ingas 6-months meeting, prague, czech republic, 25-26 may 2009 ingas integrated gas powertrain 1...
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INGAS INGAS 6-months Meeting6-months Meeting, , PraguePrague, , Czech Republic, 25-26 May 2009Czech Republic, 25-26 May 2009
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Institute of Catalysis and Surface ChemistryPolish Academy of Sciences
6 months research activities
new catalyst formulations based on Cu-Mn mixed oxides
• synthesis
• physico-chemical characterization
• preliminary catalytic testing
WP2.2 Advanced Catalyst Development
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Synthetic approach for preparation of mixed oxide precursors:
• citrate method (sol-gel)
• hydrotalcite method
WP2.2 Advanced Catalyst Development
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WP2.2 Advanced Catalyst Development
Cu(II), Mn(II), Al(III) nitrates 2.5 M Citric acid
Viscous solution
Citrate Gel
Xerogel
Mixed oxide
Calcination 550oC
Drying 250oC
Stirring 65oC
Citrate method Hydrotalcite method
Cu(II), Mn(II), Al(III) nitrates
1 M Na2CO3/NaOH
Precipitation pH=9, 55oC
Hydrotalcite
Mixed oxide
Calcination 450oC
Drying 50oC
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Brucite Mg(OH)2
Hydrotalcite [(Mg0.75Al0.25)(OH)2](CO3)0.125·0.5H2O
[(Mg0.75Al0.25)(OH)2]0.25+
(CO3)2-
0.125
(H2O)0.5
Synthetic hydrotalcite [M2+
(1-x)M3+
x(OH)2]x+An-
x/nyH2O
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Synthetic hydrotalcite
[M2+(1-x)M
3+x(OH)2]
x+An-x/n
Synthetic hydrotalcite
M2+ = Mg, Ni, Zn, Fe, Co, Cu, Mn…
M3+ = Al, Mn, Fe, Cr ….
An - = CO32 –, NO3-, Cr2O7
2-, PMo12O403-…
0.20<x<0.33
[M2+(1-x)M
3+x](OH)2
[M2+(1-x)M
3+x](OH)2
[M2+(1-x)M
3+x](OH)2
An- An- An-
An- An- An-
An-An-An-An-
An-
[M2+(1-x)M
3+x](OH)2
An- H2O H2O
H2O H2O
H2O
H2O
H2O H2OH2O
Natural Hydrotalcite
M2+= Mg2+
M3+= Al3+
An-= CO32-, NO3
-
x = 0.25
WP2.2 Advanced Catalyst Development
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WP2.2 Advanced Catalyst Development
2 12 22 32 42 52 62 72
2 Theta CuKα
Inte
nsit
y [
a.u
.]
o - MnCO3
MnAlCO3 (2:1)
CuAlCO3 (2:1)
CuMnAlCO3 (2:1:1)
CuMnAlCO3 (1:1:1)
CuMnAlCO3 (1:2:1)
CuMnAlCO3 (4:4:1)
CuMnAlCO3 (12:5:1)
XRD of Cu-Mn-Al hydrotalcite-like precursors
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0
500
1000
1500
2000
2 12 22 32 42 52 622
RT
3000C
2000C
1000C
8000C
6000C
5000C
4000C
CuMn2O4
CuOHTlc CuAlCO3
Mn2AlO4MnAl2O4
WP2.2 Advanced Catalyst Development
Thermal decomposition of
CuMnAl/1:1:1/ hydrotalcite-like
precursor monitored in a high
temperature XRD chamber
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SampleOxidic phases after calcination at
373 K 473 K 573 K 673 K 773 K 873 K 973 K 1073 K 1173 K
CuAlCO3
(2:1)
HT HT --- --- CuO CuO CuOCu2Al4O7
CuOCu2Al4O7
CuOCu2Al4O7
CuMnAlCO3
(12:5:1)
HTR
R --- --- CuMn2O4
CuO
CuMn2O4
CuO
CuMn2O4
CuO
CuMn2O4
CuO
CuMn2O4
CuO
CuMnAlCO3
(4:4:1)
HTR
R --- --- CuMn2O4
CuO tracesMn2O3
traces
CuMn2O4
CuOMn2O3
Mn2AlO4
CuMn2O4
CuO
Mn2AlO4
CuMn2O4
CuO
CuMnO2
MnAl2O4
CuMnAlCO3
(2:1:1)
HT --- --- --- CuMn2O4 CuMn2O4
CuO traces
CuMn2O4
MnAl2O4
CuO
CuMn2O4
MnAl2O4
CuO
CuMn2O4
CuOMnAl2O4
CuMnAlCO3
(1:1:1)
HTR
R --- --- CuMn2O4 CuMn2O4
(weak)Mn1+xAl2-xO4
CuMn2O4
Mn2AlO4
MnAl2O4
CuMn2O4
CuOMn2AlO4
CuMn2O4
CuOMn2AlO4
CuMnAlCO3
(1:2:1)
HTR
R --- --- CuMn2O4 CuMn2O4
Mn2O3
CuMn2O4
Mn2O3
Mn2AlO4
CuMn2O4
Mn2O3
traces
Mn2AlO4
CuMn2O4
MnAlCO3
(2:1)
HTR
--- --- --- Mn3O4 Mn3O4 Mn3O4 Mn2AlO4
Mn2O3
Mn2AlO4
WP2.2 Advanced Catalyst Development
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XRD of mixed oxides derived from hydrotalcite-like precursors
2 12 22 32 42 52 62 722 Theta CuKα
Inte
nsit
y [
a.u
.]
CuO
CuMn2O4
Mn3O4
MnAl (2:1)
CuMnAl (2:1:1)
CuAl (2:1)
CuMnAl (4:4:1)
CuMnAl (1:2:1)
CuMnAl (1:1:1)
CuMnAl (12:5:1)
WP2.2 Advanced Catalyst Development
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Bulk vs. surface chemical composition
Sample Cu:Mn:Alatomic ratios-bulk values
(ICP OES)
Cu:Mn:Alatomic ratios
-surface values (XPS)
BET [m2/g]
CuMnAl (12:5:1) 13:5.1:1 4.7:2.1:1 55
CuMnAl (4:4:1) 4.1:4.2:1 0.9:1.6:1 61
CuMnAl (1:1:1) 1.1:1.2:1 1.2:1.8:1 96
CuMnAl (2:1:1) 2.1:1.1:1 1.2:0.6:1 62
CuMnAl (1:2:1) 1.1:2.2:1 0.9:1:1 132
MnAl (2:1) 2.3:1 0.4:1 237
CuAl (2:1) 2.2:1 0.2:1 30
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CuMnAl (1:1:1)
HAADF STEM shows that CuMnAl (1:1:1) is a mixture of semi-amorphous oxide phases of different composition. HRTEM proves that one of them is nanocrystalline spinel CuMn2O4.
HAADF STEM
Transmission Electron Microscopy
STEM of CuMnAl 6:2:15 nm
HRTEM
WP2.2 Advanced Catalyst Development
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WP2.2 Advanced Catalyst Development
CuAl (2:1) CuMnAl (2:1:1) CuMnAl (4:4:1)
precursor precursorprecursor
calcined calcined calcined
Scanning Electron Microscopy
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Cu 2p3/2,1/2 Mn 2p3/2,1/2 XPS
Sample % Cu+ % Cu2+ % Mn2+ % Mn4+
CuMn 1350C 5.1 42.65 31.5 68.5
CuMn 2400C 61.2 35.5 27.5 72.5
Contribution of various Cu and Mn oxidation states at the surface of a CuMnAl/2:1:1/Ht catalyst after exposure to air at different temperatures
reduction oxidation
WP2.2 Advanced Catalyst Development
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WP2.2 Advanced Catalyst Development H2 TPR of Cu-Mn-Al mixed oxides
derived from hydrotalcite precursors
300 500 700 900Temperature [K]
H2
co
ns
um
pti
on
[a
.u.] CuAl (2:1)
MnAl (2:1)
CuMnAl (2:1:1)
CuMnAl (12:5:1)
CuMnAl (1:1:1)
CuMnAl (4:4:1)
CuMnAl (1:2:1)
601 K
558 K
567 K
564 K
581 K
630 K
734 K
547 K
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WP2.2 Advanced Catalyst Development
XRD patterns of Cu-Mn-Al mixed oxides derived from citrate precursors.
0
100
200
300
400
500
600
700
800
900
1000
2,00 12,00 22,00 32,00 42,00 52,00 62,00 72,002 Theta
Cou
nts
MnAl/1:2/Cit
MnAl/2:1/Cit
CuMn/1:2/Cit
Cu1.5Mn1.5O4/CuMn2O4
Mn2O3
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WP2.2 Advanced Catalyst Development
MnAl/2:1/Ht MnAl/2:1/Cit
Influence of the nature of precursor
237 m2/g 77 m2/g
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WP2.2 Advanced Catalyst Development
CH4 combustionfixed-bed flow glass reactor, p=1 bar, temperature = 175-525oC, catalyst - 0.5 ml,
[CH4] = 1g/m3, GHSV = 10 000 h-1.
0
20
40
60
80
100
120
150 200 250 300 350 400 450 500 550
Temperature [oC]
CH
4 co
nve
rsio
n [
%]
.
ECOCAT REFERENCE
CuMnAl/4:4:1/Ht
CuMnAl/1:2:1/Ht
MnAl/2:1/Ht
CuAl/2:1/Ht
MnAl/1:2/Cit
CuMn/1:2/Cit
MnAl/2:1/Cit
Sample
T50
[oC]
BET [m2/g]
CuMnAl/4:4:1/Ht 389 61
CuMnAl/1:2:1/Ht 411 132
MnAl/2:1/Ht 412 237
CuAl/2:1/Ht 470 30
MnAl/2:1/Cit 478 77
MnAl/1:2/Cit 439 324
Cu/Mn/1:2/Cit 458 18
ECOCAT washcoat 255 n.d.
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WP2.2 Advanced Catalyst Development
Future action
• Further exploration along the compositions based on mixed Cu and Mn oxides, aiming at maximization of the specific surface area and simultaneous formation of the copper-rich spinel phase.
• Investigation of compositions enriched with promoters (e.g. Ce, Zr).
• Synthesis of perovskite and hexaaluminate precursors containing Co and La.