DOI: 10.18957/rr.8.2.410

SPring-8/SACLA 利用研究成果集

2018A1578

Section B

BL14B2窒素酸化物の選択触媒還元用材料の性能向上と構造解析
Characterization and Activity Enhancement of Materials for Selective
Catalytic Reduction of Nitrogen Oxides
vƔ ƢÙƗƫ ßÝƩĚ ÉĂ£č āºƬū Ĭâƪĉ ĿŘ¿
Yasuyuki Banno, Hiroyasu Suzuka, Hiroaki Takahashi, Masatoshi Yoshimura, Kiyohiko Saito,
Yukio Takagi
8Mb7c >X<ZGI(ē)
 N. E. Chemcat Corporation
ƘD9[7I!H6cD]8aAaõ;Bi őŚƓĵĦƌŵÃČý0 |ľļ¹ Ƌƒ/ĀÇČý ġĳŢjê ! .dÓ êŤ¥e Ģ).
10śÅã ğƂŁ¾ D9[7I ġĳŢjê¥e\aƓĻ!ć0 FZP?7I -śÅã ÏD9[7I! đ!Ĉä 1 o¬@\:5]WKğ ř 15 ƘFZP?7I\aƓĻ0ġĳŢjå ĦêŤ ¥eČý3ç0  ĖƉŴĐ ŝđ\aƓĻ đ!P  Cu Ńö ÁđĤêıĖƉ »êŤ¥e0 ! ġĳŢjă P  Al - SAPO ƦwĖƉ Ľí O ÄØƣ 4 Ƒx Cu2+Ŏ FZP?7IƨĔ . Ɵť3ñ0)
÷Ê1
<c`cJƸƎòŵÃƏőŚƓĵƘFZP?7IXANESEXAFS\aƓţĄňŏłŁƸ
ƎòŵÃƏƭSCR Selective Catalytic ReductionƮ!H6cD]8aAa .õ10õĠ;Bi¦'10őŚƓĵƭNOxƮ ƞćðŭ/ƘFZP?7IƭCu-CHAƮĦêŤ 1ŵÃČý dËƁùƃ ŵÃ|210õ;B!ÌĮ .
650°C te ƩĮ'ĮÛŖ­ Ú gġŪĠ3½ ¦()D9[7I |ľĎu! /Ƌƒ/ŵÃČý!ġĳŢjê Ģ).10'dŧ 300–400°C åĮÛƤ´! NOx !Ħ1+ 200°C tf yĮ´! NH3  NOx èƈÛ Ɗ ' 500°C te ƩĮ´! NH3 Ɠ1 NOx Ľí0èĦĹ yf0 hĮÛ´ ĦêŤ¥e Žƥ0ġĳŢjå yĮbƩĮĦêŤ3¥e0)
Cu-CHA œmŚ3ī0ĕŷ 1 0[1, 2]ċňŏ!œmŚ P
PdPrAu 3ƎÊġĳŢjå ĦêŤ¥e3ĕŷ ŝđ\aƓ-0 P īêŤ¥eđ3ŋ -êŤÔ Ĥêı0 Cu Ä¨­ Ƒxļ¹ Ô-0*Ŋ )0)ġĳŢjå ŗĊ?aU] XAFS įÊ3ŬCu ¨/ ÑîĖƉ3Ă. 0
ËƧƸ
XAFS ËƧĎuƸËÿQcX[7a BL14B2įÊÎſŚ§ŒƸCu KPd KAu LIII
YN=_ŝąƣþxƸSi (311)ƣįÊïģƸƆƋįÊļ¹ĎuƸÌĮ¾Ġi
ŹýƸCu-CHA !Trimethyladamantylammonium hydroxide ƭSachem ŌűƮ3ćěĖƉųÊ|ľ CHA 3¢íå600°C ĲíŉƓƘİĩ79anø Cu-CHA 3žűœmŚƭPPdPrAuƮ!ńà0ġİê¸3 Cu-CHA ¦ħblĴžűġĳŢjĻƸ10%ġŪĠ3¦(ŐĠf650°C  100 h óġĳŢjĻ3ŬNOx ĦêŤŸ~Ƹƅ Źý3ġú5]WKP7aEc3ľB[\c13Ēķ OL:Xƭ25.4 mm ã 50 mm ƚƮ 180 g/L ńà3·Õ 500°C ĲíŵÃeƅ ġĳŢjĻ3Ëÿ1. OL:XŵÃ3ŵÃŸ~ůŠƭSIGU-2000 µ¶ű{îƮCGI210 ppm NO40 ppm NO2 250 ppm NH3 4% H2O10%ƶƳƲDOI: 10.18957/rr.8.2.410

SPring-8/SACLA 利用研究成果集

Section BO2 $ĞƐ N2 P[aBŜí3ć0Ī¢;B Ê×Ġĥi 0őŚƓĵƏĹ3įÊįÊ!200–500°C ĮÛŖ­ŐƜƈÛ SV = 59,000 h-1 Ŭ;BĐ!
ŦƁõ;BįÊůŠƭMEXA-6000FT µ¶ű{îƮ3ľŬ
XRF įÊƸÈŜí!Źý 10 g 3±íá AxiosƭSpectrysis ŌƮ3ľįÊ
NMR įÊƸ27Al-, 29Si-, 31P- ¯z NMR !ADVANCE III HDƭBruker ŌƮ3ľįÊŝđ-$šÍƸįÊ}Źý ÈŜíƭ@\:5]WKğ (SAR)Cu ƀƕ%īŚ1. ƀƕ%Ʈ3Ů 1 ŋ'ġĳŢjå¡Źý NOx ĦêŤyĮĦêŤƩĮĦêŤ3U_GI* 3® 1 ŋU_GI ûÆ!ŮƳ Źý No.Îè0

Ů 1 NOx ĦêŤįÊ}ŹýHyoŹý
#,ƯƯÈŜíNo.
SAR Cu % īŚ 
19.4
3.7% P 4.6% 
2
11.3 3.9% ưư3
11.3 3.7% P 2.0% 
45678
9
10
11
12
13
14
15
16
17

14.5
14.5
15.1
15.4
15.4
15.4
15.5
15.7
15.7
19.4
19.4
21.1
21.1
23.7

3.8%
3.4%
4.0%
3.6%
3.1%
3.1%
3.4%
3.2%
3.2%
3.3%
3.3%
3.4%
3.3%
3.3%

PPPrPưPdPư
AuPPrư
PP

2.2%
2.4%
1.5%
1.5%
ư
0.5%
2.2%
ư
0.5%
0.9%
2.2%
ư
0.9%
2.2%

® 1 ġĳŢjå¡Źý
Ů 2ƱP]=Ŝí$ŢjåŹýNo.
1011NOx ĦêŤ
4 Ƒx Al ÄğĹP]=Ŝí4 Ƒx Al/(Si+Al)ğ
ƭXRFƮ
ƭNMRƮ
SAR
Al/(Si+Al)ğ
ŢjŢjå
ƯƭżĂü31

15.5
11.4%
9.7%Ʈ
7.2%
15.7
11.3%
10.9%
5.9%

® 1 -/yĮbƩĮĦêŤ*Ć*ŨÂ ! No.10PīŹý'īŚ Źý! No.11 ĦêŤ ğƂŁŨÂPdPrAu ī!ĦêŤ3ë0¥
P ī- NOx ĦêŤ ¥eĻĿ3÷Ê0)No. 10ƭP /Ʈ No. 11ƭP Ʈ ?aU]ğƂ3Ŭ27Al-,29Si-, 31P-¯z NMR įÊŝđ3Ů 2 ŋNo. 10ƭP /ƮŢj!D9[7IĖƉĿď0ĝ«ƣz 4 Ƒx Al ÄğĹ
ƭAl/(Si+Al)ğƮ No. 11ƭP Ʈ-/y Ţjå!ĝ«ƣz 4 Ƒx Al ÄĹ Ʃ ť Al ƝŢjêŤ ¥eŋª1'® 2 Ţjå No. 10ƭP /Ʈ CHA ĖƉ
Ň.10 SAPO-34 31P-NMR įÊŝđ3ŋNo. 10ƭP /ƮŢjÇ²\aƓ¸ńà0Rc= ŢjåĨÀs2 SAPO-34 Îè0Rc= ĺ11!ĖƉ¼ Al 
Ä \aƓŝ¢ SAPO ƦwĖƉ3áíť Al 3ñ03ŋª0'Ţjå Rc= T_cJ0 . SAPO ƦwĖƉ! P Ç²ķìÕ /ċď ƨĔĖƉ ÜĘ .1xŠ*Ç²0 ŋª10æďFZP?7I -ÏśÅƭĆ¾śÅĖíƓŚÄû 8
Ʈ D9[7I!\aƓ śÅ/Ơ \aƓĻ-0ġĳŢjê¥eđ Ĉä Ŷ21
[3]
411

® 2ƱNo.10 Ţjå$SAPO-34

31P-NMRDOI: 10.18957/rr.8.2.410

SPring-8/SACLA 利用研究成果集

Section B

SAR ř 15 å ¢íFZP?7I3ľ0\aƓĻ-* Cu-CHA ġĳŢjå êŤ3¥e0  0 Ă. ĜêŤÔ Ĥêı0 Cu Ä¨­ Ƒxļ¹ Ô-0* 0  3Ŋ )0)ġĳŢjå ŗĊ?aU] XAFS įÊ3Ŭ® 3 ŢjCu K Œ XANES BV=I] ® 4 ŢjåCu K Œ XANES BV=I]® 34 Ţjå ?aU] Cu-K Œ XANES BV=I]3ŋNo. 10bNo. 11 *%&¤ė CuO ƄBV=I]0 CuO Ç²0 8975 eV rƄ U^Rc= Ç² áķ!CuO ¤ė Øƣ 4 Ƒx ĆƄö O Ä3ć0 [Cu(H2O)6]2+ ƙ79a 1Ƅġ© Cu2+ 79a ĖƉé210[4]Ţj ® 3 CuO -$ No. 10ƭP/Ʈ Rc=IGUğƂNo. 11ƭP Ʈ!++Ʃ CuO ++ŀ0Èķì3¦40 Ťê 0Ţjå ® 4 !No. 10bNo. 11 þ Ô! ġĳŢj-Cu Èķì %&¤d3ŋª0
® 56 11Ţjå Cu K Œ EXAFS ô3 CuO ŋ.àź EXAFSô3 k-range 3.0 ~ 15.0 Å-1 Sc\8»øçãĖƉƝû3® 78 ŋ

® 5 ŢjCu K Œ EXAFS ô® 6 Ţjå

Cu K Œ EXAFS ô® 7 ŢjCu K ŒãĖƉƝû

® 8 Ţjå

Cu K ŒãĖƉƝûŢj ® 7  0ř 1.6 Å rƄ Rc=! Cu2+ Øƣ 4 Ƒx O ÄÎè0œ 1 Ƒx°ńà0ƭ® 9 (a)ƮNo. 10ƭP /Ʈ CuO !%&¤Ŕ Ƒxû0 No. 11ƭP Ʈ
412

DOI: 10.18957/rr.8.2.410

SPring-8/SACLA 利用研究成果集

Section BƑxû! Ï Cu2+ Ŏ ÑîĖƉ Ðk10 Ťê 01!® 3 Ţj No. 11 CuO !++ŀ0Èķì3¦40 Ťê ŋª1 XANES ŝđņŅ'2.7 Å rƄ œ 2 Ƒx°!D9[7I 79anø?7IƭAl-siteƮ OÄŝ¢ Cu2+Ŀď0ÖÒ1Cu-O-Al '! Cu-O-Si
Al '! Si Ä2+
ńà0[5]® 9 (b) 2 ı Al-site ŝ¢ġ© Cu Ŏ ęÞ®3® 9 (c) 1 ıŝ¢ġ© Cu2+Ŏ ęÞ®3ŋCu2+ Ƒx Ť° Al-site 2 ŕî1" 2 ıŝ¢³1 ŕî 1" 1 ıŝ¢³3Ľí0š.101 ıŝ¢³ơũŰ )Ƒxġ 1 ŴƟ OH- 79a0Ţjå ® 8 !þ ãĖƉƝû %&¤d/œ 2 Ƒx° Ƒxû ĭÐ
01! Cu2+
Al-site .¼1ŦĿġ©79a-/!Al-siteAl ÄƄ ÑîĖƉ k1)š.10No. 10ƭP /Ʈ Ţjå!Cu2+
O ÄØƣ 4 Ƒx œ 1 Ƒx°ĖƉ3şó'' SAPO ƦwĖƉ3pD9[7IƨĔöŞ0ĖƉ30 ! ÷įàźĖƉ ÷ÊęÞ®3® 9(d)ŋ® 9Ʊ÷Ê10 Cu2+ÑîĖƉ ęÞ®

te-/Ţjå Cu ¨/ ÑîĖƉ\aƓ3ľ P ī đ!tf -š.10ƭƳƮŢjå3ƇCu ! Cu2+O ÄØƣ 4 ƑxĖƉ30ƭƴƮŢjƑx O Ä dƐ!FZP?7IƨĔ Al-site Ŀď0 O Äq!ġ©ġĿď÷Ê10ƭƵƮ\aƓī ¶¢Ţj Cu ¨/ ÑîĖƉƭO ÄØƣ 4 ƑxĖƉƮ ++k10 Ťê 0ƭƶƮŢjå*Ƒx O Ä!ġ©ġFZP?7I Al-site Ŀď0 Ţj Al Ƅ ÑîĖƉk1 Ľ0ƭƷƮAl Ƅ ÑîĖƉ k1-Øƣ 4 Ƒx Cu2+ Ŏ FZP?7IƨĔ .Ɵť0Ťê 0 \aƓ SAPO ƦwĖƉ3áí0àźØƣ 4 Ƒx Cu2+ ŎƟť3ñ0oå ŽƥƸ\aƓīĻ SAR15 å Cu-CHA Îć0 ŊŻ Ţj
0 Cu ¨/ÑîĖƉ k1ñđ! ěĖ ÷Ê  oå Žƥ'o¬PdPrAu  ƍōƖÒŚ īSCR êŤ¥eđŲ  êŤ¥e Ų.1¶¢!ĖƉŴĐ- ĻĿ3ŴĂšüĸƸ
[1] F. Gao et al., ACS Catal. 5, 6780 (2015).
[2] Ķƛ 2016-210664[3] Y. Yamasaki et al., Micropor. Mesopor. Mater. 223, 129 (2016).
[4] A. A. Verma et al., J. Catal. 312, 179 (2014).
[5] C. Paolucci et al., J. Am. Chem. Soc. 138, 6028 (2016).

413

DOI: 10.18957/rr.8.2.410

SPring-8/SACLA 利用研究成果集(Received: February 25, 2019; Early edition: May 27, 2020
Accepted: July 6, 2020; Published: August 21)

414

Section B