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Design and testing of a microchannel reactor for the PROX reaction

Abstract

The different steps for manufacturing a microchannel reactor for the PROX reaction are discussed. Transient Liquid Phase bonding (TLP) using a Ni-B-Si amorphous melt spun is used for joining micromilled Al-alloyed ferritic stainless steel plates followed by recrystallization at 1200°C for 5h. A CuOx-CeO2 catalyst synthesized by the coprecipitation method was washcoated on the microchannel block resulting in a homogenous 20-30μm thick layer. The catalytic activity for CO-PROX reaction is similar in both the powder catalyst and the microchannel coated reactor but the selectivity is higher in the microchannel reactor. © 2010 Elsevier B.V.

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Design and testing of a microchannel reactor for the PROX reaction

Author: Cruz Torres, Sylvia Andrea; Sanz Iturralde, Oihane; Poyato Galán, Rosalía; Laguna Espitia, Oscar Hernando; Echave, F. Javier; Almeida, Luis C.; Centeno Gallego, Miguel Ángel; Arzamendi, Gurutze; Gandía, L. M.; Souza-Aguiar, E. F.; Montes, Mario; Odriozol
Publisher: Elsevier
Year: 2011
DOI: 10.1016/j.cej.2010.08.088
Source: https://idus.us.es/bitstreams/e077f53e-fed0-4ac3-bfd3-7a6d3198fbb0/download
Design and es ing o a mic ochannel eac o o he PROX eac ion
S. C uz1, O. Sanz1, R. Poya o1, O.H. Laguna1*, F. J. Echa e2, L.C. Almeida2,
M.A. Cen eno1, G. A zamendi3, L.M. Gandia3, E.F. Souza-Aguia 4, M. Mon es2,
J.A. Od iozola1
1 Ins . o Ma e ial Sciences o Se ille, CSIC – Uni e sidad de Se illa. A da.
Amé ico Vespuccio 49, 41092 Se ille, Spain
2 Dep . Appl. Chemis y, Uni e si iy o he Basque Coun y, Paseo Manuel
La dizábal 3, 20018, San Sebas ián, Spain
3Public Uni e si y o Na a e, Campus de A osadía, s/n, E-31006 Pamplona,
Spain
4Pe ob as, Rio de Janei o, B azil
*Co esponding au ho : Osca He nando Laguna Espi ia
e-mail add ess: [email p o ec ed]
Telephone: +34 954489501 Ex . 9221 Fax: +34 954460665
Abs ac
The di e en s eps o manu ac u ing a mic ochannel eac o o he PROX
eac ion a e discussed. T ansien Liquid Phase bonding (TLP) using a Ni-B-Si
amo phous mel spun is used o joining mic omilled Al-alloyed e i ic s ainless
s eel pla es ollowed by ec ys alliza ion a 1200ºC o 5 hou s. A CuOx-CeO2
ca alys syn hesized by he cop ecipi a ion me hod was washcoa ed on he
mic ochannel block esul ing in a homogenous 20-30 µm hick laye . The
ca aly ic ac i i y o CO-PROX eac ion is simila in bo h he powde ca alys
and he mic ochannel coa ed eac o bu he selec i i y is highe in he
mic ochannel eac o .
Keywo ds
1) Mic ochannel eac o 2) CO-PROX 3) CuOx-CeO2
4) T ansien Liquid Phase bonding 5) Al-alloyed e i ic s ainless s eel
1. In oduc ion
The widesp ead use o po able elec ic and elec onic de ices inc eases he
need o e icien au onomous powe supplies ha eplace he cu en ly
p edominan ba e y echnology. The use o common uels/chemicals
(hyd oca bons o alcohols) as ene gy sou ces is a p omising al e na i e when
combined wi h he ecen de elopmen s in mic ochannel eac o echnology.
The high powe densi y, apid s a -up ime, and low- empe a u e ope a ion o
PEMFC make hese de ices as he mos p omising o powe ing up elec ic o
elec onic de ices. Howe e , an essen ial equi emen o he e o ma e- ed
PEMFC is he emo al o CO om he H2 s eam a e he e o ming and wa e –
gas shi (WGS) eac ions. A e he WGS uni s he CO con en o he hyd ogen
s eams may a y be ween ca. 0.5 and 2 ol.% being, he e o e, manda o y
clean-up uni s o he emo al o CO o ace le el. P e e en ial CO oxida ion
(CO-PROX) is among he p e e ed echnologies o small-scale uel p ocesso
applica ions [1]. CO-PROX eac ions allow educing CO con en s om 1 % in
he eed o he ppm le el.
When using PEMFCs o po able o au omo i e applica ions packed-bed
eac o s ha e se e al d awbacks such as p essu e d op wi hin ca alys laye ,
empe a u e g adien s, and ho spo due o he high exo he mici y o he
oxida ions o CO and H2. Mic o eac o s ha e he ad an ages o as esponse
ime, easy in eg a ion, and small oo p in , which a e ideal o po able powe
sys ems. In addi ion, enhanced mass and hea anspo p ope ies a e also
widely ecognized as ad an ages o mic o eac o s [2-6]. In addi ion o his,
ecen s udies o simula ed CO-PROX eac ions ha e shown ha he e e se
wa e -gas-shi side eac ion is a ou ed in he case o packed bed eac o s wi h
espec o hin ca aly ic ilms deposi ed on mic ochannel walls [4]. The e o e,
CO-PROX uni s based on mic ochannel eac o s ha e been epo ed as pa o
in eg a ed uel p ocesso s in a wide powe ange [6-9].
Di e en ca aly ic sys ems and eac o designs ha e been p oposed o he CO-
PROX eac ion. In a ecen s udy Bion e al. [10] e iew he pe o mances o
noble me als (including P , Ru, Rh, Pd and Au) and ansi ion me al oxides
ca alys s and compa e he ad an ages and d awbacks o each ype o
ca alys s in e ms o ac i i y and selec i i y including he in luence o he
p esence o CO2 and H2O in he eac an s low. They conclude ha CuO–CeO2
ca alys s a e e y a ac i e o indus ial applica ions since hei excellen
pe o mances, s abili y and low cos compa ed o noble me al-based ca alys s.
Dud ield e al. [11, 12] ope a ed a compac in hea -exchange eac o
con aining 2.5% P -Ru ca alys in he CO-PROX eac ion. Using a wo-s age
con igu a ion his uni allowed educ ions in he CO concen a ions down o 15
ppm. Silicon wa e s [13] o aus eni ic s ainless s eel pla es [14, 15] we e used
o building mic ochannel eac o s o he PROX eac ion. Hwang e al. [16]
s udied he eac ion o e a silicon-based mic o eac o coa ed wi h a P /Al2O3
ca alys , yielding 99.4% CO con e sion. Kim e al. [15, 17] ob ained CO ou le
concen a ion below 50 ppm a O2/CO a io o 2.5 by using a 13-laye ed mic o-
channel eac o buil by s acking chemically e ched s ainless s eel pla es coa ed
wi h a P –Co/Al2O3 ca alys . Despi e mos o he wo k on CO-PROX in
mic o eac o s has been ca ied ou using noble me al based ca alys s a ew
insigh s on coppe based ca alys s ha e been epo ed. Sny niko e al. [18]
compa ed a 5 w .% Cu/CeO2 ca alys in bo h ixed bed and mic ochannel
eac o s wi h he la e exhibi ing highe con e sion and selec i i y. This ca alys
allowed he educ ion o he CO concen a ion om 1 ol.% o 10 ppm. Kim e
al. [15] compa ed a CuO/CeO2 coa ed mic o eac o wi h a P -Co coa ed
mic o eac o showing be e selec i i ies in he CO-PROX eac ion o he
coppe -based ca alys .
In he p esen wo k, we p o ide a desc ip ion o he di e en s eps equi ed o
manu ac u ing a mic ochannel eac o o he CO-PROX eac ion. The eac o is
es ed using con en ional CuOx/CeO2 ca alys s and he esul s compa ed wi h
hose ob ained o powde ed ca alys s.
2. Ma e ials and me hods
2.1. Ca alys p epa a ion
The CuOx-CeO2 ca alys was p epa ed by he cop ecipi a ion me hod. The
amoun necessa y o p epa ing a 0,5 M solu ion o Cu(NO3)2·3H2O and
Ce(NO3)3·6H2O we e mixed, unde igo ous s i ing, o ge a 9:1
Ce(OH)3:Cu(OH)2 weigh a io. A e homogenizing he sys em, a NaOH
solu ion (2 M) was added d opwise un il a s able pH o 9. The p ecipi a e was
il e ed and washed wi h dis illed wa e in o de o emo e he Na+ and NO3-
ions. Finally, he ob ained solid was d ied o e nigh a 60°C and inally, calcined
2h a 300 ºC.
2.2. Ca alys s cha ac e iza ion
BET speci ic su ace a eas we e measu ed by ni ogen adso p ion a liquid
ni ogen empe a u e in a Mic ome i ics ASAP 2000 appa a us. Be o e analysis,
he samples we e degassed 2 h a 150ºC in acuum.
The ce ium and coppe con en s o he samples we e de e mined by X- ay
luo escence spec ome y (XRF) in a Panaly ical AXIOS PW4400 sequen ial
spec opho ome e wi h a hodium ube as he sou ce o adia ion.
X- ay di ac ion (XRD) analysis was pe o med on a Siemens D 500
di ac ome e . Di ac ion pa e ns we e eco ded wi h Cu Ka adia ion (40 mA,
40 kV) o e a 10-80º 2θ ange using a posi ion-sensi i e de ec o wi h a s ep
size o 0.01º and a s ep ime o 7 s.
The Raman spec a we e eco ded in a dispe si e Ho i a Jobin Y on LabRam
HR800 mic oscope, wi h a 20 mWHe-Ne g een lase (532,14 nm), wi hou il e ,
and wi h a 600 g·mm-1 g a ing. The mic oscope used a 50x objec i e and a
con ocal pinhole o 100 μm. The Raman spec ome e is calib a ed using a
silicon wa e .
The educibili y s udies we e ca ied ou on a pilo plan buil by PID Eng&Tech
in TPR mode equipped wi h a VINCI he mal conduc i i y de ec o . The
expe imen s we e done by a he mo-p og ammed educ ion (TPR) o 50 mg o
ca alys , in a H2 low o 5 % dilu ed in A ( o al low = 50 mL/min), using a
empe a u e amp o 10 °C/min om oom empe a u e o 900 °C.
The Ze a Po en ial was measu ed by using a MALVERN Ze asize 2000
ins umen . The solids we e dispe sed in an aqueous solu ion o 0.003 M NaCl.
The pHs o he solu ions we e adjus ed wi h HNO3 o NaOH solu ions.
Rheological p ope ies o he slu ies we e measu ed in a o a ional
iscosime e HAAKE, model VT 500, geome y NV.
The adhe ence o he ca aly ic laye deposi ed on o he subs a es was
e alua ed using an ul asonic echnique. The weigh loss caused by he
exposu e o he sample o ul asound is measu ed. The s uc u ed suppo s
imme sed in pe oleum e he we e submi ed o an ul asonic ea men o 30
min a oom empe a u e. A e ha , he samples we e d ied and calcined. The
weigh loss was de e mined by he di e ence in he mass o he samples be o e
and a e he ul asonic es . The esul s a e p esen ed in e ms o he e ained
amoun o coa ing on he monoli h, exp essed as pe cen age.
2.3. Ca aly ic ac i i y measu emen s
The CO-PROX eac ion was ca ied ou a a mosphe ic p essu e in a PID
Eng&Tech Mic oac i i y se -up, employing a s ainless s eel ubula eac o wi h
in e nal diame e o 9 mm and a cons an eed s eam low a e o 100 cm3·min-1
(STP). The ca alys (100 mg, pa icle size in he 100–200 mm ange) was
dilu ed wi h c ushed glass pa icles in he same pa icle size ange o ming a
bed o abou 5 mm in leng h. The expe imen al uns we e ca ied ou in a low
con aining 50 ol.% H2, 2 ol. % CO and 1 ol. % O2 concen a ions using N2 as
balance. The eac ion empe a u e was inc eased om 50–60 o 190–250 ºC in
s eps o 10 ºC. Fo each s ep he empe a u e was s abilized and da a we e
eco ded a s eady-s a e condi ions. F esh ca alys was loaded in o he eac o
a e each comple e un. Some expe imen s ca ied ou a he same space- ime
bu a a ying gas linea eloci ies con i med he absence o ex e nal mass
ans e e ec s. On-line analyses o he eed and p oduc s s eams we e
pe o med on an Agilen 7890 gas ch oma og aph equipped wi h a Po apak Q,
wo Molecula Sie e 5A and wo Hayesep Q columns and wo TCD de ec o s
and a FID de ec o .
The same compu e ized PID Eng&Tech Mic oac i i y se -up was used o s udy
he eac ion in he mic ochannel eac o , eplacing he ubula s ainless s eel
eac o o he buil mic ochannel eac o he same composi ions we e chosen
bu 300 cm3·min-1 (STP) eed s eam low a e since 300 mg ca alys was
loaded in he mic ochannel block. To s udy he e ec o CO2 and H2O, a se ies
o expe imen s keeping cons an he H2 con en o he eed s eam se a 50
ol.%, and bo h he CO and O2 concen a ions ixed a 1 ol.% we e ca ied ou .
The CO2 and H2O concen a ions in he eed we e a ied wi hin he 2–10 ol.%

and 0–20 ol.% anges, espec i ely, using N2 as balance. The mic oac i i y
e e ence ho box con olled he eac ion empe a u e. Fo each s ep he
empe a u e was s abilized and da a we e eco ded a s eady-s a e condi ions.
3. Mic ochannel eac o
The me allic mic ochannel eac o was manu ac u ed using Al-alloyed e i ic
s ainless s eel ( o ins ance, Fec alloy®), since e i ic alloys con aining 3–5% o
aluminium p oduce by he mal ea men an Al2O3 laye ha a ou s he
in e ac ion wi h he ca aly ic coa ing [19-22]. The Fec alloy consis ed o C 22%,
Al 4.8%, Si 0.3%, Y 0.3%, and Fe balance [21].
Cha ac e iza ion o he joined s eel pla es we e ca ied ou by op ical and
elec on mic oscopy. Specimens we e ex ac ed om he samples, g inded wi h
SiC pape o #240, #400, #600 and #1200 g ain size and mi o polished wi h
0,3 and 0,1 µm Al2O3 powde . E ching wi h Vilella’s eagen de eloped he
mic os uc u e. Sample obse a ion in he as polished an e ched condi ions was
done in a Leica-DM-IRM op ical mic oscope equipped wi h a digi al came a
(Leica DC300). In o de o iden i y me allic and non-me allic inclusions as well
as o de e mine local composi ions, he as-polished samples we e also
obse ed by SEM using a JEOL 5400 sys em equipped wi h seconda y and
backsca e ed elec on and x- ay de ec o s.
Mic ochannels we e ab ica ed by mic o-milling 1 mm hick e i ic s ainless
s eel pla es. Each pla e has 10 squa e channels o 750 µm sepa a ed be ween
hem 300 µm machined in a 20x20 mm2 pla e. This p ocess esul s in channels
wi h 56 mm2 geome ic su ace and 700 µm hyd aulic adius.
In o de o minimize he high p essu es and p ocessing imes equi ed o solid
s a e bonding he e i ic s ainless s eel pla es we e joined oge he using he
ansien liquid phase (TLP) bonding p ocess. The TLP bonding p ocess uses
in e laye s, which ei he con ain mel ing poin dep essan s (e.g. B, Si o P) o
o m an eu ec ic wi h he pa en me al being bonded. The join is held a he
bonding empe a u e un il he mel ing poin dep essan s a e los om he liquid
in e laye by di usion and he liquid in e laye solidi ies iso he mally due o he
change in composi ion o he bond. This echnique has been p e iously used o
join di e en alloy sys ems including duplex s ainless s eels [23-29]. Figu e 1 is
a schema ic pic u e o he s eel pla es-me allic glass assembly used in his
wo k.
Fo TLP bonding, a nickel-based in e laye wi h a composi ion o Ni-14B-7Si (w
%, Good ellow) was used. This in e laye was an amo phous mel spun oil wi h
a hickness o 25 µm. The bonding p ocess was pe o med in acuum using a
es machine de eloped by Mic o es ha allows he con ol o he applied o ce,
empe a u e and ime allowing apid hea ing up o he bonding empe a u e.
Va ious ials we e conduc ed o es ablish he op imum bonding pa ame e s,
a ying he empe a u e, applied o ce and ime. A bonding empe a u e o
850°C wi h an applied o ce o 2,8 kN (~7 MPa) was selec ed. Low empe a u e
and ligh p essu e applied is equi ed o keeping he mechanical in eg i y o he
machined pla e since he low c eep s eng h o he selec ed alloy [30]. Figu e 2
shows he mac oscopic aspec s o joined pla es a di e en applied o ces
clea ly shown ha o applied p essu es abo e 15 MPa (6,0 kN) and 900ºC
c eep esul s in a s ong de o ma ion o he machined mic ochannels. The TLP
bonded samples we e inally ea ed a 1200ºC o 5 h.
A e he joining p ocedu e he wo e i ic s eel pla es a e sepa a ed by a
me allic alloy ca. 25 µm hick whose composi ion mainly co esponds o ha o
he Ni-based in e laye . The mic os uc u e o he joined a ea is cha ac e ized
by he exis ence o wo e i ic laye s in which he p ecipi a ion o ch omium
ca bides is e iden sepa a ed by he Ni-based in e laye . A s ong ch omium
ca bide p ecipi a ion occu s a he s ainless s eel-in e laye in e aces, igu e 3A.
Upon pos -p ocessing a 1200ºC a single phase ec ys allizes. EDX analysis
ac oss he joined a ea show ha he Fe, C , Al and Al line p o iles a e almos
la indica ing in e di usion o he Ni-based in e laye and he e i ic s eel,
excep o some ch omium maximum and i on minimum co esponding o he
p esence o ch omium ca bide p ecipi a es. Using nickel as a ma ke , i should
be no ed ha his elemen is absen in he e i ic s eel his di usion is clea ly
seen. Figu e 3D shows he Gaussian- i ed Ni line p o ile ac oss he joined a ea,
he FWHM o he Gaussian dis ibu ion, ca. 400 µm, is conside able highe han
he hickness o he used in e laye demons a ing he o ma ion o a single
phase upon he designed joining p ocedu e.
Mic omachining and joining o he s eel pla es esul ed in a mic oblock ha was
housed in Al-alloyed e i ic s eels cases designed using CFD algo i hms o
ensu ing homogeneous low h ough all he channels, he housing was join
oge he using g aphi e seals, igu e 4. Finally, he mic ochannel block was
i ed wi h he mocouples moni o ing inle and ou le empe a u es as well as
empe a u e g adien s wi hin he mic oblock. Mani olding and ins umen a ion o
he mic o eac o was implemen ed in a compu e ized Mic oac i i y Re e ence
Ca aly ic Reac o om PID Eng&Tech ha con ols he eac ion empe a u e in
he eac o h ough he empe a u e con ol o he ho box.
P io o he assembly o he mic o eac o he mic ochannel block was coa ed
wi h he ca alys . Fo imp o ing he in e ac ion be ween he washcoa ed laye
and he me allic suppo , he su ace o he mic ochannel block was modi ied
gene a ing an oxide scale ha enhances adhesion o he ca aly ic laye bo h
mechanically, h ough he gene a ed oughness, and chemically h ough he
in e ac ion be ween his oxide scale and he ca aly ic ma e ial.
Modi ied su aces a e ob ained upon hea ing in ai a ele a ed empe a u es
being he esul ing oxide scale an excellen subs a e o adhe e ca alys s [19-
22]. The op imal ea men pa ame e s emain usually undisclosed. Upon
hea ing a 900 ºC o 22 h in ai he mic ochannel block a homogeneous su ace
laye o α-Al2O3 is o med as con i med by DRX. SEM mic og aphs, igu e 5,
clea ly show he needle-like s uc u e o he o med whiske s ha ing
hicknesses anging be ween 3 and 6 µm.
Washcoa ing was selec ed o coa ing he mic ochannels wi h he CuOx/CeO2
ca alys . The i s s ep o washcoa ing a me allic subs a e is o p epa e s able
slu ies o he ca alys o be deposi ed. Pa icle size, solid con en o he
suspension and pH o he ca alys slu y a e pa ame e s ha in luence he slu y
s abili y. The pa icle size o ou ca alys , d90=0.5μm, is well below 10µm he
uppe ecommend limi o p epa ing s able slu ies [31] he e o e he usual ball
milling p ocess o educing pa icle size was a oided. The isoelec ic poin
(IEP) o he ca alys is ca. 7 and he e o e he pH was ixed a 4 o ensu ing
high alues o ze a po en ial and hen high epulsions be ween he pa icles,
a ou ing he s abili y o he slu ies [32]. The use o addi i es o he slu y
o mula ion a emp s o imp o e he ca alys adhe ence and he washcoa ing
d ying p ocess. The addi ion o colloidal alumina, ha p esen s a na ow pa icle
size dis ibu ion, imp o es he ca alys adhe ence [31, 33] acco ding o he
model p e iously p oposed by Nijhuis e al. [34] a bimodal pa icle size
dis ibu ion inc ease adhe ence since he smalle pa icles a e loca ed be ween
he bigge ones. The use o poly inyl alcohol (PVOH) helps in p e en ing c ack
o ma ion du ing he d ying p ocess imp o ing he we ing p ope ies o he
ca aly ic laye . A e se e al ials o slu y o mula ion o washcoa ing he
ollowing p opo ions o ca alys and addi i es was selec ed: 76% ca alys
con en , 7% PVOH (w/w), 17% colloidal alumina (w/w) and pH o he
suspension adjus ed o 4 wi h dilu ed HNO3.
Assuming he Eins ein model o he diluen s dispe sion o ha d sphe es, he
iscosi y o ideal wa e slu ies only depends on he solid con en , being highe
as he solid con en inc eases [35]. In he case o he CuOx/CeO2 ca alys he
iscosi y anges om 20 cps o 15% solid con en o 200 cps o a dispe sion
con aining 25% solids. The iscosi y o he ca aly ic slu y is he key pa ame e
in con olling he coa ing p ocess; a de ailed desc ip ion o he di e en ac o s
in luencing he washcoa ing p ocess is gi en elsewhe e [31, 33]. Slu y wi h
18% solid concen a ion p o ides an excellen comp omise be ween he slu y
we ing p ope ies and ca alys loading. Figu e 6 p esen s he amoun o loaded
ca alys o e he subs a es as a unc ion o he numbe o coa ings. The
speci ic load inc eases almos linea ly wi h he numbe o coa ings. The
washcoa ing me hod gi es addi i e and homogenous esul s. Low iscosi ies
allow o ob ain highly adhe en and homogeneous coa ings bu wi h low speci ic
loads. Thus o ob aining he a ge loading nume ous coa ing a e equi ed. On
he con a y, high iscosi y will allow high speci ic load pe coa ing al hough wi h
lowe homogenei ies (i.e. accumula ions, channel blocking) esul ing in less
adhe en coa ings [33]. The slu y p epa ed in hese condi ions was s able o
96 hou s. Once he mic ochannels we e imme sed in he slu y he elimina ion
o he excess was done by ai blowing o mic ochannels (2L·min-1). Finally, he
mic ochannel block was d ied a 120ºC o 30 minu es be ween coa ings and
a e he las coa ing p ocedu e he mic ochannel block was calcined a 300ºC
o 3 hou s (1ºC/min). This p ocedu e esul ed in a mic ochannel block loading
o 5,46 mg·cm-2 ca alys a e eigh washcoa ing p ocesses. The adhe ence o
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TABLE AND FIGURE CAPTIONS
Table 1. Tex u al p ope ies o he ca alys s
Table 2. Hyd ogen consump ion du ing he TPR analysis o he CuOx-CeO2
solid
Table 3. Pa ame e s chosen o welding he mic ochannel pla es
Figu e 1: Schema ic pic u e o he s eel pla es-me allic glass assembly in c oss-
low con igu a ion.
Figu e 2. Joined Al-alloyed e i ic s ainless s eel pla es a 900ºC as a unc ion
o he applied uniaxial p essu e. A) 10 MPa and B) 15 MPa
Figu e 3. Mic os uc u es o he joined a ea. A) SEM mic ig aph be o e he
ec ys alliza ion p ocess; B) Op ical mic og aph a e ec ys allizing he
mic o eac o o 5h a 1200ºC; C) EDX line p o ile ac oss he joined a e a e
ec ys alliza ion; D) Gaussian i o he Ni EDX line p o ile ac oss he joined a e
a e ec ys alliza ion. The p o ile is aken along he line ma ked in pannel B.
Figu e 4. Mic ochannel block and mic ochannel eac o o he CO-PROX
eac ion.
Figu e 5. SEM mic og aphs o he α-Al2O3 o med upon hea ing a 900 ºC o 22
h in ai he mic ochannel block
Figu e 6. E olu ion o he ca alys loading a e he d ying p ocess as a unc ion
o he numbe o coa ings pe o med. The amoun loaded upon calcina ion is
indica ed by an a ow and he speci ic loading is indica ed a e 4, 6 o 8
coa ings
Figu e 7. XRD pa e n o he CuOx-CeO2 solid
Figu e 8. Raman spec a o he CuOx-CeO2 solid a di e en empe a u es
Figu e 9. TPR p o ile o he p epa ed CuOx-CeO2 solid
Figu e 10. CO con e sion (A) and O2 selec i i y o CO2 (B) o he CO-PROX
eac ion o e CuOx-CeO2 ca alys s. Open ci cles syn hesized ca alys ; Full
ci cles a e leaching in HNO3 a pH=2
Figu e 11. CO con e sion (A) and O2 selec i i y o CO2 (B) o he CO-PROX
eac ion o e CuOx-CeO2 ca alys s in a a mosphe e wi h CO:O2:H2:N2 a ios o
2:1:50:47. F(powde ) = 100 Ncm3·min-1; F(mic ochannel) = 300 Ncm3·min-1; W(powde ) =
100 mg; W(mic ochannel) = 300 mg
Figu e 12. CO con e sion o he CO-PROX eac ion o e CuOx-CeO2 ca alys s
in he mic ochannel block as a unc ion o he CO2 and H2O concen a ions in a
a mosphe e wi h CO:O2:H2:N2 a ios o 2:1:50:balance. F = 300 Ncm3·min-1;
W(mic ochannel) = 300 mg
Table 1
Ca alys
BET Su ace A ea
m2/g
Po e Volume
cm3/g
A e age po e diame e
Å
CuOx-CeO2 75.9 0.136 74.1
CuOx-CeO2 Slu y 91.6 0.200 100.0
Table 2
Reduc on Zone H2 consump ion (mol) Chemical composi ion
(mol)
A 1.21x10-4 Cu Ce
B 3.57x10-5 1.00x10-4 2.63x10-4

Table 3
Joining Pos -p ocessing
Applied o ce (kN) 2.8 ---
Tempe a u e (ºC) 850 1200
Hea ing a e (ºC·min-1) 100
Time (minu es) 40 300
A mosphe e Vacuum Ine gas
Figu e 1
Figu e 2
Figu e 3
Figu e 10

Figu e 11
Figu e 12