Characterization of Copper-Manganese Oxide Catalysts and Their Precursors: Effect of Precipitate Aging upon the Structure and Morphology of Precursors and Catalysts

(1)

&KDUDFWHUL]DWLRQRI&RSSHU0DQJDQHVH2[LGH&DWDO\VWVDQG7KHLU

3UHFXUVRUV(IIHFWRI3UHFLSLWDWH$JLQJXSRQWKH6WUXFWXUHDQG

0RUSKRORJ\RI3UHFXUVRUVDQG&DWDO\VWV

/ 0DOHNL_{0 +DJKVKHQDV)DUG}_{0 .KRVKQRRGL}_{$ $ 0LU]DHL}_{* -+XWFKLQJ}_{DQG6 + 7D\ORU} 'HSDUWPHQWRI&KHPLVWU\8QLYHUVLW\RI6LVWDQDQG%DOXFKHVWDQ =DKHGDQ ,UDQ

'HSDUWPHQWRI&KHPLFDO(QJLQHHULQJ8QLYHUVLW\RI6LVWDQDQG%DOXFKHVWDQ =DKHGDQ ,UDQ 'HSDUWPHQWRI&KHPLVWU\8QLYHUVLW\RI:DOHV&DUGLII&)7%8.

$EVWUDFW

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± PDQJDQHVHPL[HGR[LGHFDWDO\VWVVKRZHGDGUDPDWLFFKDQJHRI VKDSHRQDJLQJ,QDOOFDWDO\VWV&X2ZDVFRPSOHWHO\UHGXFHGWRPHWDOZKLOHWKH0Q2 GLGQRWUHGXFHXQGHUWKHH[SHULPHQWDOFRQGLWLRQV

.H\ZRUGV&DWDO\VW&RSSHU0DQJDQHVH2[LGH;5'3UHFLSLWDWLRQ0HWKRG

&RUUHVSRQGLQJDXWKRU(PDLODGGUHVV+DJKVKHQDV#KDPRRQXVEDFLU

,QWURGXFWLRQ

&DWDO\VWVEDVHGRQFRSSHUPDQJDQHVHPL[HG R[LGHV DUH RI D FRQVLGHUDEOH LQGXVWULDO LPSRUWDQFH RZLQJ WR WKHLU DFWLYLW\ DV SRZHUIXO R[LGDWLRQ FDWDO\VWV >@ ,W LV NQRZQWKDWWKHVHPDWHULDOVFDQFDWDO\]HQHDU URRP WHPSHUDWXUH WKH R[LGDWLRQ RI &2 WR &2 DQGDWKLJKHUWHPSHUDWXUHV.

WKH FRPEXVWLRQ RI VHYHUDO RUJDQLF FRP SRXQGV LQFOXGLQJ K\GURFDUERQ KDOLGHDQG QLWURJHQFRQWDLQLQJ FRPSRXQGV >@ ,W KDV DOVR EHHQ UHSRUWHG WKDW LQ WKH UHGXFHG VWDWH FRSSHU PDQJDQHVH PL[HG R[LGHV DUH DFWLYH FDWDO\VWV IRU PHWKDQRO V\QWKHVLV IURP &2&2+ RU IRU OLJKW K\GURFDUERQV

V\QWKHVLVIURP&2+GHSHQGLQJRQUHDFWLRQ

SUHVVXUH DQG WHPSHUDWXUH >@ 7KH FDWDO\VWV DUH RI KLJK DFWLYLW\ LQ WKH DPRUSKRXV VWDWH EXW LW KDV JHQHUDOO\ EHHQ REVHUYHG WKDW WKH\ ORVH DFWLYLW\ DW WHPSHUDWXUHV DERYH . ZKHUH FU\VWDOOL]DWLRQ RI WKH VSLQDO&X0Q2

RFFXUV >@ +RZHYHU FU\VWDOOLQH &X0Q2

(2)

UHPDLQLQJ WKDW DUH \HW WR EH UHVROYHG 7KH DFWLYLW\ RI FRSSHU PDQJDQHVH R[LGH LV NQRZQ WR GHSHQG XSRQ WKH VWUXFWXUH SUHSDUDWLRQ RI WKHFDWDO\VWSUHFXUVRU7KLVLV WKH DVSHFW RQ ZKLFK WKH SUHVHQW ZRUN LV IRFXVHG 7KH VLJQLILFDQFH RI FKDUDFWHUL]LQJ WKH K\GUR[\ FDUERQDWH SUHFXUVRU SKDVHV RI FRSSHUPDQJDQHVH R[LGH FDWDO\VWV ZDV ILUVW KLJK OLJKWHG E\ 3RUWD HW DO >@ DQG SDUWLFXODU DWWHQWLRQ KDV VLQFH EHHQ DFFRUGHG WR PDODFKLWH &X&22+ DQG UKRGRF

KURVLWH 0Q&2 FRPSRXQG 7KH RFFXUUHQFH

RIWKHLQGLYLGXDOSKDVHVDQGWKHLUTXDQWLWDWLYH SURSRUWLRQVGHSHQGQRWRQO\RQWKHSUHFLSLWD WLRQ FRQGLWLRQV VXFKDVWHPSHUDWXUHS+DQG FRQFHQWUDWLRQV RI WKH UHDFWDQW VROXWLRQV EXW DOVR RQWKHZD\WKHSUHFLSLWDWHLVDJHG$JLQJ RI WKH SUHFLSLWDWH LQ WKH PRWKHU OLTXRU LV D FRPPRQ SURFHGXUH LQ WKH SUHSDUDWLRQ PHWKRG$JLQJRIWKHSUHFLSLWDWHVREWDLQHGE\ FRSUHFLSLWDWLRQ OHDGV WR SKDVH FKDQJHV DQG IRUPVWKDWDUHPRUHVWDEOH+RZHYHUWKHILUVW V\VWHPDWLF VWXG\ RIWKHHIIHFWVRISUHFLSLWDWH DJLQJZDVQRWUHSRUWHGXQWLOE\:DOOHU

HW DO >@ IRU WKH FDVH RI &X2=Q2 PL[HG

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

&DWDO\VW SUHFXUVRUV ZHUH SUHSDUHG XVLQJ WKH FRSUHFLSLWDWLRQSURFHGXUH$TXHRXVVROXWLRQV RI &X12 +2 PRO/ DQG

0Q12+2 ZHUH SUHPL[HG WR JLYH D

PRODU &X0Q UDWLR RI DQG WKH UHVXOWLQJ VROXWLRQ ZDV KHDWHG DW & $TXHRXV 1D&2 PRO/ZDVDGGHGGURSZLVHWR

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

$QDO\WLFDO 7HFKQLTXHV IRU 6DPSOH &KDUDF WHUL]DWLRQ

D 3RZGHU ;UD\ GLIIUDFWLRQ ;5' 7KH GLIIUDFWRPHWHU WKDW ZDV XVHG WR REWDLQ WKH GDWD SUHVHQWHG LQ WKLV LQYHVWLJDWLRQ ZDV D 3KLOLSV : PRGLILHG E\ +LOWRQ %URRNV 6FDQVZHUHWDNHQZLWKDTVWHSVL]HRI DQG D FRXQWLQJ WLPH RI VHFRQG XVLQJ &X.UDGLDWLRQJHQHUDWHG DW N9 DQG P$

7KH SHDN LQWHQVLWLHV ZHUH PRQLWRUHG DQG UHFRUGHGE\DFRPSXWHUZKLFKZDVHTXLSSHG ZLWK-&3'6LQGH[LQJV\VWHP

E 7HPSHUDWXUH SURJUDPPHG UHGXFWLRQ 735 7KH FKURPDWRJUDSKLF VRIWZDUH DQG FRQWURO PRGXOH LQWHUIDFH ERDUG LV VXSSOLHG ZLWK WKH 73'735 $ NQRZQ PDVV RI WKHFDOFLQHGVDPSOHEHWZHHQPJZDV KHDWHG WR & XQGHU IORZLQJ K\GURJHQ 7KHIORZUDWHRIJDVRYHUWKHFDWDO\VWZDV FP_{PLQDQGWKHUDPSUDWHRIWKHIXUQDFHZDV}

&PLQ7KHV\VWHPZDVFDOLEUDWHGXVLQJD NQRZQ PDVV RI FRSSHU R[LGH &RSSHU R[LGH LVDVVXPHGWRUHGXFHGLUHFWO\DQGFRPSOHWHO\ WRFRSSHUPHWDO

(3)

SUHFXUVRUV XVLQJ D -(2/ (; KLJK UHVROXWLRQ HOHFWURQ PLFURVFRSH ,OOXPLQDWLRQ ZDV DFKLHYHG XVLQJ D /D% ILODPHQW 7KH

LQVWUXPHQWXVHGWRFDUU\RXWWKHHQHUJ\GLVS ;UD\ DQDO\VLV ('$; ZDV D KLJK SHUIRUPDQFH9&+%8;PLFURVFRSH

5HVXOWVDQG'LVFXVVLRQ

7KHVWUXFWXUHDQGPRUSKRORJ\RIWKHSUHFXUVRUV DQGFDOFLQHGFDWDO\VWV

$ ;UD\ GLIIUDFWLRQ PHDVXUHPHQW 7KH ; UD\ GLIIUDFWLRQ UHVXOWV IRU WKH GLIIHUHQW DJHG SUHFXUVRUVDUHVKRZQLQ)LJXUH

)LJXUH 3RZGHU;UD\GLIIUDFWLRQ SDWWHUQVIRU DJHG FDWDO\VWSUHFXUVRUV

7KHXQDJHGSUHFXUVRUZDVIRXQGWREHZHOO FU\VWDOOLQH FRSSHU K\GUR[\ QLWUDWH WRJHWKHU ZLWK PDQJDQHVH FDUERQDWH DQG KHQFH LPPHGLDWHO\DIWHUWKHLQLWLDOSUHFLSLWDWLRQWKH FRSSHU DQG PDQJDQHVH FRPSRQHQWV DUH

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

)LJXUH 3RZGHU;UD\GLIIUDFWLRQ SDWWHUQVIRU DJHG FDWDO\VWSUHFXUVRUV

7KH XQDJHG FDWDO\VW FRPSULVHV FRSSHU PDQJDQHVH R[LGH &X0Q2 0Q2

(4)

UHODWLYH GLIIUDFWHG LQWHQVLWLHV IURP 0Q2

DQG&X2ZHUHOHVV7KHFDWDO\VWVDJHGIRU WR PLQ FRPSULVH FRSSHU PDQJDQHVH R[LGH &X0Q2 0Q2 DQG &X2

FKDUDFWHULVWLFRIWKHFDWDO\VWDJHGIRUVKRUWHU WLPHV KRZHYHU WKH LQWHQVLW\ RI WKH &X2 GLIIUDFWLRQ OLQHV DQG 0Q2 GHFUHDVHG ZLWK

DJLQJ WLPH7KH PDMRUSKDVH LGHQWLILHGDIWHU DJLQJ IRU PLQV ZDV &X0Q2 ZLWK

0Q2DQG&X2DVPLQRUSKDVHV

% 7HPSHUDWXUH SURJUDPPHG UHGXFWLRQ 7357KH735SURILOHVRIFDOFLQHGFDWDO\VWV GHULYHG IURP WKH GLIIHUHQWO\ DJHG SUHFXUVRUV ZHUHXVHGLQLGHQWLI\LQJWKHUHGXFLEOHVSHFLHV SUHVHQW 7KH 735 SURILOHV RI &X2 REWDLQHG IURP WKH SUHFLSLWDWLRQ RI FRSSHU QLWUDWH E\ 1D&2 IROORZLQJ PLQ VKRZHG D

UHGXFWLRQ SHDN DW & RULJLQDWLQJ IURP WKH UHGXFWLRQ RI WKH &X _{LRQ )LHUUR}_HWDO

>@ UHSRUWHG WKDW 735 SURILOHV RI &X2 H[KLELW WKH W\SLFDO SHDN ZLWK D VKRXOGHU DW KLJKHUWHPSHUDWXUHRULJLQDWLQJIURPWZRVWHS UHGXFWLRQRIWKH&X _{LRQWRPHWDOOLFFRSSHU}

&X _&X_{&X 7KH\ DOVR UHSRUWHG WKDW}

&X2UHGXFHVRQO\LQRQHVWHSDQGWKHVHFRQG VLJQDOUHVSHFWLYHO\WKHVKRXOGHULVDQDUWLIDFW RULJLQDWLQJ IURP VXEOLPDWLRQ RI PHWDOOLF FRSSHURQWKHXQUHGXFHG&X2SDUWLFOHV7KH 735 SURILOHV RI PDQJDQHVH R[LGH FDWDO\VW SUHSDUHG E\ SUHFLSLWDWLRQ RI PDQJDQHVH QLWUDWH XQGHU VLPLODU FRQGLWLRQV VKRZHG UHGXFWLRQSHDNVHQWHUHGDWDERXWDQG

R_{& 7KH ILUVW SHDN HQWHUHG DW} R_{& LV}

DWWULEXWHGWRWKHUHGXFWLRQRI0Q2WR0Q2

DQG WKH RWKHU SHDN DW R_{& VKRZV WKDW}

UHGXFWLRQ RI 0Q2 WR 0Q2 GRHVQRW RFFXU

XQGHU H[SHULPHQWDO FRQGLWLRQV DSSOLHG >@ 7KLV UHVXOW LV VXSSRUWHG E\ WKH H[LVWHQFH RI 0Q2 DQG0Q2DVPDLQSKDVHV7KH735

SURILOHVRIWKHPL[HGFRPSRXQGVDUHGLIILFXOW WR LQWHUSUHW EHFDXVH RI WKH ODUJH QXPEHU RI SRVVLEOH FRPELQDWLRQV RI GLIIHUHQW R[LGDWLRQ VWDWHVRIFRSSHUDQGPDQJDQHVH+HQFHLWLV SRVVLEOHWRDWWULEXWHLQGLYLGXDOSHDNVWRZHOO GHILQHGUHGR[UHDFWLRQVEXWRQO\VRPHWUHQGV FDQ EH UHFRJQL]HG )LJXUH JLYHV WKH 735 SURILOHV REWDLQHG IRU WKH GLIIHUHQW DJHG VDPSOHV

)LJXUH 735 SURILOHV RI FDWDO\VWV SUHSDUHG ZLWK YDU\LQJDJLQJWLPHV

7KH ORZ WHPSHUDWXUH SHDNV VHHP WR FRUUHVSRQGWRWKHUHGXFWLRQRI&X_&RSSHU

(5)

KLJKHU WHPSHUDWXUHV ZLWK LQFUHDVLQJ PDQJ DQHVHFRQWHQW>@

7KHKLJKWHPSHUDWXUHSHDNVFDQEHDWWULEXWHG WR D UHGXFWLRQ RI PDQJDQHVH EHFDXVH LW EHFRPHV PRUH LQWHQVLYH ZLWK LQFUHDVLQJ PDQJDQHVH FRQWHQW DQG QHDUO\ GLVDSSHDUV LI WKH FRQWHQW RI FRSSHU LV KLJK 7KH PLGGOH WHPSHUDWXUH SHDNV FRUUHVSRQG WR WKH UHGXF WLRQRI FRSSHUPDQJDQHVHPL[HGR[LGHVZLWK WKH IRUPXOD &X[0Q[2 ; DV

GHWHUPLQHG E\ ;UD\ GLIIUDFWLRQ 7KH 735 SDWWHUQ RI XQDJHG FDWDO\VW KDV VKRZQ 5HGXFWLRQ SURILOHV ZLWK WKUHH SHDNV 7KH ;5'SDWWHUQIRUWKLVFDWDO\VWDOVRKDVVKRZQ WKH H[LVWHQFH RI WKUHH SKDVHV 7DEOH DQG VKRZHG KLJKHU SHDN LQWHQVLW\ DULVLQJ IURP &X2

7KH 735 VSHFWUD RI FDWDO\VWV DJHG EHWZHHQ WRPLQKDYHVKRZQUHGXFWLRQSURILOHV ZLWK WZR SHDNV DQG WKH ;5' SDWWHUQV IRU WKHVH FDWDO\VWV H[FHSW WKH FDWDO\VW DJHG IRU PLQVKRZWKHH[LVWHQFHRIWKUHHSKDVHV 7DEOH +RZHYHU ZLWK WKH PLQ WKH LQWHQVLW\ RI WKH &X2 GLIIUDFWLRQ OLQHV RI 0Q2 GHFUHDVHG ZLWK DJLQJ WLPH 7KH

UHGXFWLRQLQLQWHQVLW\RIWKHGLIIUDFWLRQOLQHV PD\LQGLFDWHWKDWWKHDPRXQWRIWKHVHSKDVHV LVUHGXFHG

& 7UDQVPLVVLRQ HOHFWURQ PLFURVFRS\ 7(0

7KHHIIHFWRIDJLQJRQWKHPRUSKRORJ\RIWKH ERWK SUHFXUVRUV DQG FDWDO\VWV ZDV VWXGLHG XVLQJ 7(0 WHFKQLTXH 7KH HOHFWURQ PLFUR JUDSKV RI WKH GLIIHUHQWO\ DJHG SUHFXUVRUV VKRZHGGLIIHUHQWVKDSHV)LJXUH

7KH HOHFWURQ PLFURJUDSKV RI WKH FDWDO\VWV GHULYHGIURPFDOFLQDWLRQVRIWKHVHSUHFXUVRUV DOVRVKRZHGVLJQLILFDQWGLIIHUHQFHV

)LJXUHVKRZVWKHHOHFWURQPLFURJUDSKVIRU WKH FDOFLQHG FDWDO\VWV GHULYHG IURP WKH SUHFXUVRUV DJHG IRU D E DQG F PLQ

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

7DEOH735DQG;5'UHVXOWVIRUFDWDO\VWVSUHSDUHGZLWKYDU\LQJDJHLQJWLPHV

$JHLQJWLPHPLQ ;5'SKDVHV _735SHDNV$

_F

&X2&X0Q20Q2

(6)

DXQDJHG EPLQDJHG

FPLQDJHG

(7)

DXQDJHG

E PLQDJHG

F PLQDJHG

)LJXUH(OHFWURQPLFURJUDSKVRIWKHFDOFLQHGSUHFXUVRUVDXQDJHGEPLQDJHG FPLQDJHGVDPSOHV

&RQFOXVLRQ

;UD\ GLIIUDFWLRQ VWXGLHV IRU WKH XQDJHG SUHFXUVRUVKRZHGWKHZHOOFU\VWDOOLQHFRSSHU K\GUR[\ QLWUDWH WRJHWKHU ZLWK PDQJDQHVH FDUERQDWH 2Q DJLQJ WKH FRSSHU K\GUR[\

(8)

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

5HIHUHQFHV

66WRQ$GY&DWDO

$%/DPE:&)UD]HUDQG-&)UD]HU ,QG(QJ&KHP

+ $ -RQHV DQG + 6 7D\ORU - 3K\V &KHP /63XFNDEHU+&KHXQJ'/&RFNH DQG$&OHDUILHOG6ROLG6WDWH,RQLF V 69HSUHN'/&RFNHV6.HKODQG+ 52VZDOG-&DWDO

* & &KLQJHQ . & :DXJK DQG ' $ :KDQ$SSO&DWDO

9'RQGXU6/DPSDDQG'9XFHOLFLQ³ 3URF 6HFRQG (XURSHDQ 6\PSRVLXP 2Q 7KHUPDO $QDO\VLV ³' 'ROOLPRUH (G +HDGHQ/RQGRQ

9'RQGXU6/DPSDDQG'9XFHOLFLQ ³+HWURJHQHRXV &DWDO\VLV´3URF WK_,QW

6\PSRVLXP 3DUW 3 DQG 3URF WK _{(XURS6\PS 7KHUPDO $QDO '}

'ROOLPRUH HG 3 +H\GHQ /RQGRQ

6%.DQXQJR-&DWDO *06FKZDEDQG6%.DQXQJR-3K\V

&KHP1)

$ 3 6LQKD 1 5 6DQMDQD DQG $ % %LVZDV-3K\V&KHP6 0LDKDUD - 3K\V 6RF -DSDQ E, *%ODVVH-3K\V&KHP6ROLGV 33RUWD*0RUHWWL00XVLFDQLDQG$ 1DUGHOOD&DWDO7RGD\ '::DOOHU'6WLUOLQJ)66WRQHDQG 0 6 6SHQFHU )DUDGD\ 'LVFXVV &KHP 6RF

* )LHUUR 0 /R -DFRQR 0 ,QYHUVL * 0RUHWWL33RUWDDQG5/DYHFFKLD3URF WK_{,QWHUQDW&RQJ&DWDO%XGDSHVW}

,5/HLWK DQG0*+RZGHQ$SSO&DWDO

+ 5 2VZDOG : )HLWNQHFKW DQG 0 -:DPSHWLFK 1DWXUH /RQGRQ