Catalytic Reduction of Nitric Oxide in Oxygen-Rich Exhaust with Methanol over $La_2O_3$ Catalysts

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(1)C o p y rig h t 2005 K SA E 1 2 2 5 -6 3 8 2 /2 0 0 5 /0 7 4 - 1 9. Tra nsa c tio ns o f K SA E , V o l. 1 3 , N o . 2 , p p .1 3 5 -1 4 1 (2 0 0 5 ). L a2O 3 NO 1). 1). *2). 1). 2). Catalytic Reduction of Nitric Oxide in Oxygen-Rich Exhaust with Methanol over La2O3 Catalysts Sang Hwan Kim1) Hyun Ju Yoo1) Jung-Kyu Park*2) 1). Department of Chemical Engineering, Konkuk University, Seoul 143-701, Korea Department of Mechanical Engineering, Konkuk University, Seoul 143-701, Korea (Received 8 September / Accepted 31 January 2005). 2). A b s trac t : N itric o x id e (N O ) re d u c tio n b y m e th a n o l w a s in v e stig a te d o v e r L a 2 O 3 c a ta ly sts in th e p re se n c e a n d a b se n c e o f o x y g e n . In th e a b se n c e o f O 2 , C H 3 O H re d u c e d N O to b o th N 2 a n d N 2 O , w ith se le c tiv ity to N 2 fo rm a tio n d e c re a sin g fro m 8 1 -8 8 % a t 6 2 3 K to 4 7 -7 1 % a t 7 2 3 K . W ith 1 .2 % O 2 in th e fe e d , th e ra te s w e re 4 -8 tim e s h ig h e r, b u t th e se le c tiv ity to N 2 d ro p p e d fro m 5 0 % a t 6 2 3 K to 9 % a t 7 2 3 K . T h e sp e c ific a c tiv itie s w ith L a 2 O 3 fo r th is re a c tio n w e re h ig h e r th a n 2 th o se fo r o th e r re d u c ta n ts; fo r e x a m p le , a t 7 7 3 K w ith h y d ro g e n a sp e c ific a c tiv ity o f 3 4 o l N O /se c m w a s o b ta in e d 2 w h e re a s th a t fo r m e th a n o l w a s 6 3 8 o l N O /se c m . T h e A rrh e n iu s p lo ts w e re lin e a r u n d e r d iffe re n tia l re a c tio n c o n d itio n s, a n d th e a p p a ra n t a c tiv a tio n e n e rg y w a s c o n sista n tly n e a r 1 5 k c a l/m o l w ith C H 3 O H . L in e a r p a rtia l p re ssu re d e p e n d e n c ie s b a se d o n a p o w e r ra te la w w e re o b ta in e d a n d sh o w e d a n e a r-z e ro o rd e r in C H 3 O H a n d a n e a r-first o rd e r in H 2. ), N O re d u c tio n (N O ), M e th a n o l( ), L a 2 O 3 ( ), E x c e ss K e y w o rds : N itric o x id e ( oxygen( ). 1.. 1). ~ÇÂ²êãâjÚ¾ ¶z B*(N O x ).³JF«ê*¶J . b2FÚf¢ýÇ*¾ÚïJ*bjê ÎvÒ. j , æ[¾ jûb1 9 7 0 2n 1). b¾îJÊ jÊFîÎþï*JbFÊ. B¢B*^¶zB*2jJî b¯*J ^FòFÚ÷ÒjFÚj JÒ. 2 ) ~ÇF÷ÒòF¾Îv *. T o w h o m c o rre sp o n d e n c e sh o u ld b e a d d re sse d . ju n g k y u p @ k o n k u k .a c .k r.. ö(P t), j¾(P d ) ýJ¾(R h )2â®Jª¾÷Ò (T h re e -W a y C a ta ly st)NïfãÞ ¾ Ò êïb, 3 ) Â²bîÂ²FZ Þz^b¾ ¶zB*2êï*J ^ N´Ò. Bb, ÷Òîòz¾f 4). bJb¢²Ò. înrFÎ¾¾ ¶zB*.B¶2jF¾ JF ÷ÒF¾(S e le c tiv e C a ta ly tic R e d u c tio n , S C R )2 FÚ ^FÎvÎzFbF¾ ²÷ ÒFbF, B¶2Fî, ý JfJ6ò, F«ý« ïf& þbb bjNê bÒ. j , ZÞzFBrò 135.

(2) ¾ ¶zB*2êï*J ^FÎF« êFêî´« ïfF. b2 FÒ.. ?FÚF¾ ÒÎ JFîÒ. j , B²bL a 2 O 3 ÷Ò¯¾ N O .? FÚJF¾ FÛN2NîvÒÎî. Jê¾Brò¾ B²2FÚN O j. ^FC u -Z S M -5 ÷Òî b , b> 5). Nv*^æÞZ¾ zîbF« ¾L a 2 O 3 ÷Ò¯¾ B²¾FFÚN O jF¾. F jb¦(Io n -E x c h a n g e d Z e o lite ), ö{B*. Ê?¾îFÚ÷ÒFJêË2¢. (M e ta l O x id e ), â¢¾®®J®ö{(N o b le M e ta l). ¢âÎN O F¾?F?{²N2¢¢âÎ~. ýö{B*(M e ta l O x id e ) ÷Ò¾îJîÚb. JÒ.. 2®b N O j ^FòFÚ²BzjF¾. JFÞZîÒFz²wÎvÒ. 6 ,7 ) bÚJ¶J¢ãÒ.ª¾÷Ò.Òbz zFb¾FFÚ÷ÒFJbîF6 7 3 K b¯FÎ¾ ÷ÒFJb÷v¢® Î(B e n d -O v e r), WB*bbF« ¾÷ÒFJb¢®& þbvÒ. 8 ) ÚÚî®FÞZêîN O FF¾ J:Jb Òz¯FÒÎ JFîÒ. bÿ¾ H a m a d a ß9 ) .6 7 3 K bFFî¾ zîbF« ¾²B²bJF¾ FÛN2JÒ Ò2 FîÒ. B²bC u -Z S M -5 ÷Ò¯¾. N O FF¾¾îJJ2^F®¢Îv ®8*, :Öæ, 9 -1 3 ) ö{*Jâ®Ê:Ö æ. 3 ,9 ,1 1 -1 3 ). ýÒfsFF jb¦ ¾ 3 ,9 ). N O ¾îJJ2âÚê¶Ò. Bb, ö{*J â®Ê:ÖæzýFbF¾. ²N O FF¾¾îJJ, 6òýË2 ®¢¶Ò. æÚ, B²¾FFÚN O FF¾ ?2®F?Bb¶¾îJÞZ^ F²w®8ÎvÒ. H a m a d a ß .zFb 9). F¾B²b.J2®¢^bB ¶z(N O 2 )FbÒÿJÛN2JÒÎ. 6FîÎzîbF®8*b8 7 3 K bF¾ B²¾FFÚ:Öæ÷Ò¯¾ N O î¼. bF¾®8*N O 2 5 7 3 K ¾ 2ê. J2âÚê¶Ò. T a b a ta ß .ö{2â®Ê 13). ÷Ò¾v¢ö{~¢JJ2®¢®8 *ö{ê:ÖæF¯&¾FFÚ÷Ò FJ2îÊÒÎêFîÒ. H u a n g ß. 14). . zî bF «¾ N O î Bn®r (L a 2 O 3 ) ÷Ò¯¾ jB²z(C O ) ýz(H 2 ).. 136. 13. 2. , 2005. 2. æÒÆ¾ JL a 2 O 3 (A ld ric h , 9 9 .9 % ) ÷Ò *î1 0 2 3 K ¾ zjFâ¢b 1 0 Êò Ç6 zÊÎ, bF Jbï. B E T S u rfa c e A n a ly z e r(M ic ro m e tric s C o . A S A P 2 0 0 0 )2bFÚ N 2 j*OÊ FîÒ. ?{²N.b æ væz?jFÚ1 C¾. ÒÆFîÒ.. 15). ?ò²¾v¢ *W¢. F{²M a ss S p e c tro m e te r(A m e te k C o . M 2 0 0 ), G a s C h ro m a to g ra p h (Y a n a c o C o . G -3 8 0 0 ) æÎ C h e m ilu m in e sc e n c e N O -N O 2 -N O x A n a ly z e r(T h e rm o E n v iro n m e n ta l In stru m e n ts C o . 4 2 C )jFÚ* W¢FH 2 , N 2 , O 2 , N O , C O , C O 2 , N 2 O ýC H 3 O H ßF{²jFîÒ. H 2 O *Zî¶* ·ï*Jr N´¶*^N O F¾?F n*fm e th y l n itrite (C H 3 O N O ) ýfo rm a ld e h y d e (H C H O )bï¢r ¾¢®bv¶Ò. î ZJ¶æò bÒ2 rF òFÚ C h ro m o so rb 1 0 2 C o lu m n (0 .3 2 m m × 2 .5 m )2F î*^¢jr Fbò¾4 5 3 K ¾ ÚV2 3 0 c c (S T P )/m in .*J1 ÊòÇ6Fâ¢¢JB ÊÒ. ²2 3 2 K ¾ 2 -2 .5 rò®ÊÒî 3 5 -4 0 K /m in Fîâ{²J4 5 3 K :®îâÊ b ²¾ 3 -5 rò®Ê ò¢ï*Jr Êò .1 1 -1 4 rbz¶Ò. ÷ÒÒÆ2ÊFò¾9 7 3 K ¾ 9 .8 % O 2 /H e îj2 0 c c /m in .F·*J1 ÊòÇ6F â¢²zFVï*2 ^ÊÒ. ÒÆ¾ Jî4 .0 % N O /H e , 9 .8 0 % O 2 /H e æÎ¢î JH e 2Fî*^, îF ²N O ýO 2 î9 9 % b¯æÎH e 9 9 .9 9 9 % b¯*JÎ ².

(3) L a2O 3. NO. FîjFîÒ. JÚV2ª:*J2 º&2 7 3 K j®FÎvB²Ú Ëj £êÊ B²2?¾ã÷Fî*^Ú. ËJn?¾bbî.B²F? 2®FòFÚ3 2 3 K JîâÊÒ. zîbF®8«¾A rrh e n iu s p lo t2 ©òFÚ6 2 3 -8 2 3 K ¾ N O FF¾?2j* Îã÷*F·.4 5 c c (S T P )/m in .j®Ê Jsï*J?¾ã÷N O ýC H 3 O H F {²ïï1 .8 % ý0 .6 % î²KFîÒ. z îbF«¾ã÷*ÿFïïFî{ ²Fã÷*F·b4 5 c c (S T P )/m in .f «¾1 .2 % O 2 îã÷*¾bF²K^öFî Ò. zîbF«¾2 9 8 -7 7 3 K F. ²ò¾îFÚÎFîÒ. N O F¾?FN O ýC H 3 O H ¾îJ?jFòFÚ zîbF®8«¾Òf?*FrC 2jFz®Êî¢^J?*FrC2 ®BÊb 7 2 3 -7 9 8 K bFÒfî®² ¾ ÒÆ2wFîÒ. ?F^bbær ?j®Nv²KòBb2 0 % bFî ²KFî*^?jFòFÚ_ ?{²(P o w e r R a te L a w )jîFîÒ. C H 3 O H ¾îJ?jFòFÚN O FrC 21 4 T o rr(1 .8 % )¾ jFz®ÊÎC H 3 O H FrC22 .3 -1 6 T o rr(0 .3 -2 .1 % )b¾ ®BÊ *^, b¾N O ¾îJ?C H 3 O H Fr C21 2 T o rr(1 .5 % )¾®ÊÎN O FrC2 3 .6 -1 9 T o rr(0 .5 -2 .5 % )b¾ ®BÊb ÒÆ 2wFÚFîÒ.. Fig. 1 Arrhenius plots for (a) NO disappearance, (b) N2 formation and (c) N2O formation. Reaction conditions: 1.8% NO, 0.6% CH3OH in He, Pt = 760 torr. îVÆË²vÒ. NO +CH3OH. 2N2O +2H2O +CO. (2). F ig . 1 (a )¾®.bN O îN 2 ýN 2 O J òFF ^ z JB¾ö®(A c tiv a tio n E n e rg y )jFòFÚ>î®÷ÒjF ÚÒÆ2wV*J8b¾îJjJzB FîÒ. N O FF¾?¾FFÚn*JN 2 O î. 3. ÷ÒjzÊ²¾JB E T Jbï.2 .2 m 2 /g *JÒz®Ò. ã÷*¾ÚV 1 .8 % FN O .0 .6 % FC H 3 O H 2FË(1 )¾ :v.bN O j2òFzF¾Ê vNïf bÒ. 3NO + CH3OH. N2 + 2H2O + CO2. Ë*JN 2 ýN 2 O Ë¾îJJB¾ö® jFòFÚïïFA rrh e n iu s p lo t2F ig . 1 (b ) ý(c )¾²ÊFîÒ. bÒ¾îJJB¾ö ®, N 2 ý N 2 O Ë¾îJJêN 2 ¾îJË ²(S e le c tiv ity )jT a b le 1 ¾kFÚF*^N 2 ¾ îJË²Ò:FË(3 )êbFFîÒ.. (1). æÚ, N O FF¾?¾FFÚn*JN 2 O. §Ï o× ßS á ZÎ××Ü §Ï o× â §Ï ¨ o×. T rans ac tio n s o f th e K o re an S o c ie ty o f A u to m o tiv e E n g ine e rs , V o l. 1 3 , N o . 2 , 2 0 0 5. (3). 137.

(4) S ang H w an K im. H y un Ju Y o o. Jun g -K y u P ark. a. Table 1 Arrhenius runs for NO reduction by CH3OH R un NO N 2 fo rm a tio n N 2 O fo rm a tio n 2 3 2 3 Ea A c tiv ity (.m o l/s m × 1 0 ) Ea Ea A c tiv ity (.m o l/sm × 1 0 ) (k c a l/m o l) (k c a l/m o l) 623K 723K (k c a l/m o l) 623K 723K b 1 13 9 49 183 21 6 .6 74 b 2 15 12 31 82 20 7 .0 93 c 3 17 8 30 58 21 3 0 .0 607 d 3 19 (-6 ) 28 15 28 1 0 .0 596 a R e a c tio n c o n d itio n s : 1 .8 % N O , 0 .6 % C H 3 O H , b a la n c e H e , P t = 7 6 0 to rr. b 0 % O 2 in fe e d . c 1 .2 % O 2 in fe e d , n o c o rre c tio n fo r h o m o g e n e o u s re a c tio n . d 1 .2 % O 2 in fe e d , c o n trib u tio n fro m h o m o g e n e o u s su b stra c te d . Table 2 Comparison of NO reduction over La2O3(0% O2) R e d u c ta n t E a (k c a l/m o l) NO N2 N 2O a CH4 19 19 a H2 31 29 a CO 35 19 b C H 3O H 15 10 21 a T a k e n fro m [1 5 ]. R e a c tio n c o n d itio n s: 1 .7 % N O a n d 0 .4 5 % C H 4 o r 1 .7 % H 2 o r b R e a c tio n c o n d itio n s : 1 .8 % N O a n d 0 .6 % C H 3 O H in H e .. S e le c tiv ity to N 2 (% ) 623K 723K 88 81 50 74. 2. 71 47 9 2. 3. A c tiv ity a t 7 7 3 K (.m o l/sm × 1 0 ) NO N2 N 2O 3 .5 1 .7 3 4 .0 3 .5 1 3 .6 1 5 .0 0 .9 6 .6 638 128 191 1 .7 % C O in H e .. JB¾ö®N O ýC H 3 O H FòBb2 0 % bFf ÒÆ¾ ©. ~ºº2 FÚ A rr h e n iu s p lo t*JnZFîÒ. N O jF¾Ê:¾ N 2 O îÒ·*JË*JN 2 ýN 2 O FË¾ îJ JB¾ö®j ZF òFÚ bÒF A rrh e n iu s p lo t2F ig . 1 (b ) ý1 (c )¾²ÊFîÒ. N O FF¾?¾ zîbF®82«¾F ¾ JC H 3 O H jF«FJêJB ¾ö®F¾ JC H 4 , H 2 ýC O jF«. (a). FJýJB¾ö®. >FÚT a b le 2 ¾ kFÚFÒ. b¾FFbF¾ fC H 3 O H ² C O ýH 2 .bN O FF¾Ê¾N 2 *N¼. FN 2 O jËFC H 3 O H jF«¾ N 2 Ë¾îJJB¾ö®îÖï:2 :vÒ. BbJ.C H 3 O H jF¾ J N:îH 2 jF¾ JN:¾ FÚ2 0 ², C O jF¾ JN:¾ FÚ4 0 ²:2CfNv¶Ò. B².C O 2 ýC O JB^C O 2 Ë(1 )¾. :v.bN O FF¾?Ê¾N 2 . VÆËb¾, C O Ë(2 )¾®. 138. 13. 2. , 2005. (b). F ig . 2 P ro d u c t fo rm a tio n d u rin g N O red u ctio n b y C H 3 O H o v e r L a 2 O 3 in th e a b sen c e o f O 2 . (a) N -b a se d p ro d u c ts: ( ) N 2 , ( ) N 2 O , ( ) N O co n v e rsio n ; (b ) C -b a se d p ro d u c ts: ( ) C O , ( ) C O 2 , ( ) H C H O , ( ) C H 3 O H c o n v ersio n . R ea c tio n c o n d itio n s: 1 .8 % N O , 0 .6 % C H 3 O H in H e , P t = 7 6 0 to rr.

(5) C ataly tic R e d uc tio n o f N itric O x ide in O x y g e n -R ic h E x haus t w ith M e th an o l o v e r L a 2 O 3 C ataly s ts. bN O FF¾?Ê¾N 2 O .VÆË Ò.. N:¾Îj²¯?bÿJÛN2V. F ig . 2 (a ).2 (b )j >FÚâbbÚJ«2C. 2:vÒ. >î®«¾ÒÒnbþ.. fNîvÒ. N O FF¾?Ê¾ö¯Î. Î²ò¾ B²FòBbZzÒbÒ. j²¯?(H o m o g e n e o u s G a s-P h a se R e a c tio n )2. qbÒ. zîbF«¾5 7 3 K Fî. ÎFòFÚ?¾÷Òj2®8.¯. ¾ ²B²FòBb4 0 % ¾bb^¼.. Ê¾ $?ÒÆ(B la n k T e st)2FîÒ. F ig . 3. Fm e th y l n itrite îË Ò. b?.Ò¾ ². ¾ :v.bzîbF®8«. j¢v^N O , O 2 ýC H 3 O H îÚÚÖ²F. ¾6 7 3 K b¯¾ Îj²¯?bN O F. Îj²¯?2j* m e th y l n itrite jËÊ. F¾?¾.ÛN¾N´ÎL a 2 O 3 îN O. ²vÒ. K o d a ß1 6 ) .N 2 O 4 îm e th y l n itrite j. FF¾?¾ H C H O F Ë2îbFÎv:. F^&ÚFÎvÒÎ 6FîÒ.. 2CfNv¶Ò.. 2 NO + O2. ò?¾ 1 .2 % O 2 îbF«¾·, N O ýC H 3 O H {²îÇjJ^b¾ zFï. 2 NO2. 2 NO2. (4). N2O4. (5). 2¢¢æê¾FFbzîbF®82 :. >FÚF ig . 4 ¾®.bzîb. (a) (a). (b). (b). F ig . 3 N O re d u c tio n b y C H 3 O H in th e ab se n ce o f O 2 in em p ty rea c to rs. (a ) N -b a se d p ro d u c ts: ( ) N 2 , ( ) N 2 O , ( ) N O c o n v e rsio n ; (b ) C -b ased p ro d u cts: ( ) C O , ( ) C O 2 , ( ) H C H O , ( )C H 3 O H c o n v e rsio n . R ea c tio n co n d itio n s: 1 .8 % N O , 0 .6 % C H 3 O H in H e, P t = 7 6 0 to rr. F ig . 4 N O re d u c tio n b y C H 3 O H in th e p re se n ce o f O 2 in em p ty re ac to rs. (a ) N -b a se d p ro d u cts: ( ) N 2 , ( ) N 2 O , ( ) N O co n v e rsio n ; (b ) C -b a se d p ro d u c ts: ( ) C O , ( ) C O 2 , ( ) H C H O , (× ) m eth y l n itrite, ( ) C H 3 O H c o n v ersio n . R ea c tio n c o n d itio n s: 1 .8 % N O , 0 .6 % C H 3 O H in H e , P t = 7 6 0 to rr. T rans ac tio n s o f th e K o re an S o c ie ty o f A u to m o tiv e E n g ine e rs , V o l. 1 3 , N o . 2 , 2 0 0 5. 139.

(6) N2O4 + CH3OH. CH3ONO + HNO3. (6). M e th y l n itrite 6 7 3 K b¯F²:®Ë*¾ ¼.bbF^N 2 .N 2 O FË.îbj :2:vÒ. F ig . 5 ¾N O , C H 3 O H ýO 2 bF?¾ L a 2 O 3 Fï2²ÊFîÒ. Îj²¯?bJ F zj¢Î6 7 3 K bF¾ b?¾÷Òîÿ JÛN2F®©F^7 0 0 K bF¾ m e th y l n itrite î¼.b2:vÒ. æÚ 6 7 3 K b¯¾ L a 2 O 3 N O FòB2îÊ Î, H C H O FË2£ F^.JC O j ËÊ¢2CfNv¶Ò. F ig . 6 ¾?{²¾. F ig . 6 D e term in a tio n o f re ac tio n o rd e rs o n N O an d C H 3 O H p a rtia l p re ssu re s: (a ) 7 2 3 , (b ) 7 4 8 , (c ) 7 7 3 , a n d 7 9 8 K . S o lid lin e s an d p o in ts re p resen t C H 3 O H a n d d ash e d lin e s a n d o p e n sy m b o ls rep re se n t N O. îJ_G2bFÚZJ?*rC¾î J?JnC H 3 O H ¾îJ?0 ¾î:¢ b^N O ¾îJ?^F1 ¾ î:¢ r2:v*^T a b le 3 ¾²¾f. (a). ?jkFÚFÒ. Table 3 Reaction order for NO reduction with CH3OH(0% O2). N O d is a p p e a ra n c e. T e m p e ra tu re (K ) 723 748 773 798. R e a c tio n o rd e r (C H 3 O H ) (N O ) -0 .1 0 .9 -0 .1 0 .7 -0 .1 1 .0 -0 .1 1 .0. 4. zîbF®82:.bN:¾L a 2 O 3. (b). F ig . 5 N O re d u c tio n b y C H 3 O H o v e r L a 2 O 3 in th e p re se n c e o f O 2 . (a ) N -b a se d p ro d u c ts: ( ) N 2 , ( ) N 2 O , ( ) N O co n v e rsio n ; (b ) C -b a se d p ro d u c ts: ( ) C O , ( ) C O 2 , ( ) H C H O , (× ) m eth y l n itrite, ( ) C H 3 O H co n v e rsio n . R e ac tio n co n d itio n s: 1 .8 % N O , 0 .6 % C H 3 O H in H e , P t = 7 6 0 to rr. 140. 13. 2. , 2005. ÷Ò¯¾ C H 3 O H 2bJN O FF¾¾îFÚ ¢¢âFÒ. zîbF®82«¾N 2 Ë¾îJJ.ÒfF¾ fC H 4 , H 2 ýC O jN«âÒÖj2:vÒ. æÚ C H 3 O H C H 4 ¾ FÚN 2 /N 2 O F ¾îJ..

(7) L a2O 3. Ë²j®¢¢bjîÊÞZî2 FH 2 ýC O . >F«¾ ¥J 2 âÚê¶Ò. N O FF¾?¾ C H 3 O H ¾îJ JB¾ö®1 5 k c a l/m o l2®¢¶ÎC H 3 O H ýN O ¾îJ?ïï-0 .1 ý1 .0 2: v¶Ò. zîbN«¾N O FF¾?. 3 0 0 K ¾ C H 3 O H î3 0 % b¯m e th y l n itrite JòF FÎj²¯?¾FFÚÒãb¾2 :vÒ. bÚJ?.6 2 3 K bF¾ î b¾Î¾ òïfB¾FJË* fC O 2 ýH 2 O îË¶Ò. §v6 2 3 -8 2 3 K ¾. N O FN 2 ýN 2 O JFòF.zîbF® 82:âÒ2ê. 2âÚê¶Ò. B² ¾FJN O FF¾.Òf÷Ò¾ FÚL a 2 O 3 î .²ò¾f¾J2®¢ÎB J÷ÒJ2âÚú2CfNv¶Ò.. æÞZ2 0 0 2 2²b[îG>>¾ÞZ2F ®¾ê ÞZ22 âª v²K ¶kFÚ î P e n n sy lv a n ia S ta te U n iv e rsity Fÿ^Jw¶* ^b¾þÊ«¶Ò.. R e fe re nc e s 1 ) M . S h e le f, “ S e le c tiv e C a ta ly tic R e d u c tio n o f N O x w ith N -fre e R e d u c ta n ts ,” C h e m . R e v ., V o l.9 5 , p .2 0 9 , 1 9 9 5 . 2 ) K . C . T a y lo r a n d J . C . S c h la tte r, “ S e le c tiv e R e d u c tio n o f N itric O x id e o v e r N o b le M e ta ls ,” J . C a ta l., V o l.6 3 , p .5 3 , 1 9 8 0 . 3 ) K . C . T a y lo r, “ A u to m o b ile C a ta ly tic C o n v e rtte rs ,” C a ta l. R e v . S c i. E n g ., V o l.3 5 , p .4 5 7 , 1993. 4 ) K . M a s u d a , K . T s u jim u ra , K . S h in o d a a n d T . K a to , “ S ilv e r-P ro m o te d C a ta ly s ts fo r R e m o v a l o f N itro g e n O x id e s fro m E m is s io n o f D ie s e l E n g in e s ,” A p p l. C a ta l. B , V o l.8 , p .3 3 , 1 9 9 6 . 5) M . Iw a m o to , H . F u ra k a w a , Y . M in e , F . U em u ra , S . M ik u y ira a n d S . K a g a w a , J . C h e m .. NO. S o c . C h e m . C o m m u n ., p .1 2 7 2 . 1 9 8 6 . 6 ) J . N . A rm o r, “ E n v iro n m e n ta l C a ta ly s ts ,” A p p l. C a ta l. B , V o l.1 , p .2 2 1 , 1 9 9 2 . 7 ) F . J . J e n s s e n , H a n d b o o k o f H e te ro g e n e o u s C a ta ly s is , W ile y -V C H , F R G , 1 9 9 7 . 8 ) K . C . C . K h a ra s , H . J . R o b o ta a n d D . J . L iu , “ D e a c tiv a tio n in C u -Z S M -5 L e a n -B u rn C a ta ly s ts ,” A p p l. C a ta l.B , V o l.2 , p .2 2 5 , 1 9 9 3 . 9 ) H . H a m a d a , Y . K in ta ic h i, M . S a d a k i, T . Ito a n d T . Y o s h in a ri, “ H ig h E ffic ie n c y o f A lu m in a a n d H -Z e o lite C a ta ly s ts fo r S e le c tiv e R e d u c tio n o f N itro g e n M o n o x id e b y M e th a n o l in th e P re s e n c e o f O x y g e n a n d W a te r V a p o r,” A p p l. C a ta l.A , V o l.8 8 , p .L 1 , 1 9 9 2 . 1 0 ) T . Y a m a m o to , A . N o d a , T . S a k a m o to a n d Y , S a to , S o c . A o tu m o t. E n g ., S o e c . P u b l., V o l.1 1 4 0 , p .1 1 3 , 1 9 9 6 . 1 1 ) M . T a b a ta , H . T s u c h id a , K . M iy a m o to , T . Y o s h in a ri, H . Y a m a z a k i, H . H a m a d a , Y . K in ta ic h i, M . S a s a k i a n d T . Ito , “ R e d u c tio n o f N O x in D ie s e l E x h a u s t w ith M e th a n o l o v e r A lu m in a C a ta ly s ts ,” A p p l. C a ta l.B , V o l.6 , p .1 6 9 , 1 9 9 5 . 1 2 ) S . G . M a s te rs a n d D . C h a d w ic k , “ S e le c tiv e C a ta ly tic R e d u c tio n o f N itric O x id e fro m S ta tio n a ry D ie s e l S o u rc e s b y M e th a n o l o v e r P ro m o te d A lu m in a C a ta ly s ts ,” C a ta l. T o d a y , V o l.4 2 , p .1 3 7 , 1 9 9 8 . 1 3 ) M . T a b a ta , H . H a m a d a , F . S u g a n u m a , Y . Y o s h in a ri, H . T s u c h id a , Y . K in ta c h i, M . S a s a k i a n d T . Ito , C a ta l. L e tt., V o l.2 5 , p .5 5 , 1 9 9 4 . 1 4 ) S . J . H u a n g , A . B . W a lte rs a n d M . A . V a n n ic e , “ N O R e d u c tio n w ith H 2 o r C O o v e r L a 2 O 3 a n d S r-P ro m o te d L a 2 O 3 ,” J . C a ta l., V o l.1 7 3 , p .2 2 9 , 1998. 1 5 ) S . H . K im a n d J .-K . P a rk , “ C a ta ly tic R e m o v a l o f N itric O x id e in O x y g e n -R ic h E x h a u s t w ith M e th a n e o v e r M e ta l Io n -E x c h a n g e d Z e o lite s ,” T ra n s a c tio n s o f K S A E , V o l.1 0 , p .3 2 , 2 0 0 2 . 1 6 ) S . K o d a , K . Y o s h ik a w a , J . O k a d a a n d K . A k ita , “ R e a c tio n K in e tic s o f N itro g e n D io x id e w ith M e th a n o l in th e G a s P h a s e ," E n v iro n . S c i. T e c h n o l., V o l.1 9 , p .2 6 2 , 1 9 8 5 .. T rans ac tio n s o f th e K o re an S o c ie ty o f A u to m o tiv e E n g ine e rs , V o l. 1 3 , N o . 2 , 2 0 0 5. 141.

(8)