High Pressure Steam Reactivation of Calcium Oxide (CaO) Sorbents

+LJK3UHVVXUH6WHDP5HDFWLYDWLRQRI&DOFLXP2[LGH&D2
6RUEHQWV)RU&DUERQ'LR[LGH&2&DSWXUH8VLQJ&DOFLXP
/RRSLQJ3URFHVV
7+(6,6
3UHVHQWHGLQ3DUWLDO)XOILOOPHQWRIWKH5HTXLUHPHQWVIRUWKH'HJUHH0DVWHURI6FLHQFHLQ
WKH*UDGXDWH6FKRRORI7KH2KLR6WDWH8QLYHUVLW\
%\
$PRRO\D'DWWDWUD\D/DOVDUH
*UDGXDWH3URJUDPLQ&KHPLFDO(QJLQHHULQJ
7KH2KLR6WDWH8QLYHUVLW\
0DVWHU
V([DPLQDWLRQ&RPPLWWHH
3URIHVVRU/LDQJ6KLK)DQ$GYLVRU
3URIHVVRU$QGUH3DOPHU
&RS\ULJKWHGE\
$PRRO\D'DWWDWUD\D/DOVDUH
$EVWUDFW
&DOFLXPORRSLQJLVDVRUEHQWEDVHGFKHPLFDOORRSLQJSURFHVVWKDWXVHVFDOFLXPR[LGHRU
VLPLODU FDOFLXP VRUEHQW SUHFXUVRUV IRU SUHSRVWFRPEXVWLRQ FDUERQ GLR[LGH FDSWXUH
([WHQVLYHVWXG\RIWKLVSURFHVVDWWKH2KLR6WDWH8QLYHUVLW\KDVOHGWRWKHGHYHORSPHQWRI
WZR YDULDQWV RI WKLV SURFHVV &DUERQDWLRQFDOFLQDWLRQ UHDFWLRQ &&5 SURFHVV IRU SRVW
FRPEXVWLRQ FDUERQ FDSWXUH LQHOHFWULFLW\JHQHUDWLRQDQGFDOFLXPORRSLQJSURFHVV&/3
IRU SUHFRPEXVWLRQ FDUERQ FDSWXUH LQ K\GURJHQ SURGXFWLRQ DQG HOHFWULFLW\ JHQHUDWLRQ
&&5 LV D F\FOLF SRVWFRPEXVWLRQ FDUERQ FDSWXUH SURFHVV GHPRQVWUDWHG DW D .:WK
VFDOHDW2687KLVGHPRQVWUDWLRQDFKLHYHGPRUHWKDQFDUERQGLR[LGHUHPRYDODQG
RYHUVXOIXUGLR[LGH62UHPRYDO,WKDVEHHQVKRZQWKURXJKSURFHVVVLPXODWLRQV
WKDW &&5 SURFHVV LQGXFHV OHVV HQHUJ\ SHQDOW\ WKDQ WKH FRQYHQWLRQDO DPLQHR[\
FRPEXVWLRQ EDVHG FDUERQ GLR[LGH FDSWXUH WHFKQRORJLHV 7KLV SURFHVV LQYROYHV
FDUERQDWLRQFDOFLQDWLRQVWHDP K\GUDWLRQ RI FDOFLXP VRUEHQWV 6WHDP K\GUDWLRQ LV D
UHDFWLYDWLRQ VWHS ZKLFK PLWLJDWHV WKH HIIHFW RI VLQWHULQJ RI VRUEHQWV GXULQJ FDOFLQDWLRQ
UHJHQHUDWHVWKHVRUEHQWVXUIDFHDQGUHWDLQVFDUERQFDSWXUHFDSDFLW\RYHUDODUJHQXPEHU
RIF\FOHV+LJKSUHVVXUHVWHDPUHDFWLYDWLRQRIFDOFLXPVRUEHQWVZDVLQYHVWLJDWHGDQGWKH
GHSHQGHQFHRIK\GUDWLRQUDWHRQVWHDPSUHVVXUHLVREWDLQHG+LJKHUVWHDPSDUWLDOSUHVVXUH
DOORZV IRU KLJKHU WHPSHUDWXUHV R& WR JHW KLJKHU K\GUDWLRQ FRQYHUVLRQV 7KH
LL
UHDFWLRQEHLQJKLJKO\H[RWKHUPLFN-PROKLJKWHPSHUDWXUHJLYHVKLJKTXDOLW\KHDW
ZKLFKFDQEHXVHGHOVHZKHUHLQWKHSURFHVV5HDFWLRQNLQHWLFVRIVWHDPK\GUDWLRQIRUIRXU
GLIIHUHQW OLPHVWRQH EDVHG VRUEHQWV ZDV VWXGLHG XVLQJ KLJK SUHVVXUH WKHUPRJUDYLPHWULF
DQDO\VLV(OHYDWHGSUHVVXUHVDWPDQGKLJKWHPSHUDWXUHR&ZHUHXVHGLQ
WKLV VWXG\ 6WHDP K\GUDWLRQ RI 3* *UD\PRQW OLPHVWRQH VRUEHQW H[SHULPHQWDOO\ VKRZHG
VHFRQGRUGHUZLWKUHVSHFWWRVWHDPSUHVVXUHGULYLQJIRUFH3+2±3+25DWHFRQVWDQWV
IRUHDFKRSHUDWLQJFRQGLWLRQVZHUHFDOFXODWHGDQGDFWLYDWLRQHQHUJ\RIWKHUHDFWLRQZDV
FRPSXWHGIURPWKHVHFDOFXODWLRQV7KHDFWLYDWLRQHQHUJ\REWDLQHGIURPWKLVVWXG\LV
.-PRO 1LWURJHQ SK\VLVRUSWLRQ VWXGLHV ZHUH SHUIRUPHG IRU FKDUDFWHUL]DWLRQ RI WKH
VRUEHQWVDQGWKHLUUHDFWLYLW\ZDVFRPSDUHGYLDWKHVWHDPK\GUDWLRQVWXGLHVLQWKH7*$DW
R&DQG3+2DWP&D2VRUEHQWGHULYHGDIWHUK\GUDWLRQVKRZVWKHKLJKHVWVXUIDFH
DUHD DQG SRUH YROXPH ZKLFK LV PRUH WKDQ WLPHV WKDW RI WKH VRUEHQW GHULYHG E\
FDOFLQDWLRQRI &D&2 7KLV VWXG\LVDVWURQJLQGLFDWLRQWKDWK\GUDWLRQZLWKZDWHUVWHDP
UHJHQHUDWHV WKH VRUEHQW PRUSKRORJ\ LQ SURFHVV UHDFWLYDWLQJ WKH VRUEHQWV ZLWK KLJK
SRURVLW\,WLVEHOLHYHGKRZHYHUWKDWLQLWLDOSDUWLFOHVL]HKDV OLWWOH RU QR EHDULQJ RQWKH
UHDFWLYDWLRQSURFHVVRUVRUEHQWUHDFWLYLW\LQWKHPXOWLF\FOLFVWXGLHVDVK\GUDWLRQFDXVHV
SDUWLFOHEUHDNDJH
7KLV VWXG\ LV VLJQLILFDQW LQ UHJDUG WR WKH SRVWFRPEXVWLRQ DQG SUHFRPEXVWLRQ FDUERQ
FDSWXUHFDOFLXPORRSLQJSURFHVVHVGHYHORSHGDW268DVWKHK\GUDWLRQWHPSHUDWXUHZRXOG
EH FRPSDUDEOH WR WKH FDUERQDWRU WHPSHUDWXUH DV LW LV H[SHFWHG WR PDNH WKH SURFHVVHV
LLL
HFRQRPLFDOO\YLDEOH7KHUHH[LVWVDWUDGHRIIKRZHYHUIRUWKHVWHDPSUHVVXUHWREHXVHG
IRU K\GUDWLRQ9HU\KLJKVWHDPSUHVVXUHZRXOGLQFXUKLJKFRPSUHVVLRQ FRVWV DQG DIIHFW
WKH HQHUJ\ SHQDOW\ RI WKH SURFHVV 7KLV FRXOG GHWHU WKH FRPSHQVDWLQJ HIIHFW RI KHDW
UHFRYHUHG IURP WKH K\GUDWRU DQG LQ WXUQ PDNH WKH SURFHVV PRUH HQHUJ\ LQWHQVLYH 7KLV
VWXG\LVOLPLWVWKHSUHVVXUHWRWLPHVWKHDWPRVSKHULFSUHVVXUHDQGVWLOOREWDLQKLJKHU
FRQYHUVLRQV
LY
This document is dedicated to my guru and to my parents for their incredible support
and encouragement.
Y
$FNQRZOHGJPHQWV
,ZRXOGOLNHWRH[SUHVVP\GHHSHVWJUDWLWXGHWRZDUGVP\DGYLVRU3URIHVVRU/LDQJ6KLK
)DQIRURIIHULQJPHWRZRUNRQWKLVH[FLWLQJUHVHDUFKLQWKHFOHDQHQHUJ\FRQYHUVLRQDQG
SDUWLFOH WHFKQRORJ\ ODERUDWRU\ DW WKH 2KLR 6WDWH 8QLYHUVLW\ , DP WKDQNIXO WR WKH 2KLR
6WDWH 8QLYHUVLW\ DQG SDUWLFXODUO\ WKH :LOOLDP * /RZULH 'HSDUWPHQW RI &KHPLFDO DQG
%LRPROHFXODU(QJLQHHULQJIRUWKHVWDWHRIWKHDUWUHVRXUFHVDQGLQIUDVWUXFWXUHRQO\PDGH
EHWWHUE\WKHQHZ&%(&IDFLOLW\WKDWPDGHP\UHVHDUFKH[SHULHQFHWUXO\HQMR\DEOH7KH
DOOQHZODERUDWRULHVDQGUHVHDUFKIDFLOLWLHVDW268KDVEURXJKWLQDOOWKHSRVLWLYHHQHUJ\
DQGVWUHVVUHOLHYLQJHQYLURQPHQWZKLFKKHOSVQXUWXUHWKHFUHDWLYLW\LQRQHRIWKHEULJKWHVW
PLQGV ZRUNLQJ KHUH 7KH HQWLUH &%( IDPLO\ DQG HVSHFLDOO\ WKH )DQ JURXS KDV DOZD\V
EHHQ KHOSIXO DQG UHVRXUFHIXO HQFRXUDJLQJ SHUVRQDO GHYHORSPHQW WR WDNH RQ QHZ
FKDOOHQJHV DQG UHVSRQVLELOLWLHV IURP GD\ RQH , DP JUDWHIXO WR 3URI $VWKDJLUL IRU KLV
VXSSRUWDQGJXLGDQFHWKURXJKWKHLQLWLDOVWDJHVRIP\GHJUHH
'U )DQ LV D WUXH VRXUFH RI LQVSLUDWLRQ IRU PH DV , VHH KLP ZRUNLQJ ZLWK WLUHOHVV
GHGLFDWLRQ GLVFLSOLQH DQG SHUVHYHUDQFH WKDW IXHOV HIIRUWV RI WKH HQWLUH JURXS WR WXUQ
DPD]LQJDQGXQLTXHLGHDVLQWRUHDOLW\+LVFRQVWDQWGHVLUHDQGRSWLPLVPWRZDUGVFOHDQHU
WHFKQRORJLHVDQGHQHUJ\FRQYHUVLRQSURFHVVHVLQVSLUHVPHDQGUDLVHVP\KRSHVRIDEHWWHU
HQYLURQPHQWIRUWKHIXWXUH
YL
,DPWKDQNIXOWR'U$QGUHZ7RQJIRUKLVJXLGDQFHDQGVXSSRUWWRSUHVHQWP\LGHDVDQG
UHVHDUFK WR SURSRVH QHZ SURMHFWV UHYLHZ P\ SURJUHVV DQG VXJJHVW WKH FRUUHFWLYH
PHDVXUHV DW HYHU\ VWDJH RI P\ UHVHDUFK 'U 1LUDQMDQL 'HVKSDQGH DQG :LOOLDP :DQJ
ZKRFRQWULEXWHGLPPHQVHO\WRWKHFDOFLXPVRUEHQWEDVHGORRSLQJSURFHVVHVDW268KDYH
EHHQRIJUHDWKHOSWRPH0\ZHHNO\PHHWLQJVZLWKWKHPJDYHPHYDOXDEOHLQVLJKWVLQWKH
GHVLJQ RI H[SHULPHQWV JHWWLQJ XVHG WR WKH VHQVLWLYH LQVWUXPHQWV OLNH WKH KLJKSUHVVXUH
7*$ GDWD DQDO\VLV SUHVHQWDWLRQ RI P\ UHVHDUFK ODUJHU SHUVSHFWLYH RI P\ SDUWLFXODU
UHVHDUFK WRSLF HWF 'U 1LUDQMDQL 'HVKSDQGH PHQWRUHG PH LQ WKH LQLWLDO VWDJHV RI P\
UHVHDUFK 'U 0DQGDU .DWKH 6RXUDEK 1DGJRXGD $QNLWD 0DMXPGDU <DVZDQWK
3RWWLPXUWK\ 3UDWHHN .XPDU 'HYHQ %DVHU <X<HQ &KHQ DUH VRPHRI WKH PDQ\ JURXS
PHPEHUVZKRP,KDYHWUXO\HQMR\HGZRUNLQJZLWKVHHNLQJDQGSURYLGLQJKHOSVKDULQJ
RIILFHVSDFHVDQGDQLPSHFFDEOHZRUNFXOWXUH
, DP GHHSO\ JUDWHIXO WR 'U 5REHUW 6WDWQLFN &OHDU6NLHV &RQVXOWLQJ IRU KLV LPPHQVH
VXSSRUW DQG LQVLJKWV WKURXJKRXW WKLV SURMHFW WKURXJK QXPHURXV SHUVRQDO GLVFXVVLRQV
FRQIHUHQFHFDOOVDQGFROODERUDWLYHHIIRUWV,DPDOVRWKDQNIXOIRUWKHFRQWULEXWLRQVRI0U
%RE%URZQLQWKHDGYLVRU\FDSDFLW\IRUWKHGHYHORSPHQWRIFDOFLXPVWXGLHVIXQGHGE\WKH
2KLR&RDO'HYHORSPHQW2IILFH2&'2
6SHFLDO WKDQNV WR 0LNH :LOVRQ DQG 7LPRWK\ +HQWKRUQH IRU WKHLU YDOXDEOH DQG WLPHO\
VXSSRUW DQG H[FHOOHQW VNLOOV LQ PDFKLQLQJ JODVV EORZLQJ DQG PDLQWHQDQFH RI ODE
HTXLSPHQW 7KDQNV WR $QJHOD %HQQHWW 6XVDQ 7HVIDL DQG /\QQ )ODQQDJDQ IRU DOZD\V
YLL
ORRNLQJRXWIRUXVZLWKWKHLUWLPHO\UHPLQGHUHPDLOVFULWLFDOEXWLPSRUWDQWJXLGHOLQHVIRU
WKHDGPLQLVWUDWLRQZRUNLQRUGHULQJFKHPLFDOVODEHTXLSPHQWHWF
0\ SDUHQWV 'U 'DWWDWUD\D /DOVDUH DQG /HHQD /DOVDUH KDYH EHHQ DPD]LQJO\ VXSSRUWLYH
DQG HQFRXUDJLQJ WKURXJKRXW P\ MRXUQH\ KHUH DW 268 7KHLU ORYH DQG VXSSRUW LV
XQGHWHUUHGE\GLVWDQFHRUDJH7KH\ZRXOGPDNHVXUHRIDOOWKHFRPIRUWLQZKDWHYHUSDWK
,KDYHFKRVHQRUPD\FKRVH,DFWXDOO\DVSLUHWREHDVJRRGDQLQGLYLGXDODQGDKXPDQ
EHLQJ DV WKH\ DUH , DP JUDWHIXO P\ H[WHQGHG IDPLO\ IRU DOO WKHLU ZHOO ZLVKHV DQG
JRRGZLOO 0\ EURWKHU $WKDUYD KDV DOZD\V EHHQ WKHUH IRU PH ZLWK KLV ZLW WKDW ZRXOG
PDNHPHIHHOFORVHUWRKRPH
, DP IRUHYHU LQGHEWHG WR $QXMD 0RUDQNDU 'HHNVKD -DLQ *DXUL 1DEDU 1DFKLNHW
3DUDQMDSH DQG .VKLWLM &KLWWDU IRU WKHLU URFN VROLG VXSSRUW DQG IRU WKH LQYDOXDEOH
IULHQGVKLS RI 6RXUDEK 1DGJRXGD $EKLODVKD 'HKDQNDU 'HYHQ %DVHU DQG 6DXUDEK
$LODZDU7KH\KDYHDOZD\VEHHQWKHUHIRUPHLQP\KDSSLHVWPRPHQWVDQGWRXJKHUWLPHV
YLLL
9LWD
$SULO66&0RGHUQ+LJK6FKRRO3XQH
0D\+6&8QLYHUVLW\RI3XQH
-XO\WR-XQH%7HFK8QLYHUVLW\RI3XQH9LVKZDNDUPD
,QVWLWXWHRI7HFKQRORJ\3XQH
WRSUHVHQW*UDGXDWH5HVHDUFK$VVRFLDWH'HSDUWPHQW
RI&KHPLFDODQG%LRPROHFXODU7HFKQRORJ\
7KH2KLR6WDWH8QLYHUVLW\
)LHOGVRI6WXG\
0DMRU)LHOG&KHPLFDO(QJLQHHULQJ
L[
7DEOHRI&RQWHQWV
$EVWUDFWLL
$FNQRZOHGJPHQWVYL
9LWDL[
)LHOGVRI6WXG\L[
7DEOHRI&RQWHQWV[
/LVWRI7DEOHV[LL
/LVWRI)LJXUHV[LLL
&KDSWHU,QWURGXFWLRQ
/LPLWDWLRQVRIWKHWZRVWDJHFDOFLXPORRSLQJSURFHVV
6RUEHQW5HDFWLYDWLRQ7HFKQLTXHV
6\QWKHVLVRIFDOFLXPEDVHGVRUEHQWVIURPSUHFXUVRUV
'RSHGRUVXSSRUWHGFDOFLXPR[LGHV
6WHDPZDWHUK\GUDWLRQ
&KDSWHU0DWHULDOVDQG([SHULPHQWDO6HWXS
[
0DWHULDOVDQGVRUEHQW3UHSDUDWLRQ
([SHULPHQWDO6HWXSDQGSURFHGXUH
&DOFLQDWLRQ
1LWURJHQSK\VLVRUSWLRQVWXGLHV
7KHUPRJUDYLPHWULF$QDO\VLV7*$VWXGLHVIRUKLJKSUHVVXUHVWHDP
K\GUDWLRQ
)L[HGEHGVWXGLHVIRUVWHDPK\GUDWLRQDQGFDOFLQDWLRQ
&KDSWHU5HVXOWVDQG'LVFXVVLRQ
5HDFWLRQNLQHWLFVVWXGLHVLQWKH7*$
(IIHFWRIWHPSHUDWXUH
(IIHFWRIVWHDPSDUWLDOSUHVVXUHRQUHDFWLRQUDWH
.LQHWLFVRIVWHDPK\GUDWLRQ
6RUEHQWFKDUDFWHUL]DWLRQDQGUHDFWLYLW\VWXGLHV
(IIHFWRIXSVWUHDPFDOFLQDWLRQFRQGLWLRQVRQVRUEHQWUHDFWLYLW\
&KDSWHU&RQFOXVLRQV
&KDSWHU)XWXUH:RUN
&KDSWHU5HIHUHQFHV
[L
/LVWRI7DEOHV
7DEOH&RPSRVLWLRQRIOLPHVWRQHVRUEHQWVDQGH[WHQWRIZDWHUK\GUDWLRQ
7DEOH'HVLJQRIH[SHULPHQWVIRUSDUDPHWULFVWHDPK\GUDWLRQVWXGLHV
7DEOH5DWHFRQVWDQWIRUDOOWHPSHUDWXUHVDQGVWHDPSUHVVXUHV
7DEOH)L[HGEHGFDOFLQDWLRQFRQGLWLRQV
[LL
/LVWRI)LJXUHV
)LJXUH8QLWHG6WDWHV(OHFWULFLW\3URGXFWLRQE\)XHO6RXUFH
)LJXUH&DUERQGLR[LGH&2FDSDFLW\ZUWWLPHLQPXOWLF\FOLF&&5SURFHVV
)LJXUH&DUERQGLR[LGH&2FDSDFLW\IRUWKUHHVWHS&&5SURFHVVLQYROYLQJVWHDP
K\GUDWLRQUHDFWLYDWLRQ
)LJXUH6FKHPDWLFRISRVWFRPEXVWLRQFDUERQFDSWXUH&&5SURFHVV
)LJXUH6FKHPDWLFRISUHFRPEXVWLRQFDUERQFDSWXUH&/3SURFHVV
)LJXUH5XERWKHUP0DJQHWLF6XVSHQVLRQ%DODQFH06%
)LJXUH7*$VHWXSLQWKHODERUDWRU\
)LJXUH)L[HGEHGUHDFWRUVHWXSIRUSUHVVXUL]HGVWHDPK\GUDWLRQRIVRUEHQWV
)LJXUH(TXLOLEULXPFXUYHRIVWHDPSDUWLDOSUHVVXUHDQGUHDFWLRQWHPSHUDWXUH
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWPDQGUHDFWLRQ
WHPSHUDWXUHR&
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWPDQGUHDFWLRQ
WHPSHUDWXUHR&
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWPDQGUHDFWLRQ
WHPSHUDWXUHR&
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DQGDWPDQG
UHDFWLRQWHPSHUDWXUHR&
[LLL
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWPDQG
UHDFWLRQWHPSHUDWXUHR&
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWP
DQGUHDFWLRQWHPSHUDWXUHR&
)LJXUH5DWHRIVWHDPK\GUDWLRQRI3*VRUEHQWVZUWVWHDPSUHVVXUH
)LJXUH$UUKHQLXVSORWIRUUDWHFRQVWDQWIRUVWHDPK\GUDWLRQUHDFWLRQ
)LJXUH6XUIDFHDUHDXVLQJ%(7PHWKRGIRUQLWURJHQSK\VLVRUSWLRQVWXGLHVRI3*)/
$$DQG($VRUEHQWV
)LJXUH3RUHYROXPHRI3*)/$$DQG($VRUEHQWVXVLQJ%-+SRUHVL]H
GLVWULEXWLRQVWXGLHV
)LJXUH6RUEHQWUHDFWLYLW\VWXGLHVIRU3*)/$$DQG($DWR&DQG3+2DWP
)LJXUH1LWURJHQSK\VLVRUSWLRQVWXGLHVIRU3*VRUEHQWFDOFLQHGDWDQG
R&LQWKHIL[HGEHGUHDFWRU
[LY
&KDSWHU,QWURGXFWLRQ
$QWKURSRORJLFDO DFWLYLWLHV VLQFH WKH DGYHQW RI LQGXVWULDO UHYROXWLRQ KDYH FDXVHG DQ
XQSUHFHGHQWHGLQFUHDVHLQFDUERQGLR[LGHFRQFHQWUDWLRQLQDLUIURPSSPEHIRUHWKH
DUULYDORIWKHLQGXVWULDOUHYROXWLRQWRWKHFXUUHQWOHYHORISSP7KLVLVWKHUHVXOWRI
XQDEDWHGDQGWRDFHUWDLQH[WHQWSURIOLJDWHFRQVXPSWLRQRIDYDLODEOHIRVVLOIXHOVOLNHFRDO
RLO DQG QDWXUDO JDV (OHFWULFLW\ JHQHUDWLRQ XVLQJ FRDO KDV KHOSHG OLJKW XS HYHQ WKH
UHPRWHVW DUHDV RI WKH JOREH DW D IUXJDO FRVW EXW LW FRQWLQXHV WR EH DQ DFXWH VRXUFH RI
FDUERQGLR[LGHHPLVVLRQV,QWKH8QLWHG6WDWHVFRDOFRPEXVWLRQFRQWULEXWHVQHDUO\DWKLUG
RIWKHWRWDOFDUERQGLR[LGHHPLVVLRQVZKLOHSURYLGLQJKDOIRIWRWDOHOHFWULFLW\JHQHUDWHG
:RUOGZLGH RI WKH WRWDO &2 HPLVVLRQV FRPH IURP WKH EXUQLQJ RI FRDO ZKLOH LW
DFFRXQWVIRUMXVWRIWKHWRWDOSRZHUJHQHUDWHG:KLOHQDWXUDOJDVFDQUHSODFHFRDO
IRU ILULQJ WKH SRZHU SODQWV FRDO FRQWLQXHV WR EH DQ HFRQRPLFDO IXHO IRU HOHFWULFLW\
JHQHUDWLRQ7KHUHLVDFRQFHUWHGHIIRUWZRUOGZLGHWRGHYHORSHIIHFWLYHDQGHIILFLHQW&2
FDSWXUH V\VWHPV ZKLFK FRQFHQWUDWH WKH GLOXWH &2 LQ IOXH JDV IRU VWRUDJH WKURXJK
VHTXHVWUDWLRQ
8QLWHG6WDWHV(OHFWULFLW\*HQHUDWLRQE\)XHO7\SH
7ULOOLRQ.:KRXU
)LJXUH8QLWHG6WDWHV(OHFWULFLW\3URGXFWLRQE\)XHO6RXUFH
)LJXUH VKRZV WKH HVWLPDWHG FRQWULEXWLRQ RI FXUUHQWO\ XVHG IXHOV IRU HOHFWULFLW\
SURGXFWLRQLQWKH8QLWHG6WDWHV$FFRUGLQJWRWKHVHSURMHFWLRQVQDWXUDOJDVDQGFRDOZLOO
EH WKH SULPDU\ VRXUFHV RI IXHO IRU HOHFWULFLW\ JHQHUDWLRQ LQ 0RUH WKDQ KDOI RI WKH
HOHFWULFLW\SURGXFHGLQWKH8QLWHG6WDWHVLQLVHVWLPDWHGWRFRPHIURPIRVVLOIXHOV
$OWKRXJKWKHFRQWULEXWLRQRIQDWXUDOJDVWRZDUGVHOHFWULFLW\SURGXFWLRQZLOOEHPRUHWKDQ
WKDWRIFRDOFOHDQFRDOFRQYHUVLRQLVHTXDOO\QHFHVVDU\IRUFKHDSHUDQGUHOLDEOHVXSSO\RI
HOHFWULFLW\ 0RUHRYHU YDULDWLRQ LQ QDWXUDO JDV SULFHV LV VLJQLILFDQW DV FRPSDUHG WR WKH
SULFHVRIIXHO7KXVDSURFHVVGHVLJQHGIRUFDUERQFDSWXUHIURPFRDOILUHGSRZHUSODQWV
ZRXOGEHHFRQRPLFDOO\UHDOLVWLF7KRXJKWKHFXUUHQWSULFHVRIQDWXUDOJDVPP%78
DUHOXFUDWLYHWKHYDULDWLRQLQSULFHVRYHUWKHODVW\HDUVKDVEHHQKLJKDQGWKHSULFHVKDG
VRDUHGXSWRPP%78DWWKHVWDUWRIZKLOHFRDOSULFHVKDYHUHPDLQHGVWDEOHDW
DURXQG PP%78 IRU WKH ODVW \HDUV ZLWK WKH FXUUHQW SULFH EHLQJ PP%78
&RDO PLQLQJ LV VWLOO D PDMRU ERRVW IRU WKH ORFDO HFRQRP\ LQ WKH 8QLWHG 6WDWHV DQG
JHQHUDWHVDODUJHQXPEHURIMREVDFURVVWKH8QLWHG6WDWHV$Q\UHGXFWLRQLQWKHXVDJHRI
FRDODGYHUVHO\DIIHFWVWKHFRDOPLQHUVDQGWKHSHRSOHGHSHQGHQWRQWKHFRDOSURGXFWLRQ
SURFHVVLQJDQG GLVWULEXWLRQ FKDLQ7KLV LV RQHRI WKH UHDVRQV WKDW FRDOPLQLQJ DQG FRDO
XWLOL]DWLRQDUHODUJHO\VXSSRUWHGE\WKHIHGHUDODQGVWDWHJRYHUQPHQWDODJHQFLHVOLNHWKH
'HSDUWPHQWRI(QHUJ\'2(DQG2KLR&RDO5HVHDUFK&RQVRUWLXP2&5&7KHLUVWURQJ
ILQDQFLDOVXSSRUWDQGLQLWLDWLYHIRUFOHDQFRDOUHVHDUFKKDYHOHGWRWKHGHYHORSPHQWDQG
VXFFHVVIXO GHPRQVWUDWLRQ RI WKH SRVWFRPEXVWLRQ &DUERQDWLRQ &DOFLQDWLRQ 5HDFWLRQ
&&5SURFHVVIRUFDUERQFDSWXUHDW2KLR6WDWH8QLYHUVLW\
7KH 86 (QYLURQPHQWDO 3URWHFWLRQ $JHQF\ (3$ KDV UHFHQWO\ VHW QHZ UHJXODWLRQV IRU
FDUERQGLR[LGHHPLVVLRQVIURPQHZDQGH[LVWLQJSRZHUSODQWVILUHGZLWKFRDORUQDWXUDO
JDV 7KHVH UXOHV PDQGDWH D PLQLPXP RI ZW &2 FDSWXUH IURP WKH H[LVWLQJ SRZHU
SODQWVDQGE\ZW&2FDSWXUHIURPQHZQDWXUDOJDVRUFRDOILUHGSRZHUSODQWV
&2 HPLVVLRQ OLPLW KDV EHHQ VHW DW SRXQGV SHU 0:KRXU RI JURVV HOHFWULFLW\
JHQHUDWHG LQ WKH H[LVWLQJ FRDO SRZHU SODQWV DQG SRXQGV SHU 0:KRXU RI JURVV
HOHFWULFLW\JHQHUDWHGIURPQDWXUDOJDVILUHGSRZHUSODQWV:LWKWKHFXUUHQWDPLQHEDVHG
FDUERQ FDSWXUH WHFKQRORJLHV IRU H[LVWLQJ SRZHU SODQWV WKH /HYHOL]HG FRVW RI HOHFWULFLW\
/&2(LQFUHDVHVE\PRUHWKDQWKDQWKDWIRUWKHVXEFULWLFDOSXOYHUL]HGFRDOERLOHU
ZLWKRXW FDUERQ FDSWXUH 3UHOLPLQDU\ WHFKQRHFRQRPLF DQDO\VLV RI WKH WKUHH VWHS
FDUERQDWLRQFDOFLQDWLRQ UHDFWLRQ &&5 SURFHVV GHYHORSHG DW 2KLR 6WDWH 8QLYHUVLW\
LQGLFDWHVDLQFUHDVHLQWKH/&2(DVFRPSDUHGWRWKHEDVHFDVHVXEFULWLFDO3&ERLOHU
ZLWKQR&2FDSWXUH7KXVWKHFDOFLXPORRSLQJSURFHVVKDVDJUHDWSRWHQWLDODVDSRVW
FRPEXVWLRQFDUERQDQGVXOIXUFDSWXUHWHFKQRORJ\ZLWKUHODWLYHHDVHRILQWHJUDWLRQLQWKH
SURFHVV ([WHQVLYH UHVHDUFK LQ WKH FDOFLXP ORRSLQJ SURFHVV IRU SUHSRVWFRPEXVWLRQ
FDUERQFDSWXUHKDVVKRZQWKDWFDOFLXPEDVHGVRUEHQWVHVSHFLDOO\OLPHVWRQHDUHVXLWDEOH
IRU KLJKWHPSHUDWXUH FDUERQ GLR[LGH FDSWXUH LQ ERWK SUHSRVWFRPEXVWLRQ
FRQILJXUDWLRQV &DOFLXP EDVHG VRUEHQWV DUH DOVR HIIHFWLYH LQ FRPSOHWHO\
FDSWXULQJVXOIXUGLR[LGHDVZHOODVDFLGJDVVHVOLNHK\GURFKORULFDFLG+&OIURPIOXHJDV
VWUHDPV LQ SUHFRPEXVWLRQ FRQILJXUDWLRQ $ORQJ ZLWK ODEVFDOH H[SHULPHQWV XVLQJ
WKHUPRJUDYLPHWULF DQDO\]HU 7*$ DQG IL[HG EHG UHDFWRU V\VWHPV FDOFLXP ORRSLQJ
SURFHVV KDV EHHQ GHPRQVWUDWHG DW 268 RQ D VXESLORW .:WK VFDOH ,Q WKH SRVW
FRPEXVWLRQ &&5 SURFHVV FRQILJXUDWLRQ 7KLV SRVWFRPEXVWLRQ &2 GHPRQVWUDWLRQ
XVLQJ FRDOQDWXUDO JDV FRILUHG VWRNHU ZKLFK SURGXFHG FRDOERLOHU W\SH IOXH JDV
FRPSRVLWLRQZDVVXFFHVVIXOO\GHPRQVWUDWHG9DULRXVDVSHFWVRIWKHSURFHVVOLNHVRUEHQW
UHDFWLYLW\ SURFHVV LQWHJUDWLRQ DQG SURFHVV HFRQRPLFV ZHUH H[WHQVLYHO\ UHVHDUFKHG
3URPLVLQJ RXWFRPHV RI WKLV GHPRQVWUDWLRQ DQG UHVHDUFK HOVHZKHUH OHG WR 0:WK
GHPRQVWUDWLRQVRIWKLVWHFKQRORJ\
/LPLWDWLRQVRIWKHWZRVWDJHFDOFLXPORRSLQJSURFHVV
&DOFLXPORRSLQJSURFHVVIRUFDUERQGLR[LGHFDSWXUHLQSUHSRVWFRPEXVWLRQFRQILJXUDWLRQ
KDVEHHQH[WHQVLYHO\UHVHDUFKHGDVWZRVWHSSURFHVV±FDUERQDWLRQDQGFDOFLQDWLRQZKLFK
XVHV D VLQJOH UHYHUVLEOH UHDFWLRQ RI FDOFLXP R[LGH &D2 ZLWK FDUERQ GLR[LGH &2 WR
IRUPFDOFLXPFDUERQDWH&D&2DWWHPSHUDWXUHVUDQJLQJIURPR&DQGWKHVDPH
&D&2LVFDOFLQHGEDFNWR&D28VLQJWKLVLGHDDQXPEHURISURFHVVHVZHUHGHYHORSHG
ZRUOGZLGH DQG PRVW RI WKHP ZHUH VXFFHVVIXOO\ GHPRQVWUDWHG XS WR SLORW VFDOH IRU
H[DPSOH WKH 2KLR 6WDWH 8QLYHUVLW\ 268 &DOFLXP /RRSLQJ 3URFHVV &/3 IRU KLJK
SXULW\ K\GURJHQ DQG HOHFWULFLW\ SURGXFWLRQ IURP V\QJDV WKH +\GURJHQ 3URGXFWLRQ E\
5HDFWLRQ ,QWHJUDWHG 1RYHO *DVLILFDWLRQ +\3U5,1* SURFHVV $/6720¶V +\EULG
&RPEXVWLRQ*DVLILFDWLRQ 3URFHVV WKH *()XHO )OH[LEOH 3URFHVV DQG &2 DFFHSWRU
SURFHVV$ PDMRU FKDOOHQJH ZLWK WKHVFDOHXS RI WKH WZRVWHS SURFHVV LVWR PDLQWDLQ
WKHVRUEHQWUHDFWLYLW\DQGUHF\FODELOLW\)RUH[DPSOHWKHUHVXOWVRIDWHVWFRQGXFWHGRQD
VRUEHQW REWDLQHG IURP WKH 3OHDVDQW *DS TXDUU\ IURP *UD\PRQW VKRZV WKDW WKH &2
FDSWXUHFDSDFLW\JRHVGRZQGUDVWLFDOO\RYHUPXOWLSOHF\FOHVDVVHHQLQ)LJXUH&2
FDSWXUHFDSDFLW\LVJLYHQE\WKHVLPSOHHTXDWLRQ
ሺ–ǦͲሻ
:HLJKW&DSWXUH Ͳ
î
:KHUH:W LVWKHZHLJKWDIWHUFDUERQDWLRQ:LVWKHLQLWLDOZHLJKWEHIRUHEHLQJVXEMHFWHG
WRFDUERQDWLRQ7KXVWKHWKHRUHWLFDOPD[LPXPRIWKHFDSWXUHFDSDFLW\LVE\ZW
7KH GHFUHDVH RI &2 FDSDFLW\ RI WKH VRUEHQW DIWHU PXOWLSOH F\FOHV KDV EHHQ ZLGHO\
UHSRUWHG +LJK FDOFLQDWLRQ WHPSHUDWXUH RI WKH RUGHU RI R& OHDGV WR D
GHWULPHQWDOHIIHFWRQWKHVRUEHQWPRUSKRORJ\ZKLFKDGYHUVHO\DIIHFWVWKHUHDFWLYLW\RIWKH
VRUEHQW7KLVHIIHFWLVFDOOHGµVLQWHULQJ¶/RVVRIUHDFWLYLW\GXHWRVLQWHULQJRFFXUV
DIWHU D IHZ F\FOHV RI FDUERQDWLRQ DQG FDOFLQDWLRQ DV WKH VRUEHQW VXUIDFH WXUQV VPRRWK
SRUHVIXVHWRJHWKHUWKXVKLQGHULQJWKHGLIIXVLRQRI&2 LQZDUG6LQWHULQJLVDFRPELQHG
HIIHFW RI PXOWLSOH IDFWRUV OLNH FDOFLQDWLRQ WHPSHUDWXUH WKH GHVLJQ RI WKH FDOFLQHU WKH
UHVLGHQFHWLPHLQWKHFDOFLQHUKHDWWUDQVIHULQWKHUHDFWRUHWF5RWDU\GUXPUHDFWRULVKDV
EHHQGHWHUPLQHGWREHRQHRIWKHEHVWFDOFLQHUUHDFWRUVUHJDUGLQJPLQLPL]LQJWKHVLQWHULQJ
HIIHFW RQ WKH VRUEHQWV 2WKHU W\SHV RI FDOFLQHU DUH D IL[HG EHG FDOFLQHU RU D NLOQ
FRPPHUFLDOO\XVHGIRUWKHSURGXFWLRQRITXLFNOLPH+RZHYHUWKLVGHVLJQLVQRWSUHIHUUHG
LQ WKH WZRVWHS FDUERQ GLR[LGH FDSWXUH SURFHVV GXH WR KLJKHU OHYHOV RI VLQWHULQJ RI WKH
VRUEHQWV
7R LPSURYH WKH UHDFWLYLW\ RI WKH VRUEHQWV VHYHUDO PHWKRGV KDYH EHHQ SURSRVHG DQG
H[SHULPHQWHG LQ WKH SDVW DPRQJ ZKLFK VWHDP K\GUDWLRQ LV WKH PRVW YLDEOH DQG FRVW
HIIHFWLYH DOWHUQDWLYH 6\QWKHVLVPRGLILFDWLRQ RI WKH VRUEHQWV GRSHG DQG VXSSRUWHG
VRUEHQWVUHDFWLYDWLRQWKURXJKVWHDPZDWHUK\GUDWLRQDUHVRPHRIWKHWHFKQLTXHVWKDWKDYH
EHHQDWWHPSWHGIRUUHDFWLYDWLRQRIWKHVRUEHQWVDVVHHQLQ)LJXUHDQG)LJXUH
)LJXUH&DUERQGLR[LGH&2FDSDFLW\ZUWWLPHLQPXOWLF\FOLF&&5SURFHVV
)LJXUH&DUERQGLR[LGH&2FDSDFLW\IRUWKUHHVWHS&&5SURFHVVLQYROYLQJ
VWHDPK\GUDWLRQUHDFWLYDWLRQ
6RUEHQW5HDFWLYDWLRQ7HFKQLTXHV
6\QWKHVLVRIFDOFLXPEDVHGVRUEHQWVIURPSUHFXUVRUV
6RUEHQWV KDYLQJ D KLJK VXUIDFH DUHD DQG SRUH YROXPH KDYH KLJKHU DFWLYLW\ DV LW LV
UHODWLYHO\ HDVLHU IRU JDV PROHFXOH GLIIXVLRQ DQG IRUPDWLRQ RI &D&2 3UHFLSLWDWHG
&DOFLXP&DUERQDWH3&&ZLWKDODUJHVXUIDFHDUHDFDQEHV\QWKHVL]HGE\EXEEOLQJ&2
WKURXJKD&D2+VOXUU\0RUSKRORJ\RIWKHVRUEHQWFDQEHWDLORUHGE\XVLQJDQDQLRQLF
GLVSHUVDQW 1 9 WR REWDLQ XQLTXH PHVRSRURXV VWUXFWXUH QP 7KLV VRUEHQW FDQ
PDLQWDLQDKLJKUHDFWLYLW\RYHUVHYHUDOF\FOHV3&&ZDVXVHGLQDVXOIXUUHPRYDOLQWKH
2KLR 6WDWH &DUERQDWLRQ $VK 5HDFWLYDWLRQ 26&$5 SURFHVV +LJK UHDFWLYLW\ RI
FDOFLXPR[LGH&D2FDQDOVREHREWDLQHGIURPLQRUJDQLFDQGRUJDQRPHWDOOLFSUHFXUVRUV
OLNH FDOFLXP QLWUDWH WHWUDK\GUDWH &D12+2 FDOFLXP DFHWDWH &D&+&22
FDOFLXPSURSLRQDWH&D&+&22FDOFLXPDFHW\ODFHWRQDWH&D&+&2&+&2&+
FDOFLXP R[DODWH &D&22 FDOFLXP HWK\OKH[DQRDWH &D&+&22 DQG FDOFLXP
'JOXFRQDWH PRQRK\GUDWH &D2 GHULYHG IURP FDOFLXP DFHWDWH FDOFLXP SURSLRQDWH DQG
FDOFLXP 'JOXFRQDWH PRQRK\GUDWH H[KLELWHG D KLJKHU &2 FDSWXUH FDSDFLW\ GXH LWV
PHVRSRURXVDQGPDFURSRURXVVWUXFWXUH&D2VRUEHQWVPRGLILHGZLWKHWKDQROVROXWLRQV
VKRZHG KLJKHU &2 FDSWXUH FDSDFLW\ $OWKRXJK VRUEHQWV FRXOG EH FKDQJHG LQ PDQ\
GLIIHUHQW ZD\V XVLQJ RUJDQRPHWDOOLFSUHFXUVRUV WKH DELOLW\ RI KLJKHU &2 FDSWXUH XVLQJ
WKHVHPRGLILHGVRUEHQWVKDVRQO\EHHQWHVWHGLQWKHWKHUPRJUDYLPHWULFDQDO\]HU7*$
DQGQRWLQDFWXDOSURFHVVV\VWHPV7KXVWKHLUDSSOLFDELOLW\DJDLQVWWKHFRVWRIPDWHULDOVLV
GHEDWDEOH
'RSHGRUVXSSRUWHGFDOFLXPR[LGHV
6RUEHQWV GRSHG ZLWK FDOFLXP DOXPLQDWH FHPHQW ZHUH WHVWHG IRU F\FOHV RI
FDUERQDWLRQFDOFLQDWLRQ UHWDLQLQJ E\ ZW 5HVLGXDO FDSWXUH FDSDFLW\ 'RORPLWH
GHULYHG&D2SHUIRUPVEHWWHUUHJDUGLQJFDSWXUHFDSDFLW\ZWDIWHUF\FOHVGXH
WR WKH VXSSRUW RI 0J2 'RSDQWV RU VXSSRUWV PDNH WKH VRUEHQWV PHFKDQLFDOO\ DQG
PRUSKRORJLFDOO\ VWURQJHU EXWWKHRYHUDOO&2FDSWXUHFDSDFLW\LVDIIHFWHGGXHWRORZHU
&D2FRQWHQW6ROLGVFLUFXODWLRQUDWHUHTXLUHGWRFDSWXUHWKHVDPHDPRXQWRI&2ZLWK
GRSHGRUVXSSRUWHGVRUEHQWVPD\EHYHU\KLJKDVFRPSDUHGWRXQVXSSRUWHG&D2VRUEHQW
7KXV WKH LPSDFW RQ SURFHVV PDWHULDO DQG HQHUJ\ EDODQFHV ZRXOG DOVR KDYH WR FRQVLGHU
WKRURXJKO\ IRU HYHU\ GRSHG VRUEHQW DV WKH DPRXQW RI VXSSRUWGRSDQW ZRXOG GHFLGH WKH
DPRXQWRILQHUWFLUFXODWLQJLQWKHORRS7KHFRVWRIWKHVHVRUEHQWVPD\DOVREHKLJKHUDV
FRPSDUHGWROLPHVWRQHSUHFXUVRUV
6WHDPZDWHUK\GUDWLRQ
$ XQLTXH DVSHFW RI FDUERQDWLRQFDOFLQDWLRQ UHDFWLRQ &&5 SURFHVV GHYHORSHG DW 268
KDV EHHQ WKH GHPRQVWUDWLRQ RI FDOFLXP K\GUR[LGH &D2+ EDVHG VRUEHQW IRU SRVW
FRPEXVWLRQ&2FDSWXUH&D2+EDVHGVRUEHQWZDVREWDLQHGE\KLJKWHPSHUDWXUHVWHDP
K\GUDWLRQ DW R& XVLQJ D EHQFK VFDOH IOXLGL]HG EHG K\GUDWLRQ &D2+ EDVHG
VRUEHQWPLWLJDWHVWKHORVVRIUHDFWLYLW\RYHUPXOWLSOHF\FOHVFDXVHGE\KLJKWHPSHUDWXUH
R& FDOFLQDWRQ ZKLFK LV NQRZQ WR FDXVH µVLQWHULQJ¶ RI WKH VRUEHQW .:WK
GHPRQVWUDWLRQ RI WKH &&5 SURFHVV DFKLHYHG ! &2 FDSWXUH DQG 62 FDSWXUH
XVLQJ&D2+VRUEHQWZLWK&D&PROHUDWLRRIDVDJDLQVWZLWK&D2VRUEHQW
,QWHUPHGLDWH K\GUDWLRQ RI WKH VRUEHQW KHOSV LQ UHWDLQLQJ WKH &2 FDSWXUH FDSDFLW\ WKXV
PLQLPL]LQJ WKH VROLG FLUFXODWLRQ DQG VRUEHQW PDNHXS UDWH ZKLFK JLYHV KLJKHU RYHUDOO
SURFHVVHIILFLHQF\+\GUDWLRQRIFDOFLXPEDVHGVRUEHQWLVDKLJKO\H[RWKHUPLFUHDFWLRQ
ZKLFK ZKHQ SHUIRUPHG DW KLJKHU WHPSHUDWXUHV XVLQJ VXSHUKHDWHG VWHDP SURYLGHV KLJK
TXDOLW\KHDW:LWKSURSHUKHDWLQWHJUDWLRQWKHHQHUJ\SHQDOW\LQGXFHGGXHWRWKHFDOFLQHU
RSHUDWLRQ FRXOG EH PLQLPL]HG :LWK &D2+ EDVHG VRUEHQW GHPRQVWUDWLRQ WKH RYHUDOO
HQHUJ\SHQDOW\FDQEHUHWDLQHGDWZLWKWKHXVHRI3XOYHUL]HGFRDO3&
&D2+2 &D2+
¨+ N-PRO
$QDOPRVWLQVWDQWDQHRXVUHDFWLRQZLWKZDWHUDWURRPWHPSHUDWXUHK\GUDWLRQRIFDOFLXP
R[LGH &D2 LV OLPLWHG E\ WKHUPRG\QDPLFV ZKHQ SHUIRUPHG ZLWK VXSHUKHDWHG VWHDP DW
KLJKWHPSHUDWXUH)LJXUHRQSDJHVKRZVWKHUHODWLRQVKLSEHWZHHQWHPSHUDWXUHDQG
HTXLOLEULXP VWHDP SDUWLDO SUHVVXUH 3+2 DW KLJK WHPSHUDWXUH 6WHDP K\GUDWLRQ DW
WHPSHUDWXUHV FRPSDUDEOH WR WKH FDUERQDWRU WHPSHUDWXUH R& LQ WKH FDOFLXP
ORRSLQJ SURFHVV ZRXOG KDYH WR EH RSHUDWHG DW HOHYDWHG VWHDP SUHVVXUH ! DWP IRU
HIIHFWLYH FRQYHUVLRQ DQG KLJKHU UDWHV RI UHDFWLRQ LQ WKH K\GUDWRU 7KH RSHUDWLRQ RI WKH
K\GUDWRUDWKLJKHUWHPSHUDWXUHVZRXOGDOORZIRUH[WUDFWLRQRIKLJKTXDOLW\KHDWXVDEOHLQ
WKHVWHDPWXUELQHF\FOHRIWKHSRZHUSODQW
)LJXUHVKRZVWKUHHVWDJHSRVWFRPEXVWLRQ&&5SURFHVVWKDWFRXOGEHUHWURILWWHGWRD
FRDOQDWXUDO JDV ILUHG SRZHU SODQW 5HDFWLRQV FRORUHG UHG LQGLFDWH HQGRWKHUPLF UHDFWLRQ
ZKLFKUHTXLUHVHQHUJ\WRRYHUFRPHWKHDFWLYDWLRQEDUULHUZKLOHUHDFWLRQVFRORUHGLQJUHHQ
DUHH[RWKHUPLFUHDFWLRQV
&D2&2 &D&2¨+R N-PRO
3UHFRPEXVWLRQFDOFLXPORRSLQJSURFHVV&/3JHQHUDWHVKLJKSXULW\+DQGHOHFWULFLW\
IURP V\QJDV REWDLQHG IURP D FRDO JDVLILHU 7KLV SURFHVV SURGXFHV K\GURJHQ WKURXJK
ZDWHU JDV VKLIW UHDFWLRQ ZKLOH &D2 VRUEHQW WDNHV XS WKH &2 JHQHUDWHG LQ WKH UHDFWLRQ
7KLVVKLIWVWKHUHDFWLRQHTXLOLEULXPWRWKHULJKWDFFRUGLQJWR/H&KDWWHOLHU¶VSULQFLSOH
&2+2
&2+
,WXVHVLQWHUPHGLDWHK\GUDWLRQUHDFWLRQVFKHPHOLNHWKH&&5SURFHVVWRUHWDLQWKHVRUEHQW
UHDFWLYLW\
)LJXUH6FKHPDWLFRISRVWFRPEXVWLRQFDUERQFDSWXUH&&5SURFHVV
&DUERQ GLR[LGH FDSWXUH FDSDFLW\ KDV EHHQ VKRZQ WR GURS GUDVWLFDOO\ RYHU PXOWLF\FOLF
RSHUDWLRQLQ WKH &D2 VRUEHQW EDVHGSURFHVV ZKLFK GHFUHDVHV WKH SURFHVV HIILFLHQF\DQG
DOVRQHFHVVLWDWHVWKHXVHRIZDWHUJDVVKLIW:*6UHDFWLRQIRU+ SURGXFWLRQ&D2+
EDVHGSURFHVVQRWRQO\REYLDWHVWKHQHHGIRUDZDWHUJDVVKLIWFDWDO\VWEXWDOVRUHPRYHV
RWKHU DFLGLF JDVVHV OLNH K\GURJHQ VXOILGH +6 K\GURJHQ FKORULGH +&O FDUERQ\O
VXOILGH&26HWFLQDVLQJOHVWHS$VWKHRSHUDWLQJWHPSHUDWXUHRIWKHFDUERQDWRULV
VXIILFLHQWO\ODUJHIRUGHK\GUDWLRQRIWKH&D2+IURPWKHK\GUDWRUWKHUHVXOWLQJVWHDP
JHQHUDWHG LV DYDLODEOH IRU WKH :*6 UHDFWLRQ WKXV ZDLYLQJ WKH DGGLWLRQDO VWHDP
UHTXLUHPHQWVIRU:*6&D2+DVVRUEHQWZRXOGGHFUHDVHWKHVROLGVFLUFXODWLRQUDWHDQG
WKHIUDFWLRQRIPDNHXSVROLGVLQWKHFDOFLQHU3UHFRPEXVWLRQFDOFLXPORRSLQJSURFHVV
KDV EHHQ VWXGLHG IRU KLJK SUHVVXUH DQG VKRZV KLJKHU &2 FRQYHUVLRQ ZLWK KLJKO\ SXUH
K\GURJHQ ! LQWKH SURGXFWVWUHDPZKHQRSHUDWHGDWKLJKSUHVVXUHVDWP
0RUHRYHU GXH WR WKH LQKHUHQW UHTXLUHPHQW RI VWHDP LQ WKH SUHFRPEXVWLRQ SURFHVV IRU
K\GURJHQSURGXFWLRQWKHLQWURGXFWLRQRIVWHDPK\GUDWLRQPD\QRWDIIHFWWKHHFRQRPLFV
RI WKH SURFHVV WR D JUHDW H[WHQW $W KLJKHU SUHVVXUHV K\GUDWLRQ RI &D2 LV PXFK PRUH
IDYRUDEOH GXH WR ODUJHU GULYLQJ IRUFH 7KXV SUHVVXUL]HG VWHDP K\GUDWLRQ DW D KLJKHU
WHPSHUDWXUH FRXOG EH LQWHJUDWHG LQWR WKH SUHFRPEXVWLRQ FDOFLXP ORRSLQJ SURFHVV ZLWK
UHODWLYHHDVH)LJXUHVKRZVWKHVFKHPDWLFRISUHFRPEXVWLRQFDUERQGLR[LGHFDSWXUH
SURFHVV
)LJXUH6FKHPDWLFRISUHFRPEXVWLRQFDUERQFDSWXUH&/3SURFHVV
)RU ERWK SUH DQG SRVWFRPEXVWLRQ FDUERQ FDSWXUH SURFHVVHV WKHUH DUH FRPPRQ
DGYDQWDJHVIRUXVLQJ&D2+EDVHGWKUHHVWDJHFDOFLXPORRSLQJSURFHVV
&D2+&D2 DV WKH VRUEHQW KDV VXSHULRU PRUSKRORJLFDO SURSHUWLHV VXUIDFH DUHD SRUH
YROXPHSRURVLW\WKXVPDNLQJLWPRUHUHDFWLYHWKDQ&D2DQGFRXOGEHXVHGDVDVRUEHQW
LQ WKH FDUERQDWRU ZKLFK FRXOG PDNH XVH RI H[WUHPHO\ VPDOO UHVLGHQFH WLPHV LQ WKH
FDUERQDWRUHYHQ IHZ VHFRQGV$ORQJZLWKLPSURYLQJWKHUHDFWLYLW\WKLVZLOODOORZ IRU
IDVW IOXLGL]DWLRQ RSHUDWLRQ LQ WKH FDUERQDWRU 7KXV WKH UHVLGHQFH WLPH IRU FDUERQDWRU
FRXOG EH UHGXFHG DJDLQVW WKDW UHTXLUHG IRU D FDUERQDWRU RSHUDWLQJ LQ D EXEEOLQJ RU
FLUFXODWLQJ IOXLGL]HG EHG 7KLV ZRXOG HQDEOH IDVWHU DQG JUHDWHU &2 FDSWXUH E\
PDLQWDLQLQJORZHUVROLGFLUFXODWLRQUDWHVDQGVDPHUHDFWRUVL]H&D&UDWLRDVORZDV
ZDVREVHUYHGIRU!FDUERQGLR[LGHFDSWXUHLQWKH&&5SURFHVVXVLQJ&D2+ EDVHG
VRUEHQWDVDJDLQVWIRU*UD\PRQW OLPH LQ WKH VDPH VWXG\/RZHU&D& PRODU UDWLR
DOORZVIRUGHVLJQLQJRIVPDOOHUHTXLSPHQWWKXVPLQLPL]LQJWKHFDSLWDOFRVW7KLVLVHYHQ
PRUHIDYRUDEOHJLYHQWKHODWHVW(3$UHJXODWLRQIRU&2FDSWXUHLQWKHQHZFRDODQG
QDWXUDOJDVILUHGSRZHUSODQWV(FRQRPLFVRIWKHSURFHVVFRXOGLPSURYHWRDJUHDWH[WHQW
E\UHPRGHOLQJWKHWKUHHVWDJHFDOFLXPORRSLQJSURFHVVWXQHGLQDFFRUGDQFHZLWKWKHODWHVW
UHJXODWLRQV7KLVVWXG\DLPVWRILQGWKHUHVLGHQFHWLPHDQGJRRGRSHUDWLQJFRQGLWLRQVIRU
VWHDP K\GUDWLRQ RI VRUEHQWV UHJDUGLQJ VWHDP SUHVVXUH DQG K\GUDWRU WHPSHUDWXUH
5HDFWLYDWLRQ E\ K\GUDWLRQ RI WKH VRUEHQW ZDV ILUVW SURSRVHG WR LPSURYH VRUEHQW
SHUIRUPDQFH IRU 62 FDSWXUH LQ )OXLGL]HG %HG &RPEXVWLRQ )%& V\VWHPV DV WKH
H[SDQVLRQ FDXVHG GXH WR K\GUDWLRQ RI &D2 WR &D2+ FUDFNV XS WKH &D62 ZKLFK
RWKHUZLVH PD\ KLQGHU &D2&2 DQG &D262 UHDFWLRQ 5HFDUERQDWLRQ RI
&D2+ EDVHG VRUEHQW RFFXUV LQ WZR ZD\V DFFRUGLQJ WR WKH UHFHQW ILQGLQJV GLUHFW
FDUERQDWLRQ DQG LQGLUHFW FDUERQDWLRQ ,QGLUHFW FDUERQDWLRQ LV WKH LVRWKHUPDO UHDFWLRQ RI
&D2 GHULYHG IURP &D2+ DQG &2 'LUHFW FDUERQDWLRQ ZLWK &D2+ RFFXUV LQ QRQ
LVRWKHUPDO FRQGLWLRQ EHIRUH &D2+ GHK\GUDWHV WR &D2 'LUHFW FDUERQDWLRQ RFFXUV
ZLWKRXW HQWHULQJ WKH VORZ GLIIXVLRQ UHJLPH FKDUDFWHULVWLF RI &D2&2 UHDFWLRQ 7KLV
DOORZV IRU FRQYHUVLRQ DQG ZRXOG WKXV JLYH PD[LPXP VRUEHQW XWLOL]DWLRQ LQ WKH
SURFHVV%\UHJHQHUDWLQJWKHVRUEHQWVXUIDFHFDUERQGLR[LGHFDSWXUHFDSDFLW\LVUHVWRUHG
QHDUO\ WR LWV WKHRUHWLFDO OLPLW RI ZW RYHU PXOWLSOH F\FOHV 'LUHFW FDUERQDWLRQ
REVHUYDWLRQKDVEHHQFRQILUPHGE\VHYHUDOUHVHDUFKHUV0RUHRYHUWKHH[RWKHUPLFKHDW
RIUHDFWLRQRIK\GUDWLRQDWKLJKWHPSHUDWXUHLQWKHK\GUDWRUFRXOGEHGLUHFWO\XVHGLQWKH
VWHDP WXUELQH F\FOH WR JHQHUDWH PRUH HOHFWULFLW\ 7KHVH DGYDQWDJHV RI XVLQJ VWHDP
K\GUDWLRQ RI VRUEHQW DV DQ LQWHUPHGLDWH VWHS LQ FDOFLXP ORRSLQJ SURFHVV HVSHFLDOO\ IRU
SURFHVVHVGHYHORSHGDW268LVDVLJQLILFDQWGULYLQJIRUFHEHKLQGWKHKLJKSUHVVXUHVWHDP
K\GUDWLRQVWXG\
(DUOLHUVWXGLHVRQLQWHUPHGLDWHVWHDPK\GUDWLRQRIFDOFLXPVRUEHQWVKDYHEHHQSHUIRUPHG
DWORZHUWHPSHUDWXUHVXVLQJZHWJDVLQVWHDGRIVWHDP)RUHQHUJ\LQWHJUDWLRQRIK\GUDWLRQ
LQWRWKHFDOFLXPORRSLQJSURFHVVHLWKHUSUHSRVWFRPEXVWLRQUHTXLUHVWKHUHDFWLRQWREH
RSHUDWHG DW LQWHUPHGLDWH SURFHVV WHPSHUDWXUHV EHWZHHQ R& 7KLV DOORZV IRU
XWLOL]DWLRQ RI WKH KHDW RI UHDFWLRQ ZKLOH UHWDLQLQJ WKH VRUEHQW UHDFWLYLW\ )L[HG EHG DQG
EHQFK VFDOH K\GUDWLRQ VWXGLHV SHUIRUPHG ZLWK VWHDP SDUWLDO SUHVVXUH 3+2 RI DWP
KDYHDQXSSHUOLPLWGXHWRWKHWKHUPRG\QDPLFVRIWKHUHDFWLRQ$WR&VWHDPSDUWLDO
SUHVVXUHDWHTXLOLEULXP3+2LVDWPZKLFKUHTXLUHVWKHK\GUDWRUWREHRSHUDWHGDW
WHPSHUDWXUHVORZHURUFORVHWRR&%HQFKVFDOHK\GUDWRUVWXGLHVSHUIRUPHGDWR&
VKRZHG FRQYHUVLRQ LQ PLQXWHV ZKLFK QHHGV WR EH IXUWKHU RSWLPL]HG E\
FRQVLGHULQJWKHLPSOLFDWLRQVRQUHDFWRUGHVLJQDQGFDSLWDOFRVW.LQHWLFVVWXGLHVDWORZHU
VWHDPSDUWLDOSUHVVXUHVDWPVKRZDVXEVWDQWLDOO\ORZHUUDWHRIUHDFWLRQLI7HT±
7R&7HT HTXLOLEULXPWHPSHUDWXUHIRUSDUWLFXODURSHUDWLQJVWHDPSUHVVXUHDQG7 UHDFWLRQ WHPSHUDWXUH 7R RYHUFRPH WKH HTXLOLEULXP EDUULHU DQG WR DOORZ IRU KLJKHU
UHDFWRUWHPSHUDWXUHKLJKHUVWHDPSDUWLDOSUHVVXUHVFRXOGEHXVHGZKLFKZRXOGUHTXLUHD
GHWDLOHG NLQHWLFV VWXG\ IRU EHWWHU UHDFWRU GHVLJQ .LQHWLFV DQG 3DUWLFOH FKDUDFWHUL]DWLRQ
VWXGLHV IRU VWHDP K\GUDWLRQ DW LQWHUPHGLDWH SUHVVXUHV ± DWP DQG WHPSHUDWXUH
EHWZHHQ R& DUH SUHVHQWHG KHUH 6WHDP K\GUDWLRQ DW HOHYDWHG SUHVVXUHV KDV EHHQ
VWXGLHG IRU SUHFRPEXVWLRQ FDUERQ FDSWXUH LQWHJUDWHG ZLWK D FRDO JDVLILHU VLPLODU LQ
GHVLJQ WR WKH +\3U5,1* V\VWHP :DQJ HW DO LQYHVWLJDWHG WKH HIIHFW RI SDUWLFOH
SURSHUWLHVXVLQJIRXUW\SHVRI-DSDQHVHOLPHVWRQHIRUVWHDPSDUWLDOSUHVVXUHVEHWZHHQ
DWP ,W ZDV REVHUYHG WKDW K\GUDWLRQ UDWH RI &D2 LV D IXQFWLRQ RI VWHDP SUHVVXUH
JUDGLHQW3+2±3+2IRUSDUWLFXODURSHUDWLQJWHPSHUDWXUH7KHUPRJUDYLPHWULF7*$
VWXGLHVRQDQRWKHU-DSDQHVHOLPHVWRQHE\/LQHWDOIRUVWHDPSUHVVXUHVEHWZHHQ±
DWP VKRZHG WKDW UDWH RI UHDFWLRQ LV D IXQFWLRQ RI VHFRQG SRZHU ZUW SDUWLDO SUHVVXUH
JUDGLHQW 3+2 ± 3+2 ,W LV HYLGHQW IURP WKHVH VWXGLHV WKDW VWHDP SDUWLDO SUHVVXUH
VXEVWDQWLDOO\ DIIHFWV WKH UHDFWLRQ UDWH KRZHYHU VXFK KLJK WHPSHUDWXUHV DQG SUHVVXUHV
ZRXOGUHTXLUHDGGLWLRQDOFDSLWDODQGRSHUDWLQJFRVWIUHTXHQWPDLQWHQDQFHDQGVWULQJHQW
VDIHW\VWDQGDUGVFRPSDUHGWRRWKHUXQLWVRSHUDWLQJDWDPXFKORZHUSUHVVXUH)RUSUHDQG
SRVWFRPEXVWLRQ FDOFLXP ORRSLQJ V\VWHPV GHYHORSHG DW 268 K\GUDWLRQ DW LQWHUPHGLDWH
VWHDPSUHVVXUHV±DWPDQGWHPSHUDWXUHR&LVDGYDQWDJHRXVFRQVLGHULQJ
SUHYLRXVVWXGLHVRISURFHVVHFRQRPLFVRI&&5SURFHVVDQG&/3SURFHVVR&DQG
DWP3+23UHOLPLQDU\WHFKQRHFRQRPLFDQDO\VLVIRUWKH&&5SURFHVVVXJJHVWV
SHUIRUPLQJ K\GUDWLRQ DW D WHPSHUDWXUH FORVH WR R& WR PDLQWDLQ WKH RYHUDOO HQHUJ\
SHQDOW\ RI WKH SURFHVV DW ZKLOH PRUH HOHFWULFLW\ FRXOG EH JHQHUDWHG IURP WKH
SURFHVV 2WKHU SDUDPHWHUV OLNH SDUWLFOH VL]H VXUIDFH FKDUDFWHULVWLFV RULJLQ DUH DOVR
NQRZQWRDIIHFWWKHK\GUDWLRQUDWH$63(1SURFHVVVLPXODWLRQVVWXGLHVZKLFKLQFOXGH
VWHDPK\GUDWLRQLQERWKWKHSUHDQGSRVWFRPEXVWLRQFDOFLXPORRSLQJSURFHVVLQGLFDWHD
GLUHFW LPSDFW RI VRUEHQW UHDFWLYLW\ DQG K\GUDWLRQ H[WHQW RQ WKH SURFHVV HQHUJ\
FRQVXPSWLRQ HFRQRPLFV DQG VROLGV FLUFXODWLRQ UDWH )RU LQVWDQFH PRUH WKDQ &2
FDSWXUH DQG ! 62 FDSWXUH FRXOG EH DFKLHYHG LQ WKH &&5 SURFHVV ZLWK WKH XVH RI
&D2+EDVHGVRUEHQWDWD&D&PROHUDWLRRI3UHYLRXVVWXGLHVRYHUVWHDPK\GUDWLRQ
RI&D2DQGSURFHVVHFRQRPLFVVWXGLHVDW268GLFWDWHVWKHLPSRUWDQFHRINLQHWLFVVWXG\
RI K\GUDWLRQ IRU LQWHUPHGLDWH VWHDP SDUWLDO SUHVVXUHV SHUIRUPHG XVLQJ 7*$ IRU IRXU
GLIIHUHQWOLPHVWRQHVIURPTXDUULHVLQ2KLR3HQQV\OYDQLDDQG.HQWXFN\
7KHRUHWLFDOO\ D SUHVVXUL]HG VWHDP K\GUDWRU VKRXOG \LHOG IDYRUDEOH UHDFWLRQ NLQHWLFV WR
UHYHUVHWKHDGYHUVHHIIHFWRIVLQWHULQJLQWKHFDOFLQHUWKXVUHWDLQLQJWKHVRUEHQWUHDFWLYLW\
RYHUDODUJHQXPEHURIF\FOHVUHGXFHVROLGFLUFXODWLRQUDWHLQWKHV\VWHPDQGPLQLPL]H
WKH&D&PROHUDWLRWRJLYHKLJKHUFDUERQGLR[LGHFDSWXUH7KLVVWXG\KDVEHHQSHUIRUPHG
WR WHVW VWHDP K\GUDWLRQ RI FDOFLXP VRUEHQWV DW DFKLHYDEOH DQG IHDVLEOH RSHUDWLQJ
FRQGLWLRQV RI WHPSHUDWXUH DQG VWHDP SUHVVXUH ZKLFK ZRXOG QRW DIIHFW LI QRW UHGXFH WKH
RYHUDOOHQHUJ\SHQDOW\RIWKHFXUUHQW&&5SURFHVV
&KDSWHU0DWHULDOVDQG([SHULPHQWDO6HWXS
0DWHULDOVDQG6RUEHQW3UHSDUDWLRQ
)RXU W\SHV RI FDOFLWH OLPHVWRQH VDPSOHV ZHUH LQYHVWLJDWHG LQ WKLV VWXG\ ZKLFK ZDV
REWDLQHG IURP *UD\PRQW ,QF DQG +DQVRQ$JJUHJDWHV*UD\PRQWVDPSOHZDVSURFXUHG
IURP 3OHDVDQW *DS 3* 3HQQV\OYDQLD DQG +DQVRQ $JJUHJDWHV VDPSOHV FDPH IURP
)OHPLQJVEXUJ)/.HQWXFN\$$IURPVRXWKHUQ2KLRDQG(DJOH($2KLR7KRXJK
WKH VHOHFWHG VDPSOHV PD\ EH GLIIHUHQW ZUW IRUPDWLRQ DQG DJH IURP RWKHU OLPHVWRQH
VDPSOHVLQWKH86LWLVEHOLHYHGWKDWUHVXOWVREWDLQHGIURPPRUHWKDQRQHVDPSOHDOORZ
IRUFRQILGHQWUHSRUWLQJRIWKHUHVXOWVDQGLQWHUSUHWDWLRQVGUDZQIURPWKHP3*VDPSOHLVD
SXOYHUL]HGVDPSOHZKLOH$$)/DQG($ZHUHFUXVKHGDQGSDUWLFOHVOHVVWKDQ—PLQ
VL]H ZHUH VHSDUDWHG DQG XVHG IRU WKLV VWXG\ 7KH SKHQRPHQRQ RI SDUWLFOH
DWWULWLRQEUHDNDJH GXH WR K\GUDWLRQ KDV EHHQ UHSRUWHG WKURXJK VHYHUDO VWXGLHV
7KHUHIRUH LQLWLDO SDUWLFOH VL]H KDV OLWWOH RU QR EHDULQJ RQ WKH K\GUDWLRQ H[SHULPHQWV
HVSHFLDOO\ LQ D PXOWLF\FOLF SURFHVV )RXU OLPHVWRQH VDPSOHV REWDLQHG IURP GLIIHUHQW
TXDUULHVLQ2KLR3HQQV\OYDQLDDQG.HQWXFN\ZHUHWHVWHGLQ3\ULV7*$IRUTXDQWLI\LQJ
WKH FDOFLXP FRQWHQW DQG H[WHQW RI K\GUDWLRQ RI WKH VRUEHQW ZLWK ZDWHU DW URRP
WHPSHUDWXUH,VRWKHUPDO'HFRPSRVLWLRQLQWKHFRPSOHWHO\LQHUWDWPRVSKHUH1DW
R& ZDV SHUIRUPHG IRU HDFK VDPSOH 3URJUDP IRU WKH 7*$ DQDO\VLV ZDV DV IROORZV
6DPSOH ZDV KHDWHG IURP WR R& LQ 1 DQG KHOG LVRWKHUPDOO\ IRU PLQ IRU ERWK
FDOFLQDWLRQRIVDPSOHDQGGHK\GUDWLRQRIK\GUDWHGVRUEHQW7KHVDPSOHZDVFRROHGEDFN
WRR&7KHUDWHRIKHDWLQJDQGFRROLQJZDVFRQWUROOHGDWR&PLQ,QFRPSOHWHO\LQHUW
DWPRVSKHUHFDOFLXPFDUERQDWH&D&2LQOLPHVWRQHVDPSOHVWDUWVFDOFLQLQJDWaR&
+ROGLQJWKHWHPSHUDWXUHDWR&IRUPLQHQVXUHGFRPSOHWHFDOFLQDWLRQRIWKHVDPSOH
:KLOH FDOFLQDWLRQ VWDUWV DW R&GHFRPSRVLWLRQRIWKHK\GUDWHLQWKHK\GUDWHGVRUEHQW
VWDUWVDWDPXFKORZHUWHPSHUDWXUHR&+RZHYHUZLWKWKHVDPHSURJUDPXVHG
IRU K\GUDWHG VRUEHQWV XVXDOO\ WZR VWHSV IRU ZHLJKW ORVV ZHUH REVHUYHG :HLJKW ORVV
GXULQJ WHPSHUDWXUH UDPSXS ZDV DWWULEXWHG WR GHK\GUDWLRQ &D2+ WR &D2 DQG
LVRWKHUPDOZHLJKWORVVRFFXUULQJDWR&LVDWWULEXWHGWRFDOFLQDWLRQRIUHVLGXDOFDOFLXP
FDUERQDWH&D&2LQWKHVRUEHQW,VRWKHUPDOZHLJKWORVVLVDVPDOOIUDFWLRQRIWKHWRWDO
ZHLJKWORVVGXULQJGHFRPSRVLWLRQRIK\GUDWHGVRUEHQW&DUERQGLR[LGHFDSWXUHFDSDFLW\
RIWKHVRUEHQWLVDGLUHFWIXQFWLRQRIWKHFDOFLXPFRQWHQWRIWKHOLPHVWRQHVDPSOH7KXV
IRXUOLPHVWRQHVDPSOHVDFTXLUHGIURPTXDUULHVDURXQG2KLRZHUHWHVWHGLQ3\ULV7*$
PJVDPSOHZDVXVHGIRUHDFKDQDO\VLV$PRXQWRIFDOFLXPFDUERQDWH&D&2LQ
WKHVDPSOHZDVFDOFXODWHGIURPWKHZHLJKWORVVGXHWRWKHUHOHDVHRI&2
൫ͲȂ…ƒŽ…‹‡†൯‫͵ƒכ‬
&D&2 ௐ଴‫כ‬ெʹ
:LVWKHZHLJKWRIWKHVDPSOHWHVWHGLQWKH7*$DQG:FDOFLQHGLVWKHZHLJKWRIWKHVRUEHQW
DIWHU PLQXWHV RI LVRWKHUPDO FDOFLQDWLRQ DW R& LQ WKH 7*$ $OO WKH OLPHVWRQH
VDPSOHV H[FHSW $$ KDYH PRUH WKDQ FDOFLXP FRQWHQW /LPHVWRQH VDPSOHV ZHUH
FDOFLQHGLQWKHPXIIOHIXUQDFHDWR&IRUKRXUVDQGFDOFLQHGVDPSOHVZHUHK\GUDWHG
ZLWK D VWRLFKLRPHWULF TXDQWLW\ RI ', ZDWHU DW URRP WHPSHUDWXUH WR FKHFN WKH H[WHQW RI
K\GUDWLRQ $OO WKH VDPSOHV FRQWDLQHG PRUH WKDQ K\GUDWH DQG D VPDOO DPRXQW RI
XQFDOFLQHG FDOFLXP FDUERQDWH DORQJ ZLWK WKH LQKHUHQW LQHUWV 7KLV VWXG\ VKRZHG WKH
FDSDELOLW\ RI VWHDP K\GUDWLRQ RI WKH VRUEHQWV IRU WKH SDUDPHWULF WKHUPRJUDYLPHWULF
VWXGLHV$OVRVRUEHQWVK\GUDWHGZLWKZDWHUDWURRPWHPSHUDWXUHZHUHDQDO\]HGIRUSRUH
VL]HGLVWULEXWLRQDQGVXUIDFHDUHDVWXGLHVXVLQJWKHQLWURJHQSK\VLVRUSWLRQ7KHH[WHQWRI
K\GUDWLRQLVNQRZQE\FDOFXODWLQJWKHH[WHQWRIK\GUDWLRQRIWKHVRUEHQW7KHZHLJKWORVV
FXUYHIRUK\GUDWHGVRUEHQWVWHVWHGLQ3\ULV7*$XVLQJWKHVDPHSURJUDPDVWKDWXVHG
IRU FDOFLQDWLRQ LV GLIIHUHQW IURP D VLQJOH VWHHS ORVV DV VHHQ LQ FDOFLQDWLRQ :HLJKW ORVV
GXH WR GHK\GUDWLRQ RI &D2+ RFFXUV DW PXFK ORZHU WHPSHUDWXUHV !R& DQG LV
FRPSOHWHG DV WKH WHPSHUDWXUH UHDFKHV R& 7ZR GLVWLQFW ZHLJKW ORVV SDWWHUQV DUH
REVHUYHGLQWKLVVWXG\7KHRQHRFFXUULQJDWDWHPSHUDWXUHORZHUWKDQR&LVDWWULEXWHG
WR WKH ZHLJKW ORVV GXH WR GHK\GUDWLRQ RI &D2+ ([WHQW RI K\GUDWLRQ LV FDOFXODWHG DV
IROORZV
൫ͲȂͳ൯ȗƒሺሻʹ
&D2+ Ͳȗʹ
7KH H[WHQW RI K\GUDWLRQ VHHQ LQ WKHVH VWXGLHV LV QRW FRPSOHWH GXH WR LQFRPSOHWH
FDOFLQDWLRQRIWKHVRUEHQWLQWKHPXIIOHIXUQDFH,QWKHSDUDPHWULF7*$VWXGLHVOLPHVWRQH
VDPSOHLVFDOFLQHGLQWKH7*$DQGK\GUDWHGXVLQJVWHDP7KXVFRPSOHWHK\GUDWLRQZDV
REVHUYHGGXULQJWKHVHVWXGLHV7DEOHVKRZVWKHFRPSRVLWLRQRIOLPHVWRQHPLQHUDOV
UHJDUGLQJFDOFLXPFDUERQDWHFRQWHQWDQGH[WHQWRIK\GUDWLRQ
7DEOH&RPSRVLWLRQRIOLPHVWRQHVRUEHQWVDQGH[WHQWRIZDWHUK\GUDWLRQ
&RPSDQ\ 6DPSOH
4XDUU\
*UD\PRQW
/RFDWLRQ
7\SH
$FURQ\P &D&2 &D2+
8VHG
:DWHU
K\GUDWLRQ
3OHDVDQW*DS 3HQQV\OYDQLD &DOFLWH
3*
+DQVRQ
)OHPLQJVEXUJ .HQWXFN\
&DOFLWH
$JJUHJDWHV
2KLR 5LYHU
%DVLQ
)/
+DQVRQ
*UD\VRQ
$JJUHJDWHV
.HQWXFN\
&DOFLWH
2KLR 5LYHU
%DVLQ
$$
+DQVRQ
(DJOH
$JJUHJDWHV
2KLR2KLR
($
&DOFLWH
5LYHU%DVLQ
([SHULPHQWDO6HWXSDQG3URFHGXUH
&DOFLQDWLRQ
&DOFLQDWLRQRIWKHVDPSOHVZDVSHUIRUPHGLQDQRYHQ)LVFKHU6FLHQWLILF,VRWHPS0XIIOH
)XUQDFH ZLWK D PD[LPXP FDSDFLW\ RI R& 6DPSOHV ZHUH SODFHG LQ D FHUDPLF
FUXFLEOHIRUFDOFLQDWLRQ6DPSOHVZHUHFDOFLQHGDWR&DQGR&IRURUKRXUV'XH
WR D ORZHU GHJUHH RI FDOFLQDWLRQZWDWR&VRUEHQWVREWDLQHGIRUWKHVWXGLHV
SUHVHQWHGKHUHKDYHEHHQFDOFLQHGDWR&IRUKRXUV/RVVRIUHDFWLYLW\RIWKHVRUEHQWV
GXHWRVLQWHULQJLVPDLQO\DIXQFWLRQRIFDOFLQDWLRQWHPSHUDWXUHWKDQWKHWLPHIRUZKLFK
VDPSOHVZHUHFDOFLQHG&DOFLQDWLRQRIWKHVDPSOHZDVDOPRVWFRPSOHWHZLWKLQKRXUV
7RDYRLGKDUGEXUQLQJRIWKHRXWHUVWUXFWXUHRIWKHVDPSOHFDOFLQDWLRQWLPHZDVOLPLWHG
WRKRXUV
1LWURJHQSK\VLVRUSWLRQVWXGLHV
3K\VLVRUSWLRQ VWXGLHV ZHUH SHUIRUPHG RQ WKH OLPHVWRQH VRUEHQWV XVLQJ QLWURJHQ JDV WR
REWDLQ WKH VXUIDFH DUHD SRUH YROXPH DQG SRUH VL]H GLVWULEXWLRQ RI WKH VRUEHQW VXUIDFH
XVLQJWKH%UDXQDXHU(PPHWW7HOOHU%(7DQG%DUUHWW-R\QHU+DOHQGD%-+PHWKRGRQ
4XDQWDFKURPH129$HVHULHVDQDO\]HUIURP4XDQWDFKURPH,QVWUXPHQWV
6ROLGVXUIDFHVPXVWEHIUHHIURPFRQWDPLQDQWVVXFKDVRLODQGZDWHUEHIRUHSHUIRUPLQJ
WKH DQDO\VLV $Q\ LPSXULW\ FKHPLFDOO\ RU SK\VLFDOO\ DGVRUEHG RQ WKH VXUIDFH FDQ EH
UHPRYHGE\GHJDVVLQJWKHVDPSOHVXQGHUYDFXXPRULQHUWJDVDWKLJKWHPSHUDWXUH
R& 7KH WHPSHUDWXUH IRU WKH GHJDVVLQJ RI WKH VDPSOH ZDV VHOHFWHG EDVHG RQ WKH
VRUEHQW+\GUDWHGVRUEHQW&D2+ZDVSHUIRUPHGDWR&WRGHFRPSRVHWKH&D2+
WR&D2WRFDSWXUHWKHHIIHFWRIH[SDQVLRQRIWKHSRUHVDQGLQFUHDVHLQVXUIDFHDUHDGXHWR
K\GUDWLRQ )UHVK VRUEHQW &D&2 DQG FDOFLQHG VRUEHQW &D2 ZDV GHJDVVHG DW D ORZHU
WHPSHUDWXUH RI R& 'HJDVVLQJ ZDV XVXDOO\ SHUIRUPHG RYHUQLJKW RU DW OHDVW KRXUV
DIWHU ZKLFK WKH VDPSOHV ZHUH ZHLJKHG DQG VXEMHFWHG WR DGVRUSWLRQGHVRUSWLRQ DQDO\VLV
7RPDLQWDLQDFRQVWDQWWHPSHUDWXUHRIWKHVDPSOHOLTXLGQLWURJHQEDWKZDVXVHGZKLFK
PDLQWDLQHG WKH VDPSOH WHPSHUDWXUH DW R& 6PDOO DPRXQWV RI QLWURJHQ JDV DUH
DGPLWWHG LQ VWHSV LQ WKH HYDFXDWHG FKDPEHU $GVRUSWLRQ RI WKH JDV RQ WKH VROLG VXUIDFH
WHQGV WR IRUP D WKLQ OD\HU WKDW FRYHUV WKH HQWLUH DGVRUEHQW VXUIDFH %DVHG RQ WKH ZHOO
NQRZQ%(7WKHRU\DQXPEHURIPROHFXOHV1PDGVRUEHGRQWKHVXUIDFHLVFRPSXWHG7KH
SURGXFW RI 1P DQG FURVVVHFWLRQDO DUHD RI DQ DGVRUEDWH PROHFXOH \LHOGV WKH VDPSOH¶V
VXUIDFHDUHD&RQWLQXHGDGGLWLRQRIWKHJDVPROHFXOHVEH\RQGPRQROD\HUIRUPDWLRQOHDGV
WRJUDGXDOVWDFNLQJRIWKHPXOWLSOHOD\HUV%-+PHWKRGLVXVHGWRFRPSXWHWKHSRUHVL]HV
IURPHTXLOLEULXPJDVSUHVVXUHV([SHULPHQWDOLVRWKHUPVRIDGVRUEHGJDVYROXPHVUHODWLYH
YHUVXV HTXLOLEULXP SUHVVXUHV DUH FRQYHUWHG WR FXPXODWLYH RU GLIIHUHQWLDO SRUH VL]H
GLVWULEXWLRQV
7KHUPRJUDYLPHWULF$QDO\VLV7*$VWXGLHVIRUKLJKSUHVVXUHVWHDPK\GUDWLRQ
3DUDPHWULFVWXGLHVIRUVWHDPK\GUDWLRQRIFDOFLXPR[LGH&D2VRUEHQWVE\YDU\LQJVWHDP
SUHVVXUH DQG WHPSHUDWXUH ZHUH SHUIRUPHG RQ WKH 5XERWKHUP 0DJQHWLF 6XVSHQVLRQ
%DODQFH 06% VFKHPDWLF LQ )LJXUH 5XERWKHUP 06% LV D WKHUPRJUDYLPHWULF
DQDO\]HU ZLWK SURYLVLRQ IRU VHQGLQJ D JDVHRXV PL[WXUH ZLWK JDVHV FDQ ZLWKVWDQG D
SUHVVXUHXSWRDWPRU36,&\OLQGULFDOTXDUW]VDPSOHKROGHUZHLJKLQJMXVWPRUH
WKDQ J ZLWK D GLDPHWHU PP DQG D KHLJKW RI PP ZDV XVHG 6DPSOH KROGHU ZDV
VXVSHQGHG IURP WKH PDJQHWLF EDODQFH XVLQJ D WLWDQLXP URG 6DPSOH KROGHU DQG WKH
WLWDQLXPLVHQFORVHGZLWKDQ,QFRQHOFDVLQJ5HDFWRUV\VWHPLVKHDWHGZLWKDQHOHFWULFDO
IXUQDFH SURJUDPPHG ZLWK D FRPSXWHU 97, )ORZ VRIWZDUH ZDV XVHG WR VHW WKH WHVW
SDUDPHWHUVWHPSHUDWXUHIRUFDOFLQDWLRQDQGK\GUDWLRQWHPSHUDWXUHHTXLOLEULXPFULWHULRQ
IRUWKHWHVWGDWDORJJLQJLQWHUYDOHWF)ORZRIJDVHVZDVFRQWUROOHGLQGHSHQGHQWO\XVLQJD
5XERWKHUP JDV PDQLIROG RSHUDWHG XVLQJ SQHXPDWLF YDOYHV )RU K\GUDWLRQ H[SHULPHQWV
QLWURJHQ ZDV XVHG DV WKH LQHUW JDV GXULQJ FDOFLQDWLRQ DQG DV D FDUULHU JDV GXULQJ VWHDP
LQMHFWLRQ
/LPHVWRQHVDPSOHEHLQJWHVWHGLQWKH7*$ZDVVXEMHFWHGWRFDOFLQDWLRQDQGVXEVHTXHQW
VWHDP K\GUDWLRQ 7KH VDPSOHV ZHUH KHDWHG IURP WR R& DQG KHOG DW R& IRU PLQXWHV DIWHU ZKLFK WKH\ ZHUH FRROHG IURP R& WR WKH K\GUDWLRQ WHPSHUDWXUH
+\GUDWLRQWHPSHUDWXUHZDVYDULHGIURPR&IRUSDUDPHWULFVWHDPSUHVVXUHVWXGLHV
&DOFLQDWLRQ RI WKH VDPSOHV ZDV SHUIRUPHG LQ 1 LQHUW DWPRVSKHUH $IWHU WKH
K\GUDWLRQ WHPSHUDWXUH KDG EHHQ UHDFKHG VWHDP LQMHFWLRQ ZDV VWDUWHG 6WHDP JHQHUDWLRQ
FRQVLVWHGRIDKLJKSUHFLVLRQV\ULQJHSXPS,6&2'0ZKLFKGHOLYHUHGZDWHUDWD
VHW IORZ UDWH LQWR WKH SUHKHDWHU ]RQH 3UHKHDWHU ]RQH FRQVLVWHG RI VWDLQOHVVVWHHO WXELQJ
ZLWK KHDWLQJ WDSHV RYHU LW DQG DSSURSULDWH LQVXODWLRQ 7KH WHPSHUDWXUH LQ WKH ]RQH ZDV
PDLQWDLQHGDWR&ZKLFKLQVWDQWDQHRXVO\FRQYHUWHGWKHLQIORZRIZDWHULQWRVWHDP
YRO WKH IORZ RI VWHDP EDODQFHG ZLWK 1 ZDV LQMHFWHG LQWR WKH UHDFWRU E\ WKH
SUHKHDWHU]RQH'HOLYHU\RIZDWHUWKURXJKWKHSXPSZDVSHUIRUPHGLQWKHLQWHUYDOVRI
PLQ IRU D GXUDWLRQ RI PLQ 7KLV KHOSHG UHJXODWH D FRQWLQXRXV IORZ RI VWHDP LQWR WKH
UHDFWRU ZLWKRXW IORRGLQJ WKH SUHKHDWHU ]RQH :DWHU IORZ ZDV VWRSSHG ZKHQ PRUH WKDQ
FRQYHUVLRQZDVREVHUYHG&RQYHUVLRQRI&D2WR&D2+LVFDOFXODWHGRQDPRODU
EDVLV,QVWDQWDQHRXVFRQYHUVLRQLVFRPSXWHGIURPWKHLQFUHDVHLQVRUEHQWZHLJKWGXHWR
WKHIRUPDWLRQRI&D2+/HW:&D2EHWKHLQVWDQWDQHRXVZHLJKWRIWKHVRUEHQW:R&D2EH
WKHZHLJKWRIWKHVRUEHQWDWWKHVWDUWRIWKHUHDFWLRQDQG0NLVWKHPROHFXODUZHLJKWRIWKH
PROHFXOH
)LJXUH5XERWKHUP0DJQHWLF6XVSHQVLRQ%DODQFH06%
)LJXUH7*$VHWXSLQWKHODERUDWRU\
&RQYHUVLRQ;&D2+ ሺ୛ƒି୛‘ƒሻ‫ƒ୑כ‬
୛‘ƒ‫ʹ୑כ‬
$LP RI WKH WKHUPRJUDYLPHWULF H[SHULPHQWV ZDV WR LQYHVWLJDWH VHYHUDO IDFWRUV DIIHFWLQJ
VWHDPK\GUDWLRQRIWKHVRUEHQWZKLFKLQFOXGHV
x 6WHDP SDUWLDO SUHVVXUH DQG RSHUDWLQJ WHPSHUDWXUH RI WKH UHDFWRU $W D SDUWLFXODU
RSHUDWLQJWHPSHUDWXUHWKHUDWHRIK\GUDWLRQRIWKHVRUEHQWZLWKVWHDPGHSHQGVRQ
WKH GULYLQJ IRUFH ZKLFK LV WKH GLIIHUHQFH EHWZHHQ RSHUDWLQJ VWHDP SUHVVXUH DQG
HTXLOLEULXPVWHDPSUHVVXUH3+2±3+2
x (IIHFW RI OLPHVWRQH RULJLQ 7R REVHUYH WKH EHKDYLRU RI RULJLQ RI OLPHVWRQH IRXU
GLIIHUHQWOLPHVWRQHVZHUHLQFOXGHGLQWKLVVWXG\IURPTXDUULHVLQDQGDURXQG2KLR
)L[HGEHGVWXGLHVIRUVWHDPK\GUDWLRQDQGFDOFLQDWLRQ
$Q H[LVWLQJ IL[HG EHG UHDFWRU V\VWHP ZDV PRGLILHG WR VWXG\ WKH VWHDP K\GUDWLRQ RI
FDOFLXPVRUEHQWV$SUHKHDWHUVHFWLRQZDVXVHGIRUFRQWLQXRXVVWHDPJHQHUDWLRQDQGIORZ
LQWRWKHIL[HGEHGUHDFWRU7KHUHDFWRULWVHOIFRQVLVWHGRIDF\OLQGULFDOFHUDPLFWXEH
FPORQJZLWKDQ,'RIFP$SSUR[LPDWHO\JUDPVRIFDOFLQHGVRUEHQWZDVXVHGIRU
WKHIL[HGEHGH[SHULPHQWV)LJXUHVKRZVWKHIL[HGEHGUHDFWRUVHWXSZLWKWKHGLIIHUHQW
VHFWLRQV ODEHOHG ZDWHU SXPS SUHKHDWHU UHDFWRU KHDWHU EDFN SUHVVXUH UHJXODWRU DQG
FRQGHQVHU$V\ULQJHSXPSWKHVDPHRQHXVHGIRUZDWHULQMHFWLRQLQWRWKHKLJKSUHVVXUH
7*$ IRU VWHDP K\GUDWLRQ H[SHULPHQWV ZDV XVHG WR LQMHFW FRQWLQXRXVO\ ZDWHU IRU
FRQWLQXRXVVWHDPJHQHUDWLRQ1ZDVXVHGDVDFDUULHUJDVIRUWKHVWHDPLQWRWKHUHDFWRU
)LJXUH)L[HGEHGUHDFWRUVHWXSIRUSUHVVXUL]HGVWHDPK\GUDWLRQRIVRUEHQWV
6DPHIL[HGEHGVHWXSZDVDOVRXVHGIRUWKHFDOFLQDWLRQVWXGLHVIRUVRUEHQWVVXEMHFWHGWR
GLIIHUHQW FDOFLQDWLRQ FRQGLWLRQV LQ WKH IL[HG EHG )RU WKLV H[SHULPHQWDO VHWXS VWHDP
LQMHFWLRQ SRLQW FRQGHQVHU DQG WKH EDFN SUHVVXUH UHJXODWRU ZHUH UHPRYHG 3DUWLFOH EHG
ZDV FUHDWHG XVLQJ D ORQJ TXDUW] F\OLQGULFDO WXEH ZLWK D SHUIRUDWHG TXDUW] SODWH DW WKH
ERWWRP:LWKGLPHQVLRQVRIPPIRUGLDPHWHUDQGPPWDOOWKHTXDUW]WXEHFDQ
KROGXSWRJRIIUHVKOLPHVWRQHVRUEHQW&D&2&HUDPLFUHDFWRUWXEHRIWKHIL[HGEHG
ZDVSDFNHGXVLQJTXDUW]FKLSVDQGTXDUW]ZRRO4XDUW]F\OLQGULFDOWXEHZDVSODFHGRYHU
WKH TXDUW] ZRRO 7KH WXEXODU TXDUW] UHDFWRU ZDV IDEULFDWHG IURP WKH JODVV EORZLQJ
ZRUNVKRS DW 268 ,W PLQLPL]HG WKH ORVV RI VDPSOH WKDW RFFXUV GXH WR WKH ILQHV LQ WKH
TXDUW]ZRRO
&KDSWHU5HVXOWVDQG'LVFXVVLRQ
3.1ReactionkineticsstudiesintheTGA
3DUDPHWULF VWHDP K\GUDWLRQ VWXGLHV ZHUH SHUIRUPHG XVLQJ D 5XERWKHUP 0DJQHWLF
6XVSHQVLRQ%DODQFH06%DWKHUPRJUDYLPHWULFDQDO\]HUDVGHVFULEHGLQGHWDLORQSDJH
XQGHU WKH H[SHULPHQWDO VHFWLRQ 6WHDP K\GUDWLRQ RI FDOFLXP VRUEHQWV ZDV
GHPRQVWUDWHGLQWKH.:WKVXESLORWSRVWFRPEXVWLRQ&&5SURFHVVXVLQJVXSHUKHDWHG
VWHDPIRUK\GUDWLRQDWR&LQDEHQFKVFDOHIOXLGL]HGEHG)RUDEHWWHUK\GUDWRUGHVLJQ
DQG SURFHVV LQWHJUDWLRQ WKHUPRJUDYLPHWULF VWXGLHV ZHUH SHUIRUPHG DW D SDUWLFXODU
WHPSHUDWXUH DQG VWHDP SUHVVXUH UDQJH 7KH HTXLOLEULXP EHWZHHQ VWHDP SDUWLDO SUHVVXUH
DQG WHPSHUDWXUH GLFWDWHV WKH PLQLPXP VWHDP SDUWLDO SUHVVXUH UHTXLUHG IRU D SDUWLFXODU
WHPSHUDWXUH )RU H[DPSOH VWHDP K\GUDWLRQ DW DWPRVSKHULF SUHVVXUH LV OLPLWHG LQ
WHPSHUDWXUH E\ WKH PLQLPXP WHPSHUDWXUH QHHGHG IRU VWHDP JHQHUDWLRQ IURP WKH
H[RWKHUPLF KHDW RI UHDFWLRQ DQG WKH PD[LPXP WHPSHUDWXUH DOORZDEOH IRU K\GUDWLRQ WR
RFFXU ZKLFK LV ƒ& . 7KH GHVLJQ RI H[SHULPHQWV IRU WKH SDUDPHWULF VWXG\ LV
GHVFULEHGLQ7DEOH7KH5XERWKHUPKLJKSUHVVXUH7*$LVXVHGWRFRQGXFWK\GUDWLRQ
WHVWV7KHDPRXQWRIVDPSOHXVHGLQWKHH[SHULPHQWVLVEHWZHHQJ1LVXVHG
DVDQLQHUWJDVDOVRDFWLQJDVDFDUULHUJDVIRUVWHDP$IORZUDWHRIVFFPZDVXVHG
DORQJ ZLWK VWHDP *DV IORZ UDWH DQG ZDWHU LQMHFWHG ZLWK D V\ULQJH SXPS DUH
FDOLEUDWHGIRUHDFKVHWSRLQWRIWHPSHUDWXUHDQGSUHVVXUHXVHGIRUVWHDPK\GUDWLRQ+LJK
SUHVVXUH H[SHULPHQWV ZHUH SHUIRUPHG XVLQJ D EDFN SUHVVXUH UHJXODWRU %35 WR FRQWURO
WKH7*$UHDFWRUSUHVVXUHDQGVHWEHIRUHEHJLQQLQJZDWHULQMHFWLRQ7DEOHSURYLGHVWKH
WHPSHUDWXUHDQGSDUWLDOSUHVVXUHRIVWHDPDWZKLFKIRXUVDPSOHVZHUHWHVWHG7KLVVWXG\
ZDVSHUIRUPHGLQWKHWKLUGTXDUWHUDQGLVLQFOXGHGKHUHWRGLVFXVVWKHSRVVLEOHFRUUHODWLRQ
RIVXUIDFHVWXGLHVDQGUHDFWLYLW\RIWKHVRUEHQWVWHVWHGLQWKH7*$
7DEOH'HVLJQRIH[SHULPHQWVIRUSDUDPHWULFVWHDPK\GUDWLRQVWXGLHV
7HPS
6WHDPSUHVVXUH3
R
&
DWP
+2
3+2 DWP
&D2+2
&D2+
3+2 3+2 3+2
3+2 7HPSHUDWXUHR&
)LJXUH(TXLOLEULXPFXUYHRIVWHDPSDUWLDOSUHVVXUHDQGUHDFWLRQWHPSHUDWXUH
(IIHFWRIWHPSHUDWXUH
7KH WHPSHUDWXUH IRU SHUIRUPLQJ WKH VWHDP K\GUDWLRQ UHDFWLRQ VKRXOG EH DV KLJK DV
SRVVLEOH WR PD[LPL]H KHDW UHFRYHU\ 7KH HFRQRPLFV RI SRVWFRPEXVWLRQ FDUERQ FDSWXUH
XVLQJFDOFLXPORRSLQJSURFHVVFRXOGEHLPSURYHGLIWKHVWHDPK\GUDWLRQRIWKHFDOFLXP
VRUEHQWLV SHUIRUPHG DW WHPSHUDWXUHV FRPSDUDEOH WR WKDW RI WKHFDUERQDWRU %HFDXVH WKH
K\GUDWLRQ RI FDOFLXP R[LGH LV D KLJKO\ H[RWKHUPLF UHDFWLRQ KLJKTXDOLW\ KHDW FDQ EH
REWDLQHG IURP WKH K\GUDWRU DW D KLJKHU WHPSHUDWXUH LI WKH K\GUDWRU LV RSHUDWHG XQGHU
HOHYDWHGSUHVVXUH7KLVKHDWFRXOGWKHQEHLQWHJUDWHGLQWRWKHSURFHVVWRUHGXFHWKHHQHUJ\
LPSDFWRQWKHSURFHVVDQGSRWHQWLDOO\UHGXFHFDUERQFDSWXUHFRVWV7HPSHUDWXUHVKLJKHU
WKDQ R& VSHFLILFDOO\ R& DQG R& ZHUH VHOHFWHG IRU 7*$ VWXGLHV (TXLOLEULXP
SDUWLDOSUHVVXUHRIVWHDPDWWKHVHWHPSHUDWXUHVDUHDQGDWPUHVSHFWLYHO\7*$
VWXGLHV ZHUH SHUIRUPHG DW SDUWLDO SUHVVXUHV JUHDWHU WKDQ DWP 0D[LPXP SDUWLDO
SUHVVXUHRIVWHDPXVHGLQWKHVHVWXGLHVLVDWP7KHFRVWRIVWHDPSURGXFWLRQLQFUHDVHV
DV WKH SDUWLDO SUHVVXUH RI VWHDP LV LQFUHDVHG ,W FRXOG EH FRPSHQVDWHG IRU WKH K\GUDWRU
RSHUDWLQJDWWHPSHUDWXUHVDURXQGR&DOORZLQJIRUDVXSHUKHDWHGVWHDPJHQHUDWLRQE\
GLUHFWO\ XWLOL]LQJ WKH KHDW HYROYHG IURP WKH H[RWKHUPLF K\GUDWLRQ UHDFWLRQ 7KLV PD\
SRVLWLYHO\DIIHFWWKHSURFHVVVLPXODWLRQVRIWKH&&5SURFHVVE\SRWHQWLDOO\UHGXFLQJWKH
HQHUJ\SHQDOW\LQGXFHGE\WKHFDOFLQHU$OVRDVWKHFDSWXUHFDSDFLW\RIWKHVRUEHQWVZLOO
EHUHWDLQHGOHVVHUVROLGFLUFXODWLRQZLOOEHUHTXLUHGWKXVGHFUHDVLQJZKLFKLPSOLHVORZHU
HQHUJ\ IRU WKH FDOFLQHU 7KXV KLJKHU WHPSHUDWXUH RI WKH K\GUDWRU LV H[SHFWHG WR KDYH D
SRVLWLYHLPSDFWRQWKHRYHUDOOSURFHVVHIILFLHQF\DQGHFRQRPLFV
6WHDP K\GUDWLRQ LQ WKH 7*$ LV VORZHU DV WKH WHPSHUDWXUH LQFUHDVHV 7KLV FRXOG EH
DWWULEXWHG WR WKH GHFUHDVLQJ GULYLQJ IRUFH DV WKH UHDFWLRQ LV SHUIRUPHG DW KLJKHU
WHPSHUDWXUHV IRU VDPH VWHDP SDUWLDO SUHVVXUH $W R& HTXLOLEULXP VWHDP SUHVVXUH LV
DWPZKLOHDWR&HTXLOLEULXPVWHDPSUHVVXUHLVDWP(IIHFWRIWHPSHUDWXUHRQ
WKHUDWHRIVWHDPK\GUDWLRQZDVVWXGLHGIRUWZRVWHDPSUHVVXUHVDWPDQGDWP7KH
UDWH RI WKH UHDFWLRQ FRPSXWHG DW WKHVH WHPSHUDWXUHV LQGLFDWH WKDW VWHDP K\GUDWLRQ RI
FDOFLXP R[LGH LV WZLFH DV IDVW DW R& WKDQ DW R& IRU 3+2 DWP 7KH UDWH RI
UHDFWLRQ DW GLIIHUHQW WHPSHUDWXUHV LV VKRZQ LQ )LJXUH )LJXUH DQG )LJXUH 5HDFWLRQ DW R& IRU VWHDP SUHVVXUH FORVH WR DWP VKRZV WKDW DV WKH SUHVVXUH LV
VOLJKWO\LQFUHDVHGIURPDWPWRDWPWKHUHLVDVLJQLILFDQWLQFUHDVHLQWKHK\GUDWLRQ
UDWH7KLVLQGLFDWHVDQRQOLQHDURUGHURIWKH UHDFWLRQZUWVWHDPSUHVVXUHH[SODLQHG LQ
GHWDLO LQ WKH IROORZLQJ VHFWLRQ 7KLV HIIHFW KDV EHHQ REVHUYHG LQ RQH RI WKH VWXGLHV IRU
VWHDPK\GUDWLRQDWKLJKWHPSHUDWXUHa.
3 +2
$70
&219(56,21;
GHJ&
7,0(0,187(
GHJ&
GHJ&
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWPDQGUHDFWLRQ
WHPSHUDWXUHR&
3 +2
$70
&219(56,21
GHJ&
GHJ&
7,0(0,187(
GHJ&DWP
GHJ&DWP
GHJ&
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWPDQGUHDFWLRQ
WHPSHUDWXUHR&
3 +2
$70
&219(56,21;
GHJ&
7,0(0,187(
GHJ&
GHJ&
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWPDQGUHDFWLRQ
WHPSHUDWXUHR&
(IIHFWRIVWHDPSDUWLDOSUHVVXUHRQUHDFWLRQUDWH
$VWKHSDUWLDOSUHVVXUHRIVWHDPLQFUHDVHVWKHUDWHRIK\GUDWLRQDOVRLQFUHDVHV7KLVLVGXH
WRWKHLQFUHDVHLQWKHGULYLQJIRUFH3+2±3+26WHDPK\GUDWLRQDWSUHVVXUHVJUHDWHU
WKDQDWPFRXOGEHIDYRUDEOHIRUWKHHFRQRPLFVRIWKHFDOFLXPORRSLQJSURFHVVDVLWZLOO
DOORZWKHK\GUDWRUWREHRSHUDWHGEHWZHHQWKHWHPSHUDWXUHVRIƒ&0RGLILFDWLRQV
PDGH RQ WKH KLJKSUHVVXUH 7*$ LQ WKLV TXDUWHU IL[HG WKH SUREOHP RI LQFRPSOHWH
FRQYHUVLRQGXULQJVWHDPK\GUDWLRQDQGHQVXUHGFRQWLQXRXVVWHDPLQMHFWLRQLQWKHUHDFWRU
7KXV D QHZ VHW RI H[SHULPHQWV ZHUH SHUIRUPHG IRU WKUHH WHPSHUDWXUHV DQG
R& 6WHDP SUHVVXUHV XVHG IRU WKHVH WHPSHUDWXUHV DUH JLYHQ LQ 7DEOH 5HVXOWV
REWDLQHGIURPWKHVHH[SHULPHQWVDUHLQWHUHVWLQJDVWKH\KDYHUHYLVHGWKHHDUOLHUHVWLPDWH
RI UHVLGHQFH WLPH IRU FRQYHUVLRQ LQ WKH 7*$ $ ODUJH QXPEHU RI GDWD SRLQWV ZHUH
JHQHUDWHGIRUHDFKUXQDQGUHDFWLRQFRQYHUVLRQRFFXUVXQGHUDPRUHVWDEOHVWHDG\VWHDP
LQMHFWLRQ WKDQ EHIRUH )RU GHWHUPLQLQJ WKH RUGHU RI WKH UHDFWLRQ ZUW VWHDP SDUWLDO
SUHVVXUHDGHWDLOHGVWXG\ZLWKVL[SUHVVXUHGDWDSRLQWVZDVSHUIRUPHGDWR&)LJXUH
VWDUWLQJDWDWPDQGLQFUHDVLQJVWHDPSUHVVXUHE\DWPXSWRDWP7KHUDWH
DQG VWHDP SUHVVXUH UHODWLRQVKLS REWDLQHG DW WKLV WHPSHUDWXUH VKRZ D SRZHU ODZ
UHODWLRQVKLSZLWKUHDFWLRQRUGHURIa6RPHRIWKHPRGLILFDWLRQVGRQHRQWKHLQVWUXPHQW
LQFOXGH XQLIRUP KHDWLQJ RI WKH HQWLUH VHFWLRQ WKURXJK ZKLFK JDV FDUULHV WKH VWHDP IURP
SUHKHDWHUWRWKHUHDFWRU6WHDPFRQFHQWUDWLRQZDVOLPLWHGWRZLWK1JDVDVEDODQFH
7KXVZDWHUIORZUDWHIURPWKHV\ULQJHSXPSZDVVOLJKWO\OHVVHU7KHWHPSHUDWXUHRIDOO
WKHVHFWLRQVRIWKHSUHKHDWHUWRSDQGPLGGOHSRUWLRQRIWKH7*$UHDFWRUZDVPHDVXUHGWR
HQVXUH VXSHUKHDWHG VWHDP DW KLJKHU SUHVVXUHV )RU VWHDP SUHVVXUHV MXVW RYHU DWP
VDWXUDWLRQWHPSHUDWXUHRIVWHDPH[FHHGVR&
$W R& HTXLOLEULXP VWHDP SUHVVXUHLVFORVHWRDWP 7KXVWKHUHDFWLRQUDWHDW DWPLVVLJQLILFDQWO\VORZHUWKDQWKDWDWDWP,WWDNHVFORVHWRPLQXWHVIRUFRPSOHWH
FRQYHUVLRQRIWKHDYDLODEOH&D2)RU3+2RIDWPWKHVDPHUHDFWLRQLVFRPSOHWHGLQ
OHVVWKDQPLQXWHV$WDWPWKHUHDFWLRQLVLQLWLDOO\IDVWHU7*$GDWDVKRZLQJ
FRQYHUVLRQ LQ OHVV WKDQ D PLQXWH +RZHYHU LWV SURJUHVVLRQ LV VORZHU DW KLJKHU
FRQYHUVLRQV DQG JRHV WR FRPSOHWLRQ LQ DERXW WKH VDPH WLPH DV WKH RQH SHUIRUPHG DW DWPDVVHHQLQ)LJXUH
$W R& HTXLOLEULXP VWHDP SUHVVXUHLVDWP7KXVVWHDPK\GUDWLRQFDUULHGRXW DW
SUHVVXUHVKLJKHUWKDQDWP7KHUHDFWLRQLVDOPRVWWZLFHDVIDVWDWDVWHDPSUHVVXUHRI
DWPDVFRPSDUHGWRWKHUHDFWLRQSHUIRUPHGDWDWP7KHUDWHRIWKHUHDFWLRQGRHVQRW
YDU\WRDODUJHH[WHQWIURPDWPWRDWP+RZHYHUWKHUHDFWLRQLVVLJQLILFDQWO\IDVWHU
DWDWPDQGDWPDVVHHQLQ)LJXUH
&
7 5;1
;
DWP
7,0(0,187(
DWP
DWP
DWP
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DQGDWP
DQGUHDFWLRQWHPSHUDWXUHR&
7 5;1
&
;
DWP
DWP
7,0(0,187(
DWP
DWP
DWP
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2DWP
DQGUHDFWLRQWHPSHUDWXUHR&
75;1 R&
&RQYHUVLRQ
DWP
DWP
WLPHPLQXWH
DWP DWP DWP
DWP
)LJXUH6WHDPK\GUDWLRQVWXGLHVRI3*VRUEHQWIRU3+2
DWPDQGUHDFWLRQWHPSHUDWXUHR&
.LQHWLFVRIVWHDPK\GUDWLRQ
(PSLULFDOGDWDREWDLQHGIRUGLIIHUHQWVWHDPSDUWLDOSUHVVXUHVDWGLIIHUHQWWHPSHUDWXUHVZDV
DQDO\]HGDQGSORWWHGWRJHWKHUWRHPSLULFDOO\FRPSXWHWKHRUGHURIWKHUHDFWLRQ$VVXPLQJ
DSRZHUODZUHODWLRQVKLSEHWZHHQUDWHRIWKHUHDFWLRQDQG3+2±3+2ZLWKSRZHUµQ¶
WKHYDOXHIRUQFDQEHFRPSXWHGDVIROORZV
Q
ሺ௟௢௚ሺି௥ƒͳሻȂ௟௢௚ሺି௥ƒʹሻሻ
ሺ௟௢௚ሺ௉ʹȂ௉ȗʹሻͳି௟௢௚ሺ௉ʹȂ௉ȗʹሻʹሻ
)URPWKHSORWVKRZQLQ)LJXUHWKHRUGHURIWKHUHDFWLRQZUW3+2±3+2LVa
7KXVWKHUDWHFRQVWDQWIRUVWHDPK\GUDWLRQFDQEHJLYHQDVIROORZV
N ି௥ƒ
൫௉ʹȂ௉ȗʹ൯ʹ
5DWHFRQVWDQWFRPSXWHGIRUHDFKVWHDPSUHVVXUHDQGWKHWHPSHUDWXUHLVJLYHQLQ7DEOH
5DWHV
5DWH9V'HOWD3#GHJ&
5DWH9VGHOWD3#GHJ&
3+2 3+2
5DWH9V'HOWD3#GHJ&
)LJXUH5DWHRIVWHDPK\GUDWLRQRI3*VRUEHQWVZUWVWHDPSUHVVXUH
7DEOH5DWHFRQVWDQWIRUDOOWHPSHUDWXUHVDQGVWHDPSUHVVXUHV
5HDFWLRQ
7HPSHUDWXUH75[Q
R&
6WHDP3UHVVXUH
3+2DWP
5DWH&RQVWDQWN
03DV
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(
(TXDWLRQ5DWHHTXDWLRQIRUVWHDPK\GUDWLRQ
N $H[S(D57 UD3+2±3+2
7KXVWKH$UUKHQLXVSORWRIUDWHFRQVWDQWNREWDLQHGIURP7DEOHLVVKRZQ
LQ)LJXUH
5DWHFRQVWDQWNV 03D
(
$
(
V 03D
(D N-PRO
(
(
(
(
(
(
(
7HPSHUDWXUH.
UDWHFRQVWDQW9V7
/LQHDUUDWHFRQVWDQW9V7
)LJXUH$UUKHQLXVSORWIRUUDWHFRQVWDQWIRUVWHDPK\GUDWLRQUHDFWLRQ
7KXV WKH DFWLYDWLRQ HQHUJ\ LV FRPSXWHG WR EH .-PRO IURP WKH H[SHULPHQWDO
FDOFXODWLRQV
6RUEHQWFKDUDFWHUL]DWLRQDQGUHDFWLYLW\VWXGLHV
6XUIDFHPRUSKRORJ\DQGSRUHGLVWULEXWLRQVWXGLHVZHUHSHUIRUPHGLQWKH4XDQWDFKURPH
129$ H VHULHV DQDO\]HU XVLQJ WKH %(7 PHWKRG DV GHVFULEHG LQ VHFWLRQ 1LWURJHQSK\VLVRUSWLRQVWXGLHV3RUHVL]HGLVWULEXWLRQZDVREWDLQHGXVLQJWKH%-+SRUH
VL]HGLVWULEXWLRQPHWKRG7KHVHVWXGLHVZHUHSHUIRUPHGIRUOLPHVWRQHVDPSOHVLQGLIIHUHQW
IRUPV7KHKLJKFDOFLXPVDPSOHPRVWO\&D&2IUHVKVRUEHQWF&D2K\GUDWHGIRUP
PRVWO\&D2+DQGVRUEHQWGHULYHGIURPK\GUDWHGVDPSOHK&D27KHVXUIDFHDUHD
RIWKHVDPSOHVLQWKHVHIRUPVREWDLQHGIURPWKH%UDXQQHDXU(OPHWW7HOOHU%(7PHWKRG
LVVKRZQLQ)LJXUH6XUIDFHDUHDRIF&D2FDOFLQHGVRUEHQWLVLPSRUWDQWIRULQWKH
LQLWLDO F\FOHV RI VROLGV FLUFXODWLRQ DV LW UHSUHVHQWV WKH DYDLODEOH VXUIDFH IRU WKH UHDFWLRQ
ZLWK&2IURPWKHIOXHJDV$IWHUF\FOHVZKHQWKHUHDFWLYLW\FDUERQGLR[LGHVWDUWV
JRLQJGRZQRZLQJWRVLQWHULQJGXULQJFDOFLQDWLRQVROLGVFLUFXODWLRQWKURXJKWKHK\GUDWRU
FRXOG EH VWDUWHG 7KXV VXUIDFH DUHD SRVWK\GUDWLRQ DQG RI WKH VRUEHQWV GHULYHG IURP
&D2+LVDQLPSRUWDQWLQGLFDWLRQRIWKHUHDFWLYDWLRQRIWKHVRUEHQWV7KXV%(7VWXGLHV
IRU WKHVH WZR IRUPV LV WKXV FULWLFDO 6XUIDFH VWXGLHV DQG SRUH YROXPH VWXGLHV DUH WKH
LQGLFDWRUV RI UHDFWLYDWLRQ RI WKH VRUEHQW DV WKH VXUIDFH EHFRPHV URXJK DQG GHYHORSV
FUDFNV5HDFWLRQZLWKZDWHUVWHDPFDXVHVLQZDUGGLIIXVLRQRIZDWHULQWKHVRUEHQWZKLFK
H[SDQGVWKHSRUHVRQWKHVXUIDFH7KLVSRUHYROXPHH[SDQVLRQDOORZVWKHODUJHU&2WR
SHQHWUDWHWKHVRUEHQWVXUIDFHGXULQJUHFDUERQDWLRQ
6XUIDFH$UHDPSHUJ
2ULJLQDO
F&D2
)/
+\GUDWHG
K&D2'HJDVVHG
'HJDVVHG&
&
3*
$$
($
)LJXUH6XUIDFHDUHDXVLQJ%(7PHWKRGIRUQLWURJHQSK\VLVRUSWLRQVWXGLHVRI
3*)/$$DQG($VRUEHQWV
)URP)LJXUHLWFDQEHVHHQWKDWWKHVXUIDFHDUHDRIVRUEHQWVGHULYHGIURPFDOFLXP
K\GUR[LGH K&D2 LV WLPHV PRUH WKDQ WKDW RI WKH FDOFLXP R[LGH GHULYHG GLUHFWO\
IURPFDOFLXPFDUERQDWHF&D27KHHIIHFWRIK\GUDWLRQRQSDUWLFOHVL]HGLVWULEXWLRQIRU
WKH*UD\PRQWOLPHVWRQH3*VDPSOHKDVEHHQGRFXPHQWHGLQWKHHDUOLHUVWXGLHV/DUJH
LQFUHDVHLQWKHVXUIDFHDUHDSRVWK\GUDWLRQLVDQLPSRUWDQWLQGLFDWRURIWKHUHDFWLYDWLRQRI
WKH VRUEHQW VXUIDFH E\ HIIHFWLYH PLWLJDWLRQ RI GHWULPHQWDO VLQWHULQJ HIIHFW FDXVHG E\
FDOFLQDWLRQ6WHDPK\GUDWLRQFDXVHVWKHH[SDQVLRQRISRUHVLQWKHVRUEHQWVGHULYHGIURP
FDOFLXPK\GUR[LGHK&D23RUHYROXPHRIK&D2LVWLPHVWKDWRIF&D2VRUEHQWV
7KLV YROXPHWULF H[SDQVLRQ RFFXUV GXH WR GLIIHUHQFH LQ PROHFXODU VL]H RI &D2+ DQG
&D2)LJXUHVKRZVWKHSRUHYROXPHRIWKHVRUEHQWVREWDLQHGIURPWKHVDPHVWXG\
7KHUHDFWLYDWLRQHIIHFWGXHWRK\GUDWLRQZRXOGEHVLPLODUZLWKVWHDPK\GUDWLRQ0XOWLSOH
VRUEHQW UHDFWLYLW\ VWXGLHV LQ WKH 7*$ DW R& DQG 3+2 RI DWP LV VKRZQ LQ )LJXUH
5DWH RI VWHDP K\GUDWLRQ RI VRUEHQW LV WKH KLJKHVW IRU 3* DQG ORZHVW IRU $$ 7KHVH
VRUEHQWVZHUHVXEMHFWHGWRVWHDPK\GUDWLRQIRUWKHILUVWWLPH7KXVWKHVXUIDFHDUHDRIWKH
FDOFLQHGVRUEHQWF&D2FRXOGEHFRUUHODWHGZLWKWKHUHDFWLRQUDWH6XUIDFHDUHDRI3*LV
KLJKHVW IRU F&D2 VRUEHQW DQG WKDW RI ($ LV WKH ORZHVW 7*$ VWHDP K\GUDWLRQ
H[SHULPHQWV VKRZ WKH IROORZLQJ RUGHU IRU WKH UDWH RI K\GUDWLRQ 3* ! )/ ! ($ ! $$
7KLVVWXG\ZDVSHUIRUPHGDWDORZHUVWHDPSDUWLDOSUHVVXUHDWPDQGR&
325(92/80(FFJ
2ULJLQDO
F&D2
3*
)/
+\GUDWHG
K&D2'HJDVVHG
'HJDVVHG&
&
($
$$
)LJXUH3RUHYROXPHRI3*)/$$DQG($VRUEHQWVXVLQJ%-+SRUHVL]H
GLVWULEXWLRQVWXGLHV
&219(56,21;
7,0(0,187(
)/
($
3*
$$
)LJXUH6RUEHQWUHDFWLYLW\VWXGLHVIRU3*)/$$DQG($DWR&DQG3+2
DWP
(IIHFWRIXSVWUHDPFDOFLQDWLRQFRQGLWLRQVRQVRUEHQWUHDFWLYLW\
8SVWUHDP FDOFLQDWLRQ FRQGLWLRQV PD\ DIIHFW WKH UHDFWLYLW\ RI VRUEHQWV WRZDUGV VWHDP
ZKHQK\GUDWHG7RVHHWKHHIIHFWRIFDOFLQDWLRQRQ7*$UHDFWLYLW\RIVRUEHQWVOLPHVWRQH
VDPSOH3*ZDVFDOFLQHGLQWKHIL[HGEHGDWDQGR&XQGHUSDUWLDOFRPSOHWH
&2DLU DWPRVSKHUH &RQGLWLRQV RI DLU&2 PL[WXUH ZHUH GHWHUPLQHG IURP WKH
WKHUPRG\QDPLFVRIFDOFLQDWLRQ7KXVIRUR&FDOFLQDWLRQZDVSHUIRUPHGXQGHU
DLU$WR&&2±DLUE\YROZDVXVHG(TXLOLEULXP&2FRQFHQWUDWLRQDW
R& LV FORVH WR DWP $W D WHPSHUDWXUH VOLJKWO\ DERYH R& &2
DWPRVSKHUH ZDV XVHG IRU FDOFLQDWLRQ (TXLOLEULXP SDUWLDO SUHVVXUH RI &2 LV DWP DW
R&7KLVHQVXUHGVWHDG\LVRWKHUPDOFDOFLQDWLRQRIWKHVDPSOHFDXVLQJKDUGEXUQLQJRI
WKHVDPSOHZKLFKLVPRUHH[SRVHGWRWKHKHDWHGVXUIDFHVRIWKHUHDFWRUWXEH7KHFRUHRI
WKHEHGUHPDLQVXQFDOFLQHGDWR&DQGSDUWLDOO\FDOFLQHGDWR&+RZHYHUDWR&
PRUH WKDQ RI WKH VDPSOH LV FDOFLQHG &DOFLQDWLRQ H[SHULPHQWV ZHUH SHUIRUPHG LQ
IL[HG %HG VHWXS XVLQJ DQ 07, &RUSRUDWLRQ KLJKWHPSHUDWXUH WXEH IXUQDFH $ TXDUW]
UHDFWRUZDVSODFHGLQWKHFHQWHURIWKHFHUDPLFWXEHRIDLQORQJZLWKDQ,'RILQ
DQGWKHERWWRPSDFNHGZLWKTXDUW]FU\VWDOV$WWKHERWWRPRIWKHTXDUW]WKHUHDFWRUZDVD
SRURXVSODWHWRVXSSRUWWKHVROLGV$SSUR[LPDWHO\JUDPVRI3*OLPHVWRQHZDVXVHGIRU
WKH IL[HG EHG H[SHULPHQWV 7KH H[SHULPHQWV ZHUH SHUIRUPHG DW WKUHH GLIIHUHQW
WHPSHUDWXUHVIRUGLIIHUHQW&2SDUWLDOSUHVVXUHVEDVHGRQWKHFDOFLQDWLRQWKHUPRG\QDPLF
HTXLOLEULXPFXUYH7KHFRQGLWLRQVDQGH[WHQWRIFDOFLQDWLRQDUHVKRZQLQ7DEOH$Q
0)&ZDVXVHGWRFRQWUROWKHJDVIORZRIDLUDQG&2LQWKHUHDFWRU)LJXUHVKRZVWKH
IL[HG EHG UHDFWRU VHWXS ZLWK D SUHKHDWHU UHDFWRU DQG HOHFWULF IXUQDFH 6LQFH WKH
H[SHULPHQWDO VHWXS LV FRPSDUDEOH WR WKH VL]H RI WKH 7*$ VHWXS D JDV IORZ UDWH RI VFFPZDVXVHGWRFDOFLQHWKHVDPSOH0DVV)ORZ&RQWUROOHUV0)&ZHUHXVHGWRFRQWURO
WKHIORZUDWHVRIDLUDQG&2VHQWWRWKHIL[HGEHG7KHWHPSHUDWXUHLQWKHIXUQDFHZDV
UDPSHG XS LQ WZR VWDJHV WR WKH VHW SRLQW 7KH VDPSOHV ZHUH FDOFLQHG IRU KRXUV $W
ƒ&VFFPRIDLUIORZUDWHZDVXVHG$Wƒ&DIORZUDWHRIVFFP&2DQG
VFFP DLU ZDV XVHG IRU FDOFLQDWLRQ $W ƒ& WKH VDPSOHV ZHUH FDOFLQHG LQ &2
DWPRVSKHUH
7DEOH)L[HGEHGFDOFLQDWLRQFRQGLWLRQV
3*EHG
FDOFLQDWLRQ
$LUPOPLQ
&2POPLQ
([WHQWRI
FDOFLQDWLRQ
R&
R&
R&
1LWURJHQ SK\VLFVRUSWLRQ VWXGLHV ZHUH SHUIRUPHG IRU WKH VRUEHQWV FDOFLQHG LQ WKH IL[HG
EHGXQGHUWKHFRQGLWLRQVJLYHQLQ7DEOH%(7PHWKRGIRUVXUIDFHFKDUDFWHUL]DWLRQDQG
%-+ SRUH VL]H GLVWULEXWLRQ PHWKRG ZDV XVHG WR REWDLQ WKH VXUIDFH DQDO\VLV DQG SRUH
YROXPH RI WKH VRUEHQWV DIWHU FDOFLQDWLRQ 5HVXOWV DUH SUHVHQWHG DORQJ ZLWK WKH FKDUW LQ
)LJXUH 5HVXOWV LQGLFDWH D GHFUHDVH LQ WKH VXUIDFH DUHD DQG SRUH YROXPH RI WKH
VRUEHQWV DV WKH FDOFLQDWLRQ WHPSHUDWXUH LQFUHDVHV 7KLV LV DQ LQGLFDWLRQ RI WKH
GHWHULRUDWLQJHIIHFWRIVLQWHULQJRIWKHVRUEHQWGXHWRKDUGEXUQLQJ 7KLV PD\ DIIHFW WKH
UHDFWLYLW\ IRU VWHDP K\GUDWLRQ LQ WKH 7*$ 2QJRLQJ VWXGLHV IRU WKH HIIHFW RI XSVWUHDP
FDOFLQDWLRQFRQGLWLRQVRQWKHUHDFWLYLW\RIVWHDPK\GUDWLRQZLOOEHSUHVHQWHGLQWKHQH[W
TXDUWHUO\UHSRUW
(
(
(
3RUH9ROXPFFJ
6XUIDFHDUHDPJ
(
(
(
(
(
(
(
)%GHJ&
6XUIDFHDUHDPJ
3RUH9ROXPHFFJ
)%GHJ&
)%GHJ&
(
)LJXUH1LWURJHQSK\VLVRUSWLRQVWXGLHVIRU3*VRUEHQWFDOFLQHGDWDQG
R&LQWKHIL[HGEHGUHDFWRU
&KDSWHU&RQFOXVLRQV
3DUDPHWULF 7KHUPRJUDYLPHWULF VWXGLHV IRU KLJKHU K\GUDWRU UHDFWLRQ WHPSHUDWXUH DQG
HOHYDWHGVWHDPSDUWLDOSUHVVXUHKDVSURGXFHGUHOLDEOHUHDFWLRQNLQHWLFVUHVXOWVWKDWFRXOG
EH DSSOLHG IRU D EHWWHU GHVLJQ RI WKH K\GUDWRU XVLQJ VPDOOHU UHVLGHQFH WLPHV KLJKHU
WHPSHUDWXUHDQGDSSURSULDWHVWHDPSDUWLDOSUHVVXUH7KURXJKWKLVVWXG\LWLVREVHUYHGWKDW
WKHK\GUDWRUFRXOGEHRSHUDWHGDWDWHPSHUDWXUHFORVHWRR&ZLWKVWHDPSDUWLDOSUHVVXUH
DWP WR REWDLQ KLJKHU FRQYHUVLRQV LQ UHODWLYHO\ OHVV WLPH 7KH UHVLGHQFH WLPH IRU
QHDUFRPSOHWHFRQYHUVLRQGXULQJK\GUDWLRQLQWKH7*$YDULHGIURPVHFRQGVPLQ
WRVHFRQGVPLQIRU3*VRUEHQWDQGUHVLGHQFHWLPHDVKLJKDVVHFRQGV
PLQIRUVRUEHQWVVKRZLQJORZHUUHDFWLYLW\WRVWHDPDWORZHUVWHDPSDUWLDOSUHVVXUH7KLV
VKRZVWKDWDFRPPHUFLDOK\GUDWRUZLWKVWHDPLQSXWDUHVLGHQFHWLPHRIPLQ
VKRXOGJLYHIDLUO\ODUJHFRQYHUVLRQV!WKXVVDWLVIDFWRULO\UHDFWLYDWLQJWKHVRUEHQW
2UGHU RI WKH UHDFWLRQ ZLWK UHVSHFW WR WKH GULYLQJ IRUFH DYDLODEOH IRU UHDFWLRQ 3+2 ±
3+2 LV DSSUR[LPDWHO\ 7KH H[SHULPHQWDOO\ FRPSXWHG DFWLYDWLRQ HQHUJ\ IRU WKH
UHDFWLRQ LV N-PRO 7HPSHUDWXUH FRXOG EH LQFUHDVHG IXUWKHU WR R& XVLQJ D
VWHDP SUHVVXUH RI XQGHU WR DWP $W DQG R& WKH VWHDP SDUWLDO SUHVVXUH DW
HTXLOLEULXP LV DQG DWPUHVSHFWLYHO\7KH+LJKHURSHUDWLQJWHPSHUDWXUHRI WKH
K\GUDWRU ZLOO OHDG WR EHWWHU KHDW LQWHJUDWLRQ GXH WR H[WUDFWLRQ DQG XWLOL]DWLRQ RI KLJKHU
TXDOLW\ KHDW LQ WKH VWHDP WXUELQH 7KLV FXPXODWLYHO\ ZRXOG IXUWKHU GHFUHDVH WKH DOUHDG\
ORZHU HQHUJ\ SHQDOW\ RI WKH &&5 SURFHVV UHWURILWWHG LQ D FRDO SRZHU SODQW $OVR LW
GHFUHDVHV WKH VRUEHQW PDNHXS UHTXLUHPHQWV DQG DOVR WKH VROLGV FLUFXODWLRQ UDWHV GXH WR
UHSOHQLVKHGFDSWXUHFDSDFLW\RIWKHVRUEHQWLQWKHHDFKF\FOH+RZHYHURSHUDWLQJFRVWRI
WKH K\GUDWRU VKRXOG QRW EH WRR KLJK WR LQFUHDVH WKH HQHUJ\ SHQDOW\ RI WKH SURFHVV DV
SUHVVXUL]HGVXSHUKHDWHGVWHDPLVDQH[SHQVLYHXWLOLW\HVSHFLDOO\IRUDFRPPHUFLDOVFDOH
XQLW ZKHUH WKH DPRXQW RI VROLGV SURFHVVHG FRXOG EH LQ WKRXVDQGV RI WRQ SHU GD\ 7KXV
WKHUH PXVW EH D WUDGHRII ZLWK WKH RSHUDWLQJ FRQGLWLRQV RI WKH K\GUDWRU ,I WKH VWHDP
K\GUDWLRQRIWKHVRUEHQWVSRVLWLYHO\DIIHFWVWKHSURFHVVWRUHGXFHWKH&D&PROHUDWLRWR
FORVH WR WKHQ WKH SURFHVV KDV LPPHQVH HFRQRPLF DGYDQWDJHV RYHU RWKHU SRVW
FRPEXVWLRQFDUERQFDSWXUHWHFKQRORJLHVFXUUHQWO\LQXVHRUWKHGHYHORSPHQWVWDJH7KLV
HIIHFW LV SURSRVHG WR EH LQYHVWLJDWHG ZLWK ODE VFDOH IL[HG EHG FRQWLQXRXV PXOWLF\FOLF
WKUHH VWHS FDUERQDWLRQ FDOFLQDWLRQ K\GUDWLRQ VWXGLHV WKDW ZRXOG XVH WKH FRQGLWLRQV
REWDLQHGIURPWKH7*$VWXGLHVIRUK\GUDWLRQ
&KDSWHU)XWXUH:RUN
$63(1 VLPXODWLRQ VWXGLHV RQ WKH WKUHH VWHS &&5 SURFHVV VXJJHVW WKDW FDUERQ FDSWXUH
FDSDFLW\ RI WKH VRUEHQW LV KLJKO\ VHQVLWLYH WR WKH K\GUDWLRQ FRQYHUVLRQ 7KH H[WHQW RI
K\GUDWLRQ KDV D GLUHFW HIIHFW RQ WKH VRUEHQW UHDFWLYLW\ LQ WKH VXEVHTXHQW F\FOH
5HJHQHUDWLQJWKHVRUEHQWYLDK\GUDWLRQLVLPSRUWDQWWRPLQLPL]HWKH&D&PROHUDWLRIRU
WKHVDPHOHYHORIFDUERQVXOIXUUHPRYDOWKXVRSHUDWLQJWKHSURFHVVDWPXFKORZHUVROLGV
FLUFXODWLRQ UDWH $PRQJ RWKHU DGYDQWDJHV RI OHVVHU VROLGV FLUFXODWLRQ UDWH OLNH VPDOOHU
UHDFWRUV OHVVHU RSHUDWLQJ FRVWV DQG KLJKHU SURFHVVLQJ FDSDFLW\ OHVVHU FDOFLQHU HQHUJ\
UHTXLUHPHQWLVWKHVLQJOHPRVWVLJQLILFDQWDGYDQWDJH&DOFLQHUHQHUJ\UHTXLUHPHQWKDVWKH
KLJKHVW FRQWULEXWLRQ WR WKH RYHUDOO HQHUJ\ SHQDOW\ RI WKH SRVWFRPEXVWLRQ SURFHVV DV
FDOFLQDWLRQ LV D KLJKO\ HQGRWKHUPLF UHDFWLRQ DQG LV WKHUPRG\QDPLFDOO\ IHDVLEOH DW
WHPSHUDWXUHV!R&'HFUHDVLQJWKHFDOFLQHUVL]HFDQVLJQLILFDQWO\EULQJGRZQWKH
HQHUJ\ SHQDOW\ 0RUHRYHU WKH VWHDP UHTXLUHPHQW IRU K\GUDWLRQ LV DQRWKHU LPSRUWDQW
SDUDPHWHULQWKHHQHUJ\HIILFLHQF\RIWKHSURFHVV,WLVLPSRUWDQWWRPLQLPL]HWKHVWHDP
&DPROHUDWLRQIRUWKHSURFHVVWREHYLDEOH,IDSUHVVXUL]HGVWHDPK\GUDWRUFDQDFKLHYH
KLJKHU FRQYHUVLRQ LQ OHVVHU WLPH LW FDQ SRWHQWLDOO\ HQKDQFH WKH SURFHVV DQG
HQHUJ\HIILFLHQF\3UHOLPLQDU\WHFKQRHFRQRPLFDQDO\VLVRIWKH&&5SURFHVVVXJJHVWVD
LQFUHDVHLQWKH/HYHOL]HG&RVW2I(OHFWULFLW\/&2(DVFRPSDUHGWRWKHEDVHFDVH
$VXEFULWLFDO3&ERLOHUZLWKRXW&2FDSWXUHZDVVHOHFWHGDVWKHEDVHFDVH&&5SURFHVV
ZDV PRGHOHG RQ WKH VDPH EDVH FDVH VXEFULWLFDO 3& ERLOHU :KHQ DQ DPLQH VFUXEEHU LV
PRGHOOHG ZLWK WKH EDVH FDVH LW LQFUHDVHV WKH /&2( E\ 0RUHRYHU WKHVH SURFHVV
VLPXODWLRQV ZHUH GHVLJQHG IRU &2 UHPRYDO DGKHULQJ WKH 'HSDUWPHQW RI (QHUJ\
'2(VWDQGDUG:LWKWKHFXUUHQW(3$UHJXODWLRQVRIPLQLPXP&2UHPRYDOWKH
/&2(IRUFDUERQFDSWXUHXVLQJWKH&&5SURFHVVZRXOGQRWEHWRRKLJKDVFRPSDUHGWR
WKDWRIWKHQRFDUERQFDSWXUHFDVH7KXVWKHIL[HGEHGPXOWLF\FOLFVWXGLHVDUHLPSRUWDQW
WRNQRZKRZLQWHUPHGLDWHKLJKSUHVVXUHVWHDPK\GUDWLRQDIIHFWVWKHVRUEHQWUHDFWLYLW\LQ
PXOWLSOHF\FOHV
6XFFHVVIXOFRPSOHWLRQRIWKHSURSRVHGZRUNZLOOSURYLGHDVWURQJH[SHULPHQWDOEDVLVIRU
IXWXUH VFDOH XS RI WKH WKUHH VWHS FDUERQDWLRQFDOFLQDWLRQ SURFHVV DV D YLDEOH FDUERQ
FDSWXUHWHFKQRORJ\JLYHQLWVUHODWLYHHDVHRILQWHJUDWLRQZLWKWKHH[LVWLQJFRDOQDWXUDOJDV
ILUHGSRZHUSODQWV:LWKRXWVRDULQJXSWKHFRVWRIHOHFWULFLW\WRDODUJHH[WHQWWKH&&5
SURFHVV FRXOG EH DQ HFRQRPLFDO RSWLRQ WR PHHW WKH FXUUHQW (3$ UHJXODWLRQV 7KLV ODE
VFDOH PXOWLF\FOLF VWXG\ ZLOO JLYH YDOXDEOH LQIRUPDWLRQ DQG LQVLJKWV DERXW WKH VRUEHQW
UHDFWLYLW\ DQG SHUIRUPDQFH PHFKDQLFDO VWUHQJWK RI WKH VROLG VRUEHQW ZKHQ VXEMHFWHG WR
KLJKSUHVVXUH VWHDP UHDFWLYDWLRQ RSHUDELOLW\ DQG YLDELOLW\ RI WKH F\FOLF SURFHVV
7KHRUHWLFDOO\ D SUHVVXUL]HG VWHDP K\GUDWLRQ VKRXOG \LHOG IDYRUDEOH UHDFWLRQ NLQHWLFV
SURGXFHUHDFWLYHVRUEHQWVDQGUHGXFHWKHVROLGVFLUFXODWLRQUDWH+RZHYHUWKHUHH[LVWVD
WUDGHRII EHWZHHQ KLJK K\GUDWLRQ FRQYHUVLRQ VWHDP FRQVXPSWLRQ HQHUJ\ UHTXLUHG IRU
KLJKSUHVVXUH VWHDP JHQHUDWLRQ DQG WKH FRVW RI KLJKSUHVVXUH VXSHUKHDWHG VWHDP $OO
WKHVH SDUDPHWHUV ZLOO FRXOG EH MXGJHG ZLWK JUHDWHU UHOLDELOLW\ DQG FRQILGHQFH DIWHU WKH
FRPSOHWLRQRIWKLVVWXG\,IWKHFXUUHQWIL[HGEHGVHWXSDOORZVIRUWKHSURSRVHGF\FOHV
RI&&5SURFHVVWKLVGHPRQVWUDWLRQZLOOEHORQJHUWKDQWKHIL[HGEHGVWXGLHVFRQGXFWHGDW
268WLOOGDWH0XOWLF\FOLFIL[HGEHGVWXGLHVIRUWKUHHVWHS&&5SURFHVVZLWKK\GUDWLRQDW
DWPRVSKHULF SUHVVXUH DQG ORZHU WHPSHUDWXUH SHUIRUPHG LQ DW 268 FRXOG
UHDFKRQO\F\FOHV+RZHYHUWKLVZDVGXHWRORVVRIVDPSOHWDNHQRXWIRU7*$DQDO\VLV
DIWHU HYHU\ VWHS ,Q WKLV VWXG\ ZH SURSRVH WR SHUIRUP FDUERQDWLRQ DQG FDOFLQDWLRQ LQ
FRQWLQXRXVPRGHDQGK\GUDWLRQLQDGLVFRQWLQXRXVPRGH6DPSOHZRXOGEHWDNHQRXWIRU
7*$DQDO\VLVRQO\DIWHUK\GUDWLRQDIWHUDFRPSOHWHF\FOH7KXVLWVKRXOGEHSRVVLEOHWR
UHDFKWKHWDUJHWRIF\FOHV
2QHRIWKHDUWLFOHVIRUVWHDPK\GUDWLRQRIFDOFLXPVRUEHQWVIRUWKHSRVWFRPEXVWLRQ&2
FDSWXUHSURFHVVSUHGLFWVDQGGHVFULEHVDVKULQNLQJFRUHPRGHOIRUVWHDPK\GUDWLRQRIWKH
VRUEHQWV$FFRUGLQJWR%ODPH\HWDOK\GUDWLRQRFFXUVDWWKHLQWHUIDFHRIDSRURXVDQG
XQUHDFWHG &D2 FRUH DQG SRURXV &D2+ SURGXFW OD\HU 'LIIXVLRQ WKURXJK WKH EXON
SKDVH WR WKH SDUWLFOH VXUIDFH IROORZV WKH &KDSPDQ (QVNRQJ WKHRU\ 7KLV FRXOG EH
YHULILHG E\ FKDUDFWHUL]DWLRQ VWXGLHV RI WKH VRUEHQWV XVHG IRU SHUIRUPDQFH WHVWV LQ WKH
PXOWLF\FOLFVWXGLHV$ORQJZLWK%(7VXUIDFHDUHDDQG%-+SRUHVL]HGLVWULEXWLRQVWXGLHV
EXONSKDVHRIWKHVRUEHQWVFRXOGEHDQDO\]HGXVLQJ;5D\'LIIUDFWLRQ;5'WHFKQLTXHV
3DUWLFOH VXUIDFH DQG FRUH FRXOG EH DQDO\]HG XVLQJ DGYDQFHG WHFKQLTXHV OLNH ;5D\
3KRWRHOHFWURQ6SHFWURVFRS\;36GHSWKSURILOLQJWHFKQLTXHXVLQJ;36RU6FDQQLQJ,RQ
0DVV6SHFWURPHWU\6,06WHFKQLTXHV'HSWKSURILOLQJXVLQJ6,06FRXOGEHSDUWLFXODUO\
XVHIXOLQWKLVFDVHDVLWJLYHVWKHFRPSRVLWLRQRIWKHPDWHULDORQWKHVXUIDFHDVZHOODVWKH
FRUHE\HWFKLQJWHFKQLTXHV
7KXVWKHSURSRVHGVWXGLHVDUHH[SHFWHGWRYDOLGDWHIXUWKHUWKHFRQFOXVLRQVREWDLQHGIURP
WKH UHDFWLRQ NLQHWLFV VWXGLHV RI WKH VRUEHQWV DV ZHOO DV SDUWLFOH FKDUDFWHUL]DWLRQ VWXGLHV
6LJQLILFDQWRXWFRPHVDUHH[SHFWHGIURPWKHF\FOLFIL[HGEHGVWXGLHVRIWKHWKUHHVWHS&&5
SURFHVVXVLQJSUHVVXUL]HGVWHDPK\GUDWLRQ,QGHSHQGHQWVWXGLHVDW2KLR6WDWH8QLYHUVLW\
IRUWKHWHFKQRHFRQRPLFDQDO\VLVDQGHFRQRPLFYLDELOLW\RIWKHWKUHHVWHSSURFHVVZRXOG
XVHWKHUHDFWLRQNLQHWLFVUHVXOWVREWDLQHGIURPWKLVVWXG\IRUDEHWWHUSURFHVVPRGHOLQJRI
WKH K\GUDWRU $OVR KHDW UHFRYHU\ IURP WKH K\GUDWRU DW KLJK WHPSHUDWXUH ZLOO EH VWXGLHG
DQG LWV DSSOLFDWLRQ LQ WKH VWHDP WXUELQH F\FOH WR JHQHUDWH PRUH HOHFWULFLW\ ZLOO EH
VLPXODWHGE\PRGLI\LQJWKHH[LVWLQJ$63(13OXVVLPXODWLRQV
5HIHUHQFHV
1DWLRQDO2FHDQLFDQG$WPRVSKHULF$GPLQLVWUDWLRQ5HFHQW0RQWKO\0HDQ&2
'DWD)URP0DXQD/2$KWWSZZZHVUOQRDDJRYJPGFFJJWUHQGV
,QWHUQDWLRQDO(QHUJ\$JHQF\.H\:RUOG(QHUJ\6WDWLVWLFV
GRLHQ
86(QYLURQPHQWDO3URWHFWLRQ$JHQF\&DUERQ3ROOXWLRQ(PLVVLRQ*XLGHOLQHVIRU
([LVWLQJ6WDWLRQDU\6RXUFHV(OHFWULF8WLOLW\*HQHUDWLQJ8QLWV3DUW,,,
:DQJ:5DPNXPDU6:RQJ')DQ/66LPXODWLRQVDQGSURFHVV
DQDO\VLVRIWKHFDUERQDWLRQFDOFLQDWLRQUHDFWLRQSURFHVVZLWKLQWHUPHGLDWH
K\GUDWLRQFuel±
5RPDQR0&et al.3URFHVVVLPXODWLRQRI&DORRSLQJSURFHVVHVUHYLHZDQG
JXLGHOLQHVEnergy Procedia±
*XSWD+)DQ/6&DUERQDWLRQí&DOFLQDWLRQ&\FOH8VLQJ+LJK5HDFWLYLW\
&DOFLXP2[LGHIRU&DUERQ'LR[LGH6HSDUDWLRQIURP)OXH*DVInd. Eng. Chem.
Res.±
,\HU09*XSWD+6DNDGMLDQ%%)DQ/60XOWLF\FOLFVWXG\RQWKH
VLPXOWDQHRXVFDUERQDWLRQDQGVXOIDWLRQRIKLJKUHDFWLYLW\&D2Ind. Eng. Chem.
Res.±
5DPNXPDU6)DQ/6&DOFLXPORRSLQJSURFHVV&/3IRUHQKDQFHG
QRQFDWDO\WLFK\GURJHQSURGXFWLRQZLWKLQWHJUDWHGFDUERQGLR[LGHFDSWXUHEnergy
and Fuels±
3KDODN1'HVKSDQGH1)DQ/6,QYHVWLJDWLRQRIKLJKWHPSHUDWXUHVWHDP
K\GUDWLRQRIQDWXUDOO\GHULYHGFDOFLXPR[LGHIRULPSURYHGFDUERQGLR[LGHFDSWXUH
FDSDFLW\RYHUPXOWLSOHF\FOHVEnergy and Fuels±
3KDODN1:DQJ:)DQ/6&D2+%DVHG&DOFLXP/RRSLQJ3URFHVV
'HYHORSPHQWDW7KH2KLR6WDWH8QLYHUVLW\Chem. Eng. Technol.±
:DQJ:et al.6XESLORWGHPRQVWUDWLRQRIWKHFDUERQDWLRQ&DOFLQDWLRQUHDFWLRQ
&&5SURFHVV+LJKWHPSHUDWXUH&2DQGVXOIXUFDSWXUHIURPFRDOILUHGSRZHU
SODQWVInd. Eng. Chem. Res.±
5DPNXPDU6)DQ/67KHUPRG\QDPLFDQGH[SHULPHQWDODQDO\VHVRIWKH
WKUHHVWDJHFDOFLXPORRSLQJSURFHVVInd. Eng. Chem. Res.±
&RQQHOO'3et al.3URFHVVVLPXODWLRQDQGHFRQRPLFDQDO\VLVRIWKH&DOFLXP
/RRSLQJ3URFHVV&/3IRUK\GURJHQDQGHOHFWULFLW\SURGXFWLRQIURPFRDODQG
QDWXUDOJDVFuel±
/LQ6<6X]XNL<+DWDQR++DUDGD0'HYHORSLQJDQLQQRYDWLYH
PHWKRG+\3U5,1*WRSURGXFHK\GURJHQIURPK\GURFDUERQVEnergy Convers.
Manag.±
/LQ6+DUDGD06X]XNL<+DWDQR+3URFHVVDQDO\VLVIRUK\GURJHQ
SURGXFWLRQE\UHDFWLRQLQWHJUDWHGQRYHOJDVLILFDWLRQ+\3U5,1*Energy
Convers. Manag.±
0DQDJHU*77HFKQRORJ\1(%UHDXOW50DQDJHU3,QYHVWLJDWRU3
+\EULG&RPEXVWLRQ*DVLILFDWLRQ&KHPLFDOORRSLQJ&RDOSRZHUWHFKQRORJ\
GHYHORSPHQWFRQWDFWV
5L]HT*et al.)XHOIOH[LEOHJDVLILFDWLRQFRPEXVWLRQWHFKQRORJ\IRUSURGXFWLRQRI
K\GURJHQDQGVHTXHVWUDWLRQUHDG\FDUERQGLR[LGHOctober±DW
KWWSZZZRVWLJRYHQHUJ\FLWDWLRQVSURGXFWELEOLRMVS"RVWLBLG !
&XUUDQ*35LFH&+*RULQ(&DUERQ'LR[LGH$FFHSWRU*DVLILFDWLRQ
3URFHVV
-RKQVHQ.5\X+-*UDFH-5/LP&-6RUSWLRQHQKDQFHGVWHDP
UHIRUPLQJRIPHWKDQHLQDIOXLGL]HGEHGUHDFWRUZLWKGRORPLWHDVDFFHSWRUChem.
Eng. Sci.±
$EDQDGHV-&$OYDUH]'&RQYHUVLRQ/LPLWVLQWKH5HDFWLRQRI&2ZLWK
/LPHEnergy & Fuels±
6WDWHV86WDWHV8/LPHDQG/LPHVWRQH±
GRLDSXE
6XQ3*UDFH-5/LP&-$QWKRQ\(-7KHHIIHFWRI&D2VLQWHULQJRQ
F\FOLF&2FDSWXUHLQHQHUJ\V\VWHPVAIChE J.±
.XUDPRWR.et al.5HSHWLWLYH&DUERQDWLRQí&DOFLQDWLRQ5HDFWLRQVRI&D%DVHG
6RUEHQWVIRU(IILFLHQW&26RUSWLRQDW(OHYDWHG7HPSHUDWXUHVDQG3UHVVXUHVInd.
Eng. Chem. Res.±
$EDQDGHV-&7KHPD[LPXPFDSWXUHHIILFLHQF\RI&2XVLQJDFDUERQDWLRQ
FDOFLQDWLRQF\FOHRI&D2&D&2Chem. Eng. J.±
&KHQ&=KDR&/LDQJ&3DQJ.&DOFLQDWLRQDQGVLQWHULQJFKDUDFWHULVWLFV
RIOLPHVWRQHXQGHU2&2FRPEXVWLRQDWPRVSKHUHFuel Process. Technol.
±
&KULVVDILV.3DUDVNHYRSRXORV0.7KHHIIHFWRIVLQWHULQJRQWKHPD[LPXP
FDSWXUHHIILFLHQF\RI&2XVLQJDFDUERQDWLRQFDOFLQDWLRQF\FOHRIFDUERQDWHURFNV
J. Therm. Anal. Calorim.±
0DUWDYDOW]L&6/HPRQLGRX$$'HYHORSPHQWRIQHZ&D2EDVHGVRUEHQW
PDWHULDOVIRU&2UHPRYDODWKLJKWHPSHUDWXUHMicroporous Mesoporous Mater.
±
'*2'HPRQVWUDWLRQRI2KLR6WDWH&DUERQDWLRQDQG$VK5HDFWLYDWLRQ
26&$53URFHVVDQG%\SURGXFW&KDUDFWHUL]DWLRQ
)DQ/6-DGKDY5$&OHDQFRDOWHFKQRORJLHV26&$5DQG&$5%212;
FRPPHUFLDOGHPRQVWUDWLRQVAIChE J.±
<X)&3KDODN16XQ=)DQ/6$FWLYDWLRQVWUDWHJLHVIRUFDOFLXPEDVHG
VRUEHQWVIRU&2FDSWXUH$SHUVSHFWLYHInd. Eng. Chem. Res.±
/L=&DL1+XDQJ<(IIHFWRI3UHSDUDWLRQ7HPSHUDWXUHRQ&\FOLF&2
&DSWXUHDQG0XOWLSOH&DUERQDWLRQí&DOFLQDWLRQ&\FOHVIRUD1HZ&D%DVHG&2
6RUEHQWInd. Eng. Chem. Res.±
/L=&DL1+XDQJ<+DQ+6\QWKHVLV([SHULPHQWDO6WXGLHVDQG
$QDO\VLVRID1HZ&DOFLXP%DVHG&DUERQ'LR[LGH$EVRUEHQWEnergy & Fuels
±
5HGG\(36PLUQLRWLV3*+LJK7HPSHUDWXUH6RUEHQWVIRU&20DGHRI
$ONDOL0HWDOV'RSHGRQ&D26XSSRUWVJ. Phys. Chem. B±
)DQ/6*XSWD+,\HU096HSDUDWLRQRIFDUERQGLR[LGH&2IURPJDV
PL[WXUHVDWKWWSZZZJRRJOHFRPSDWHQWV86!
6HUULV(et al.6WXG\RIWKHK\GUDWLRQRI&D2SRZGHUE\JDVVROLGUHDFWLRQCem.
Concr. Res.±
6KHDUHU-$6PLWK*:0\OHV.0-RKQVRQ,+\GUDWLRQHQKDQFHG
VXOIDWLRQRIOLPHVWRQHDQGGRORPLWHLQWKHIOXLGL]HGEHGFRPEXVWLRQRIFRDOJ Air
Pollut Control Assoc±
&RQYHUVLRQ&et al.6(QYLURQPHQWDO3URWHFWLRQ$JHQF\XQGHU$JUHHPHQW,$*
'(
%UXFH.5*XOOHWW%.%HDFK/2&RPSDUDWLYH62UHDFWLYLW\RI&D2
GHULYHGIURP&D&RDQG&D2+AIChE J.±
%ODPH\-0DQRYLF9$QWKRQ\(-'XJZHOO'5)HQQHOO362QVWHDP
K\GUDWLRQRI&D2EDVHGVRUEHQWF\FOHGIRU&2FDSWXUHFuel±
6FKDXEH).RFK/:|UQHUD0OOHU6WHLQKDJHQ+$WKHUPRG\QDPLFDQG
NLQHWLFVWXG\RIWKHGHDQGUHK\GUDWLRQRI&D2+DWKLJK+2SDUWLDOSUHVVXUHV
IRUWKHUPRFKHPLFDOKHDWVWRUDJHThermochim. Acta±
:DQJ</LQ66X]XNL<(IIHFWRI&D2FRQWHQWRQK\GUDWLRQUDWHVRI&D
EDVHGVRUEHQWVDWKLJKWHPSHUDWXUHFuel Process. Technol.±
/LQ6+DUDGD06X]XNL<+DWDQR+&D2K\GUDWLRQUDWHDWKLJK
WHPSHUDWXUHa.Energy and Fuels±
:DQJ:5DPNXPDU6)DQ/6(QHUJ\SHQDOW\RI&2FDSWXUHIRUWKH
&DUERQDWLRQ&DOFLQDWLRQ5HDFWLRQ&&53URFHVV3DUDPHWULFHIIHFWVDQG
FRPSDULVRQVZLWKDOWHUQDWLYHSURFHVVHVFuel±
3DQLDJXD-'LD]/=DUUDJD('H/ySH]-$OYDUH]-/D3HUHGD&2ௗD
0:SLORWWRWHVWSRVWFRPEXVWLRQ&2FDSWXUHZLWK&D2±
0DUWtQH],0XULOOR5*UDVD*$EDQDGHV-&,QWHJUDWLRQRIDFDOFLXP
ORRSLQJV\VWHPIRU&2FDSWXUHLQDQH[LVWLQJSRZHUSODQW
/L=:DQJ<<DR+/LQ61RYHO&2VRUEHQWௗ&D2+ZLWKKLJK
VWUHQJWKFuel Process. Technol.±
<DQJ+et al.3URJUHVVLQFDUERQGLR[LGHVHSDUDWLRQDQGFDSWXUH$UHYLHZJ.
Environ. Sci.±
%R\QWRQ56Chemistry and technology of lime and limestone:LOH\
%ODPH\-et al.$6KULQNLQJ&RUH0RGHOIRU6WHDP+\GUDWLRQRI&D2%DVHG
6RUEHQWV&\FOHGIRU&2&DSWXUHChem. Eng. J.±
$VIRXU$$'LIIXVLRQ0DVVWUDQVIHULQIOXLGV\VWHPV%\(/&XVVOHU
&DPEULGJH8QLYHUVLW\3UHVVSSAIChE J.±
86(QHUJ\,QIRUPDWLRQ$GPLQLVWUDWLRQ$QQXDO(QHUJ\2XWORRN