catalysts for sorption enhanced reforming with...
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Catalysts for sorption enhanced reformingwith oxidation/reduction cycles
M.V. Navarro, J.M. Pardo, J.M. López, T. García, G. Grasa, R. Murillo, *A. Scullard, *G. Williams
Instituto de Carboquímica (ICB-CSIC), Zaragoza/Spain*Johnson Matthey Public Limited Company, London/United Kingdom
6th High Temperature Solid Looping cycles Network MeetingIEA Greenhouse Gas R&D ProgrammeMilan, 1-2 September, 2015
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CATALYSTS SER OXI/RED CYCLES: OVERVIEW
1.- Introduction2.- Objectives3.- Experimental4.- Results5.- Conclusions
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CATALYSTS SER OXI/RED CYCLES: INTRODUCTION
ReformingWGS
(Catalyst)Carbonation
(CaO → CaCO3)
H2
600-700ºC
By Le Chatelier’s principal, elimination of CO2 shifts the reaction to productsincreasing H2 production
CH4+H2O
SORPTION ENHANCED REFORMING-SER
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CATALYSTS SER OXI/RED CYCLES: INTRODUCTION
Heat 900ºC
CH4+H2O
H2
600-700ºC
Calcination needed for CaO regeneration and CO2 capture
(Catalyst)Calcination
(CaCO3 → CaO)
Fresh Sorbent
Used Sorbent
CaCO3
CaO
CO2
SORPTION ENHANCED REFORMING-SER
ReformingWGS
(Catalyst)Carbonation
(CaO → CaCO3)
Different solutions have been proposed- Gas combustion- Steam calcination
CaCO3 (s) CaO (s) + CO2 (g) ∆H298K= + 178.5 kJ/mol
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CATALYSTS SER OXI/RED CYCLES: INTRODUCTION
SORPTION ENHANCED REFORMING-SERCOUPLED TO Ca-Cu CHEMICAL LOOPS
ReformingWGS
(Catalyst)Carbonation
(CaO → CaCO3)(Cu)
CH4+H2O
H2
600-700ºC
(Catalyst)Calcination
(CaCO3 → CaO)Reduction(CuO→ Cu)
Reduction Gas
(Catalyst)(CaCO3)
Oxidation(Cu→ CuO)
850ºC
870ºC
Air N2
CO2
CuO(s) + H2(g) Cu(s) + 2H2O(g) ∆H298K= - 89.6 kJ/mol
CuO(s) + CO(g) Cu(s) + CO2(g) ∆H298K= -131.9 kJ/mol
4CuO(s) + CH4(g) 4 Cu(s) + CO2(g) + 2H2O(g) ∆H298K= -195.3 kJ/mol
Fresh Sorbent Used Sorbente
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CATALYSTS SER OXI/RED CYCLES: OBJECTIVES
• To obtain stable materials to run the reforming coupled to Ca-Cu loopingprocess throughout successive oxidation/reduction cycles
Reforming catalysts
General Process
• High reforming activity
• Maintain activity throughout successive oxidation/reduction cycles
• Resistant against deactivation
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CATALYSTS SER OXI/RED CYCLES: EXPERIMENTAL
Thermally stabilized systemat 200ºC
Massspectrometer
Flows and temperature controllers
Reforming reactor
Steam generator
Gas lines
INSTALLATION: Fixed bed+ MS
m/z =2 for H2m/z =15 for CH4m/z=18 for H2Om/z =28 for COm/z=32 for O2m/z =40 for Arm/z=28 and 44 for CO2.
𝐶𝐻4 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 =𝑚𝑙 𝐶𝐻4,𝐼𝑁 −𝑚𝑙 𝐶𝐻4,𝑂𝑈𝑇
𝑚𝑙 𝐶𝐻4,𝐼𝑁∙ 100
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CATALYSTS SER OXI/RED CYCLES: EXPERIMENTAL
• TPR:
• SEM-EDX:
• XRD:
Micromeritics PulseChemisorb 2700
Difractometre:Bruker D8 Advance Series 2
Microscope SEM EDX Hitachi S-3400 N
Variable pressure up to 270 Pa
Pretreatment:30mLN/min Ar, 150 ºC, 30min.
Treatment:10% H2 in Ar 30mLN/min, 10ºC/min, Tf, 30 min
Radiation source:Cu-Kα with l of 532 nm.
Mesures:Range 10°-80° with step 0.05°, time 3s, temperature 25 ºC.
Sample Provider Composition Preparation Size, mm
HiFUEL R110 pellets Johnson-Matthey 17wt% NiOCaAl2O4
(1)
CrushedSieved
<200
PGM-based reforming catalyst powder Johnson-Matthey Sieved <200(1)Energy Fuels 2015, 29, 2656−2663
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Reactor bed catalyst: 200mg CSi: 2.5g
Reduction: 33.3 mLN/min, 10%H2 in Ar, 650ºC, 30 min
Reforming S/C: 3CH4: 10mLN/min Ar: 30mLN/min ArSV=2.15kgCH4/h·kgcat
Theoretical calculations in HSC Chemistry 5.1
Lines are theoretical equilibrium dataPoints are experimental data, increasing temperatureAsterisks are experimental data, decreasing temperature
CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110
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CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110
SV=2.15kgCH4/h·kgcat SV=8.59kgCH4/h·kgcat
EFFECT OF kgCH4/h·kgcat
Initial
10 cyclesoxid/red
Oxid: 850ºC, 5%O2Red: 650ºC, 10%H2
HIGH ACTIVITY
CYCLIC STABILITY
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CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110
Reactor bed catalyst: 200mg CSi: 2.5g Reduction before reforming 33.3 mLN/min, 10%H2 in Ar, 650ºC, 30 minReforming S/C 3, 10mLN/min CH4, 30mLN/min Ar, SV=2.15kgCH4/h·kgcat
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CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110
Reactor bed catalyst: 50mg CSi: 0.625g Reduction before reforming 33.3 mLN/min, 10%H2 in Ar, 650ºC, 30 minReforming S/C 3, 10mLN/min CH4, 30mLN/min Ar, SV=8.59kgCH4/h·kgcat
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10 20 30 40 50 60 70 80
0
CSi
Ni
Inte
nsity (
a.u
.)
2Theta
CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110 XRD
Reduced 10 cycles
Ni crystallite size, nm 9 16
SEM-EDX
Reduced
10 cycles
Sample Phases
Ni
CaAl4O7
Al2O3
Reduced
10 cycles
Maintains structure and main phasesIncrease in crystallite sizeMaintains surface morphology
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CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110TPR
Treatment:10% H2 in Ar 30mLN/min, 10ºC/min, 650ºC, 30 minH2: 54.04 mlH2/gcat
Part of the sample was notreduced before the reforming step
Treatment:10% H2 in Ar 30mLN/min, 10ºC/min, 900ºC, 30 minH2: 69.54 mlH2/gcat
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CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110
Reactor bed catalyst: 50mg CSi: 0.625g TB cycling: 0-850ºC in N2, reduction 850ºC 10%H2 5min, oxidation 850ºC 20%O2 5minReforming S/C 3, 5mLN/min CH4, 15mLN/min Ar, SV=4.30kgCH4/h·kgcat
10mLN/min CH4, 30mLN/min Ar, SV=8.59kgCH4/h·kgcat
HIGH ACTIVITY
EFFECT OF 100 CYCLES
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10 20 30 40 50 60 70 80
0
CSi
Ni
Inte
nsity (
a.u
.)
2Theta
CATALYSTS SER OXI/RED CYCLES: RESULTS
HiFUEL R110XRD
Reduced 10 cycles 25 cycles 50 cycles 100 cycles
Ni crystallite size, nm 9 16 31 30 31
SEM-EDX
Reduced
10 cycles
Sample Phases
Ni
CaO·2(Al4O7)
Al2O3
100 cycles
Reduced
10 cycles
100 cycles
Maintains structure and main phasesMaximum of crystallite sizeMore white spots on surface
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CATALYSTS SER OXI/RED CYCLES: RESULTS
SEM-EDX
Reduced
10 cycles
100 cycles
HiFUEL R110
Homogeneous surface distribution of elements
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CATALYSTS SER OXI/RED CYCLES: RESULTS
SEM-EDXParticle cut
HiFUEL R110
Homogeneous distribution of elements in the particle
20 mm100 cycles
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Reactor bed catalyst: 200mg CSi: 2.5g
Reduction: 33.3 mLN/min, 10%H2 in Ar, 650ºC, 30 min
Reforming S/C: 3CH4: 10mLN/min Ar: 30mLN/min ArSV=2.15kgCH4/h·kgcat
Theoretical calculations in HSC Chemistry 5.1
Lines are theoretical dataPoints are experimental data, increasing temperatureAsterisks are experimental data, decreasing temperature
CATALYSTS SER OXI/RED CYCLES: RESULTS
PGM-based reforming catalyst
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CATALYSTS SER OXI/RED CYCLES: RESULTS
PGM-based reforming catalyst
HIGH ACTIVITY
Initial
10 cyclesoxid/red
Oxid: 850ºC, 5%O2Red: 650ºC, 10%H2
CYCLIC STABILITY SV=2.15kgCH4/h·kgcat
HIGH ACTIVITY
EFFECT OF kgCH4/h·kgcat
SV=8.59kgCH4/h·kgcat
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CATALYSTS SER OXI/RED CYCLES: RESULTS
PGM-based reforming catalyst
Reactor bed catalyst: 200mg CSi: 2.5g Reduction before reforming 33.3 mLN/min, 10%H2 in Ar, 650ºC, 30 minReforming S/C 3, 10mLN/min CH4, 30mLN/min Ar, SV=2.15gCH4/h·kgcat
HIGH ACTIVITY
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CATALYSTS SER OXI/RED CYCLES: RESULTS
PGM-based reforming catalyst
Reactor bed catalyst: 50mg CSi: 0.625g Reduction before reforming 33.3 mLN/min, 10%H2 in Ar, 650ºC, 30 minReforming S/C 3, 10mLN/min CH4, 30mLN/min Ar, SV=8.59gCH4/h·kgcat
HIGH ACTIVITY
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CATALYSTS SER OXI/RED CYCLES: RESULTS
PGM-based reforming catalyst
Reactor bed catalyst: 50mg CSi: 0.625g Reduction before reforming 33.3 mLN/min, 10%H2 in Ar, 650ºC, 30 minReforming S/C 3, 10mLN/min CH4, 30mLN/min Ar, SV=8.59gCH4/h·kgcat
HIGH ACTIVITY
PGM reduces at low temperaturesMaintains structure, phasesCrystallite size under detection limitsSurface morphology through oxidation/reduction cycles
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CATALYSTS SER OXI/RED CYCLES: CONCLUSIONS
CONCLUSIONS
• A commercial catalyst applied industrially in reforming processes hasshown to be a stable material to run the reforming step coupled toCa-Cu looping process up to 100 oxidation/reduction cycles
• Promising results on PGM-based reforming catalyst of high activityand high space velocity up to 10 cycles.
High reforming activity
Maintain activity throughout successiveoxidation/reduction cycles
Resistant against deactivation
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AKNOWLEDGEMENTS
CATALYSTS SER OXI/RED CYCLES: AKNOWLEDGEMENTS
• Advance Solid Cycles with Efficient Novel Technologies ASCENT EU FP7, Nº: 608512
• Hydrogen production with CO2 capture using novel Ca-Cu reforming cyclesCiCaCuH Spanish Government, ENE 2012-37936-CO2-1
• Grupo de Investigaciones MedioambientalesGIM Diputación General de Aragón, Research group funding
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Catalysts for sorption enhanced reformingwith oxidation/reduction cycles
6th High Temperature Solid Looping cycles Network MeetingIEA Greenhouse Gas R&D ProgrammeMilan, 1-2 September, 2015
Thank you for yourattention
e-mail: [email protected]
M.V. Navarro, J.M. Pardo, J.M. López, T. García, G. Grasa, R. Murillo, *A. Scullard, *G. Williams