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Microreactors technology for hydrogen purification: Effect of the catalytic layer thickness on CuOx/CeO2-coated microchannel reactors for the PROX reaction

Abstract

Two blocks of microreactors composed by 100 microchannels and coated, respectively, with 150 and 300 mg of a CuOx/CeO2 catalyst, were prepared and tested in the preferential oxidation of CO in presence of H2 (PROX). The deposition of different amount of catalyst resulted in different catalytic layer thicknesses thus modifying the catalytic performances of the microreactor. The evaluation of the main reaction variables (the space velocity, the O2-to-CO ratio and the presence of H2O and/or CO2 in the stream) was performed over both microreactors and compared to that of the parent powder catalyst. The least loaded microreactor, with a coating thickness around 10 μm, presented the highest CO conversion and selectivity levels at temperatures below 160 ºC. This result evidences i) the improvement of the catalytic performances got by the structuration of the powder catalyst and ii) the importance of the selection of the adequate thickness of the catalytic layer on the microreactor, which have not to exceed and optimal value. An adequate coating thickness allows minimizing the mass and heat transport limitations, thus resulting in the enhancement of the catalytic performance during the PROX reaction

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Microreactors technology for hydrogen purification: Effect of the catalytic layer thickness on CuOx/CeO2-coated microchannel reactors for the PROX reaction

Author: Laguna Espitia, Oscar Hernando; González Castaño, Míriam; Centeno Gallego, Miguel Ángel; Odriozola Gordón, José Antonio
Publisher: Elsevier
Year: 2015
DOI: 10.1016/j.cej.2015.04.023
Source: https://idus.us.es/bitstreams/28c60549-56c3-418b-93f1-539cf367d2a2/download
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Mic o eac o s echnology o hyd ogen pu i ica ion: E ec o
he ca aly ic laye hickness on CuOx/CeO2-coa ed
mic ochannel eac o s o he PROX eac ion
O.H. Laguna*, M. González Cas año, M.A. Cen eno, J.A. Od iozola
Ins i u o de Ciencia de Ma e iales de Se illa, Cen o Mix o CSIC – Uni e sidad
de Se illa, A enida Amé ico Vespucio 49, 41092 Se ille, Spain
*Co esponding au ho e-mail: [email protected]
Keywo ds
Mic o eac o ; P ocess in ensi ica ion; CO-PROX; Ca aly ic laye hickness
Abs ac
Two blocks o mic o eac o s composed by 100 mic ochannels and coa ed,
espec i ely, wi h 150 and 300 mg o a CuOx/CeO2 ca alys , we e p epa ed and
es ed in he p e e en ial oxida ion o CO in p esence o H2 (PROX). The
deposi ion o di e en amoun o ca alys esul ed in di e en ca aly ic laye
hicknesses hus modi ying he ca aly ic pe o mances o he mic o eac o . The
e alua ion o he main eac ion a iables ( he space eloci y, he O2- o-CO a io
and he p esence o H2O and/o CO2 in he s eam) was pe o med o e bo h
mic o eac o s and compa ed o ha o he pa en powde ca alys . The leas
loaded mic o eac o , wi h a coa ing hickness a ound 10 µm, p esen ed he
highes CO con e sion and selec i i y le els a empe a u es below 160 ºC.
This esul e idences i) he imp o emen o he ca aly ic pe o mances go by
he s uc u a ion o he powde ca alys and ii) he impo ance o he selec ion o
he adequa e hickness o he ca aly ic laye on he mic o eac o , which ha e
no o exceed and op imal alue. An adequa e coa ing hickness allows
minimizing he mass and hea anspo limi a ions, hus esul ing in he
enhancemen o he ca aly ic pe o mance du ing he PROX eac ion.
2
1. In oduc ion
Cu en ly, he need o al e na i e ene gy sou ces mo i es he de elopmen o
new echnologies based on uels di e en o hose based in pe oleum. In his
sense, many e o s ha e been ocused in he use o H2 o anspo and
po able applica ions [1, 2]. Howe e he p oduc ion o H2 is a mul i-s age
p ocess including e o ming o hyd ogen-con aining uels, such as hyd oca bons
and alcohols, ollowed by successi e cleaning up s eps o up- aking he CO,
such us he high and low empe a u e wa e -gas-shi (HT and LT-WGS) and
he p e e en ial oxida ion o CO (PROX). These p ocesses should educe he
CO le els a ound 1% in he case o he WGS, and hen below 50 ppm wi h he
PROX, in o de o ensu e a longe li e ime o he elec ochemical de ices whe e
he H2 uelled is con e ed in elec ic powe . In his sense, highly ac i e
ca alys s in he CO aba emen eac ions a e equi ed. Ac ually many sys ems
wi h di e en suppo s and ac i e phases ha e been es ed in CO oxida ions
eac ions [2-7].
The eal applica ion o he H2 echnology in au omo i e and po able de ices
s ongly depends on he inco po a ion o he di e en eac ions in ol ed in o he
engine o hese sys ems. Besides his, he size o he compac uel p ocesso s
whe e he di e en eac ions occu mus be adequa e o he e iciency du ing
he anspo [1]. In his ega d, he mic o eac o s a e an in e es ing op ion i
hei di e se ad an ages a e conside ed [8, 9]. The mic o eac o s can be
conside ed as small scale chemical eac o s ha achie e high con e sion a es
wi hin a educed olume [10, 11]. These de ices allow he p ocess
in ensi ica ion because hey a e able o enhance he hea ing exchange, being
especially a ac i e o exo he mic eac ions whe e a s ic empe a u e con ol
has o be achie ed. Mo eo e , he o al low o he eeding and he p essu e in
he inle can be conside ably inc eased, compa ed wi h hose o he common
packed-bed eac o s. In addi ion, a mo e di ec ansi ion om he labo a o y o
he indus ial p oduc ion scale is easily achie able o mic o eac o s [8, 9].
Se e al wo ks ha e p esen ed in e es ing p og esses on he applica ion o
mic o eac o s in di e en eac ions [12, 13]. Fo example, Jang e al. [14]
3
s udied a mic o-me hanol s eam e o me and es ablished ha he geome y o
he mani old and he channel size, among o he a iables, had a c ucial
in luence on he e iciency and consequen ly mus be op imized o e e y
mic o eac o . This ag ees wi h he esul s p esen ed by Ma hieu-Po in e al.
[10] ha analysed, by a nume ical simula ion s udy, he op imal geome y o
ca aly ic mic o eac o s. They conclude ha he compe i ion be ween di usion,
ad ec ion and kine ic phenomena dic a e he design o he mic o eac o s. In his
sense, some adimensional numbe s mus be conside ed, such us he Schmid
and he Bejan numbe ha a e ela ed o he beha iou o he luid in o he
channels. Addi ionally, i was poin ed ou ha he simula ion o he mic o eac o
beha iou equi es he op imiza ion o he mass o ca alys in oduced in o he
mic ochannels and o he o al low used, in o de o achie e he adequa e
aspec a io ha imp o es he maximum con e sion.
Among he di e en a iables conside ed du ing he designing and
manu ac u ing o mic o eac o s, he op imiza ion o he amoun o loaded
ca alys is a capi al pa ame e o ob aining he maximum ca aly ic pe o mance
and consequen ly, he con ol o he ca aly ic laye hickness esul s
de e minan . This a iable may s ongly in luence he hea and mass anspo
phenomena on he ca aly ic beha iou o he mic o eac o . In his sense, he
modi ica ion o he p oduc s dis ibu ion by he a ia ion o he selec i i y and he
dec easing o he hea anspo could be no iceable i he ca aly ic laye
hickness is ou side he op imal alue.
The e icien eleasing o hea du ing he eac ion is c ucial o exo he mic
p ocesses such as PROX. Mic o eac o s may imp o e he eleasing o he hea
p oduced in such exo he mal eac ions a oiding he o ma ion o ho spo s and
allowing a s ic con ol o he eac ion empe a u e. Fo ins ance, ecen ly
Llo ca e al. [15] ha e p esen ed he s udy o a silicon mic omonoli h con aining
ca. 40000 egula channels o 3.3 µm in diame e pe squa e millime e
con aining Au/TiO2 as he ca alys s coa ed in he walls o he channels, o he
PROX eac ion. The au ho s demons a ed ha al hough hei silicon
mic o eac o did no achie e high CO con e sions le els a low empe a u es
(150 – 240 ºC), his sys em was conside ably mo e e icien han a con en ional
4
400 cpsi (cells pe squa e inch) co die i e monoli hs, which p esen ed a poo
hea ans e du ing he p ocess.
Ouyang e al. [16] ha e showed he lowe adial and axial empe a u e
g adien s in mic o eac o s compa ed o hose o packed bed eac o s, which
minimize he ex end o he e e se WGS eac ion, and a ou highe CO
con e sions. Howe e , i he amoun o ca alys coa ed in he walls o he
mic ochannels is e y high, his be e hea eleasing a e may be less ob ious,
and he occu ence o some mass anspo limi a ions inside he ca aly ic laye
canno be ully disca ded. This p oblem was s udied by Po emkin e al. [17] o e
a mic o eac o loaded wi h a 5 w .% Cu/CeO2-X ca alys . The au ho s p oposed
he calcula ion o an in e nal e ec i eness ac o (ηCO), de e mined as he a io
o he eac ion a e calcula ed assuming he exis ence o mass ans e
limi a ions o ha calcula ed in he assump ion o ze o mass ans e limi a ions.
The analysis o he ηCO ac o o di e en hickness o ca aly ic laye s
sugges ed ha he lowes con ibu ion o mass anspo limi a ions in
mic o eac o s is p oduced when he hickness does no exceed ~20 µm.
Ob iously, we mus ake in o accoun ha his alue is app oxima e and only
alid o he speci ic ca alys used in ha wo k, since he ex u al p ope ies o
he ca alys (po e size dis ibu ion, e c.) may con ol he kind and a e o
di usion o he eagen s and p oduc s along he channels.
F om all abo e, i is clea ha he de elopmen o mic o eac o s s ill equi es
addi ional s udies whe e many a iables ha e o be op imized in o de o
gene a e a comple e knowledge abou he designing, manu ac u ing and
applying o mic o eac o s as ca aly ic sys ems. The p esen wo k p e ends o
analyse di e en ca aly ic expe imen al esul s ob ained wi h wo blocks o
mic o eac o s, composed by 100 mic ochannels, coa ed wi h di e en o al
amoun s o a CuOx/CeO2 ca alys (150 and 300 mg) o he PROX eac ion.
2. Ma e ials and me hods
2.1. Syn hesis o he CuOx/CeO2 ca alys and manu ac u ing o he
mic o eac o s
5
Recen ly we ha e published he expe imen al p ocedu es o he syn hesis and
he cha ac e iza ion by means o N2 adso p ion-deso p ion, XRD, Raman
spec oscopy and H2-TPR s udies o he CuOx/CeO2 powde ca alys [18, 19].
The manu ac u ing p ocess o ou mic o eac o p o o ype coa ed wi h 300 mg o
ca alys [4, 18-20] is summa ized in Figu e 1. In he p esen wo k, his
mic o eac o is named as MR300 and will be compa ed wi h a new block coa ed
wi h 150 mg o ca alys , deno ed as MR150.
2.2. Ca aly ic ac i i y measu emen s
P io o e e y ca aly ic es he ca alys s we e ea ed unde 30 mL/min o al low
o 21% O2 in N2 a 300 ºC o 2 h. Fo he powde ca alys , he PROX eac ion
was ca ied ou in a ixed-bed cylind ical s ainless s eel eac o wi h in e nal
diame e o 9 mm unde he expe imen al condi ions p esen ed in [21]. Fo
hese expe imen s, 100 mg o ca alys (pa icle size= 100 < ϕ < 200 μm) we e
employed and dilu ed wi h c ushed glass (in he same pa icle size) o ming a
bed o abou 50 mm in leng h. The CO con e sion and he selec i i y o CO
con e sion we e calcula ed acco ding o Eq. 1 and Eq. 2, espec i ely. Fin and
Fou e e o mola low a es a he eac o inle and ou le , espec i ely [4, 20].
CO con e sion (%)
in
CO
ou
CO
in
CO
F
FF
,
,, 100)(


 (Eq.1)
Selec i i y o CO con e sion (%) )(2
100)(
,,
,,
22 ou OinO
ou
CO
in
CO
FF
FF



 (Eq.2)
In he case o mic o eac o s, he same eac ion se -up was used; howe e he
cylind ical eac o was eplaced by wo s ainless s eel cases connec ing he
inle and ou le posi ions o he mic ochannels, and allowing he con ac
be ween he coa ed walls o he channels and he eed-s eam acco ding o ha
desc ibed in [4, 20]. The empe a u e was con inuously moni o ed by 4 K- ype
he mocouples. Two o hem we e placed in con ac wi h he me allic block a

6
he inle and ou le posi ions o some cen al mic ochannels. The o he wo
senso s eco ded he empe a u e a la e al posi ions in he walls o he
mic o eac o [4]. The eed-s eam composi ions and he λ alues used in he
ca aly ic es s a e p esen ed in Table 1. The λ alue was calcula ed o e e y
mix u e o eac ion acco ding o Eq. 3 [22].


.%
.%2 2
CO ol
olO



(Eq. 3)
A i s compa ison o he ca aly ic pe o mances o he h ee ca alys s s udied,
he powde and he MR150 and MR300 mic o eac o s, was ca ied ou
employing he eed-s eam A and main aining he low- o-ca alys weigh a io in
60 L·h-1·g-1. Addi ionally, he in luence o he space eloci y (30, 60 and 120 L·h-
1·g-1) was analyzed o bo h mic o eac o s applying he eed-s eam B. The
in luence o he λ alue was also e alua ed by using he eed-s eams B, C and
D a a cons an space eloci y o 60 L·h-1·g-1. Finally, he e ec o he p esence
o CO2 and/o H2O was s udied wi h he eed-s eam composi ions A, E, F, and
G a a cons an space eloci y o 60 L·h-1·g-1.
3. Resul s and discussion
3.1. Compa ison o he CuOx/CeO2 powde ca alys and he
mic o eac o s MR150 and MR300 o he PROX eac ion
The ca aly ic esul s ob ained o he CuOx/CeO2 powde ca alys and o he
wo mic o eac o s unde a space eloci y o 60 L·h-1·g-1 a e p esen ed in Figu e
2.
In all h ee ca alys s, he CO con e sion inc eases wi h empe a u e nea o ull
con e sion a 160ºC and abo e (Figu e 2A). Howe e a empe a u es below
160 ºC, di e en beha iou s a e app eciable. MR150 p esen s he highes
7
ca aly ic ac i i y while he MR300 exhibi s he lowes CO con e sion le els. The
powde ca alys p esen s an in e media e beha iou .
The selec i i y o CO con e sion (Figu e 2B) dec eases wi h he empe a u e in
he h ee cases. Bo h mic o eac o s p esen simila selec i i ies each o he bu
highe han ha o he powde ca alys , which sugges s ha he H2 consump ion
eac ions (H2 oxida ion and/o R-WGS) would be inhibi ed in hem.
F om he e, i is clea ha he mic o eac o loaded wi h he lowes amoun o
ca alys (MR150) p esen s be e ca aly ic pe o mances han hose o he
powde ca alys . Besides his, al hough bo h mic o eac o s has a simila
selec i i y o CO2, he highes CO con e sion le els showed by he lowes
loaded mic o eac o (MR150), makes i he sys em wi h he bes pe o mance.
The obse ed di e ences in CO con e sion and selec i i y among he h ee
e alua ed sys ems may be a ibu ed o he exis ence and di e en ex ension o
mass and hea anspo phenomena. The highes ca aly ic ac i i y o he
MR150 mic o eac o , mus be ela ed wi h he bes e iciency in he elease o
he hea p oduced by he exo he mic eac ions implied (CO and H2 oxida ions
and WGS). This allows a be e he mal con ol in o he mic ochannels and
ensu es he iso he mal condi ions a e e y e alua ed empe a u e, a oiding he
ho spo s o ma ion. Consequen ly, al hough he di e ence be ween he
appa en ac i a ion ene gies o he CO and H2 oxida ion eac ions is no so big
(36.9 and 110 kJ/mol espec i ely) [21], he achie ed s ic con ol o he
empe a u e in he MR150 delays he appea ance o he H2 oxida ion eac ion,
especially a lowe empe a u es. Ou esul s a e in good ag eemen wi h he
highly e icien hea ans e ha has been widely desc ibed o o he
mic o eac o s employed in he PROX eac ion, some o hem coa ed wi h
CuOx/CeO2 ca alys s [16, 23, 24]. Fo ins ance Sny niko e al. [25] ha e
s udied a coppe -ce ium oxide ca alys o he PROX eac ion as a powde
ca alys in a ixed-bed eac o and coa ed in mic o eac o s. They ha e p oposed
ha in he case o mic o eac o s, he eleasing o he hea p oduced du ing he
oxida ion eac ion is e y as because o he di ec con ac be ween he
ca aly ic laye and he me al subs a e. Howe e , in he case o he ixed-bed
8
eac o , he p esence o qua z, which is used as diluen , may p esen hea
anspo limi a ions due o i s a he low he mal conduc i i y. A simila e ec
could occu in ou case o he powde ca alys s, since i was es ed in a ixed-
bed eac o and dilu ed wi h g ound glass.
Besides his, he supe io ca aly ic beha iou o he MR150 mic o eac o
espec o ha o he powde ca alys may be also associa ed o he diminu ion
o he mass ans e limi a ions in he s uc u ed sys ems. P obably, he con ac
be ween he ca alys and he eac ion mix u e is di e en in bo h si ua ions and,
addi ionally, he p esence o g ound glass wi h he powde ca alys in he ixed-
bed eac o also ep esen s an addi ional ba ie o he adequa e mass
anspo .
Despi e he ad an age o he MR150 s uc u ed sys em, he lowe ca aly ic
pe o mance a empe a u es below 160ºC o he MR300, e en in e io o ha o
he powde ca alys highligh s he need o op imize he amoun o coa ed
ca alys in he mic o eac o s, ha consequen ly means he need o op imize he
hickness o he ca aly ic laye . As said in he in oduc ion sec ion, he ele ance
o op imizing o he ca aly ic laye hickness was emphasized by Po emkin e al.
[17] who demons a ed ha ha op imum alues o he in e nal e ec i eness
ac o o he CO oxida ion, ηCO, which assu es no mass limi a ions, o he
PROX eac ion o e a mic o eac o coa ed wi h a Cu/CeO2-x ca alys in he
170–230ºC empe a u e ange, a e achie ed when he washcoa ed hickness
did no exceed 20 µm.
3.2. E ec o he space eloci y o e he mic o eac o s
In o de o e alua e he in luence o he space eloci y on he ca aly ic
pe o mances o he s uc u ed sys ems, h ee o al low o weigh o ca alys
a ios we e s udied (30, 60 and 120 L·h-1·g-1), keeping he same composi ion o
he eac i e eed and wi h a λ = 1 alue. The esul s o CO con e sion and
selec i i y o CO oxida ion a e p esen ed in Figu e 3.
9
The MR150 mic o eac o p esen s a maximum in he CO con e sion a a ound
140 ºC wha e e he space eloci y used, al hough he alue o such maximum
con e sion dec eased when inc easing he space eloci y. Mo eo e , highe he
space eloci y o he expe imen , lowe he ca aly ic ac i i y o he sys em a
empe a u es below 140 ºC. On he o he hand, he MR300 mic o eac o shows
a ema kable inc easing o he CO con e sion wi h he empe a u e, no ma e
he space eloci y, up o 160 ºC. A highe empe a u es, he ca aly ic ac i i y
ends o s abilize. In e e y case, he con e sion cu es shi o highe
empe a u es when inc easing he space eloci y.
The block coa ed wi h 300 mg o ca alys exhibi s highe con e sions han hose
o he MR150 mic o eac o a high empe a u es. Howe e , in his empe a u e
ange, he MR150 p ese es a supe io selec i i y o CO oxida ion. Fo bo h
mic o eac o s, he inc emen o he space eloci y esul s in he dec ease o he
ca aly ic ac i i y, especially a empe a u es below 160 ºC. Conside ing ha
maldis ibu ions o eed-s eam in o he channels o he s udied mic ochannels
blocks may be disca ded acco ding o p e ious CFD s udies ca ied ou o
designing he mic o eac o s and he cases o inse ing hem in he eac ion
sys em [26], he low CO con e sion shown by bo h blocks, especially a low
empe a u es occu s because he ac i e si es a e wo king unde demanding
condi ions (a high amoun o CO molecules o be con e ed pe uni o ime and
an insu icien he mal ac i a ion), showing hei ull po en ial. Sny niko e al.
[23] epo ed simila obse a ions s udying mic o eac o s coa ed wi h Cu/CeO2-x
o he PROX eac ion. They concluded ha , when he low a e is inc eased,
he minimum ou le CO concen a ion is inc eased and he op imum eac o
wo king empe a u e, co esponding o he minimum CO concen a ion
emission, was shi ed o highe alues.
Conce ning he selec i i y o CO oxida ion (Figu e 3B), a gene al iew allows
es ablishing ha he MR150 mic o eac o p esen s highe selec i i ies han
hose o MR300 in all cases, especially a empe a u es abo e 160 ºC.
Howe e , he modi ica ion o he space eloci y seems o p oduce an opposi e
e ec in e e y mic o eac o . In he case o he MR150, when he space eloci y
is inc eased, he selec i i y also inc eased. Howe e , o he MR300
16
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18
Tables
Table 1. Feed-s eam composi ions o he di e en ca aly ic ac i i y es s
Feed-
S eam
CO
ol.%
O2
ol.%
H2
ol.%
N2
ol.%
CO2
ol.%
H2O
ol.% λ
A 1.0 1.0 50.0 48.0 -- -- 2.0
B 2.0 1.0 50.0 47.0 -- -- 1.0
C 2.0 1.5 50.0 46.5 -- -- 1.5
D 2.0 3.0 50.0 45.0 -- -- 3.0
E 1.0 1.0 50.0 46.0 2.0 -- 2.0
F 1.0 1.0 50.0 38.0 -- 10 2.0
G 1.0 1.0 50.0 36.0 2.0 10 2.0
19
Figu e Cap ions
Figu e 1. Manu ac u ing o he mic o eac o p o o ype: (a) Mic omilled pla es;
(b) Joining o he pla es; c) Final mic ochannels block
Figu e 2. Ca aly ic ac i i y o he h ee e alua ed sys ems (CuOx/CeO2 powde ,
MR150 and MR300) in he PROX eac ion: (A) CO con e sion; B) Selec i i y o
CO oxida ion
Figu e 3. Ca aly ic ac i i y o he mic o eac o s (MR150 and MR300) modi ying
he space eloci y: (A) CO con e sion; (B) Selec i i y o CO oxida ion
Figu e 4. Ca aly ic ac i i y du ing he PROX eac ion o MR150 and MR300
modi ying he λ alue in he eed-s eam: (A) CO oxida ion; (B) Selec i i y o CO
oxida ion
Figu e 5. Ca aly ic ac i i y o he MR150 and MR300 including CO2 and/o H2O
in he eed-s eam: (A) CO oxida ion; (B) Selec i i y o CO oxida ion
Figu e 6. E ec i eness ac o as a unc ion o he empe a u e du ing he PROX
eac ion o he CuOx/CeO2 powde ca alys s, MR150 and MR300
20
Figu e 1
21
Figu e 2

120 140 160 180 200
0
10
20
30
40
50
60
70
80
90
100
CuOx/CeO2 (powde )
MR150
MR300
Con e sion o CO (%)
Tempe a u e (ºC)
(B)
(A)
Space eloci y = 60 L·h-1·g-1
Feed-s eam A (Table 1)
 = 2
120 140 160 180 200
0
10
20
30
40
50
60
70
80
90
100
Space eloci y = 60 L·h-1·g-1
Feed-s eam A (Table 1)
 = 2
CuOx/CeO2 (powde )
MR150
MR300
Selec i i y o CO oxida ion (%)
Tempe a u e (ºC)

22
Figu e 3

120 140 160 180 200
0
10
20
30
40
50
60
70
80
90
100
30L·h-1·g-1
60L·h-1·g-1
120 L·h-1·g-1
CO con e sion (%)
Tempe a u e (ºC)
= 1
Feed-s eam B (Table 1)
MR150 MR300
120 140 160 180 200
0
10
20
30
40
50
60
70
80
90
100
= 1
Feed-s eam B (Table 1)
30L·h-1·g-1
60L·h-1·g-1
120 L·h-1·g-1
Selec i i y o CO oxida ion
Tempe a u e (ºC)
(A) (B)
MR150 MR300
23
Figu e 4

120 140 160 180 200
0
10
20
30
40
50
60
70
80
90
100
CO con e sion (%)
Tempe a u e ºC
 = 1.5  = 2.0  = 3.0
MR150
MR300
60 L· h
-1
· g
-1
120 140 160 180 200
0
10
20
30
40
50
60
70
80
90
100
60 L· h
-1
· g
-1
Selec i i y o CO oxida ion (%)
Tempe a u e ºC
 = 1.5  = 2.0  = 3.0
MR150
MR300
(A) (B)
24
Figu e 5

125 150 175 200 225 250
0
10
20
30
40
50
60
70
80
90
100
H2O
CO2MR300
CO con e sion (%)
Tempe a u e (ºC)
MR150
0% 0%
2% 0%
0% 10%
2% 10%
60 L·h-1·g-1
 = 2
125 150 175 200 225 250
0
10
20
30
40
50
60
70
80
90
100
60 L·h-1·g-1
 = 2
Selec i i y o CO oxida ion (%)
Tempe a u e (ºC)
CO2H2OMR150 MR300
0% 0%
2% 0%
0% 10%
2% 10%
(A) (B)
25
Figu e 6

120 140 160 180 200
0
1
CO
Tempe a u e (ºC)
CuOx/CeO2 (powde )
MR150
MR300