 11. Alns, L., Palacis, J. M., Garcia, E. and Mliner, R., Characterizatin f Mn and Cu Oxides as Regenerable Srbents fr Ht Cal Gas Desulfurizatin, Fuel Prc. Tech., 62, 31-44(2000). 12. Tang, X., Li, Y., Huang, X., Xu, Y., Zhu, H., Wang, J. and Shen, W., MnOx-CeO 2 Mixed Oxide Catalysts fr Cmplete Oxidatin f Frmaldehyde: Effect f Preparatin Methd and Calcinatin Temperature, Appl. Catal. B:Env., 62, (2005). 13. Kim, Y. H. and Lee, H. I., Redx Prperty f Transitin Metal Oxides in Catalytic Oxidatin, J. Krean. Ind. Eng. Chem., 10(8), (1999). 14. Chn, H. Z. and Se, G., Catalysis an Intrductin, 4rd ed., Hanlimwn, Seul(2002) Niemantsverdriet, J. W., Spectrscpy in Catalysis, secnd., Netherlands(2000). 17. Wang, C. H., Al 2 -Supprtsd Transitin-Metal Oxide Catalysts fr Catalytic Incineratin f Tluene, Chemsphere, 55, 11-17(2004). Krean Chem. Eng. Res., Vl. 44, N. 2, April, 2006