Catalysts for sorption enhanced reforming with …ieaghg.org/docs/General_Docs/6_Sol_Looping/3_HTSLC-CSIC...CATALYSTS SER OXI/RED CYCLES: RESULTS PGM-based reforming catalyst Reactor

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

CATALYSTS SER OXI/RED CYCLES: OVERVIEW

1.- Introduction2.- Objectives3.- Experimental4.- Results5.- Conclusions

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


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


(CaO → CaCO3)

Different solutions have been proposed- Gas combustion- Steam calcination

CaCO3 (s) CaO (s) + CO2 (g) ∆H298K= + 178.5 kJ/mol


SORPTION ENHANCED REFORMING-SERCOUPLED TO Ca-Cu CHEMICAL LOOPS

ReformingWGS


(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

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

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

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

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


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


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


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

10 20 30 40 50 60 70 80

0

CSi

Ni

Inte

nsity (

a.u

.)

2Theta


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


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


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

10 20 30 40 50 60 70 80

0

CSi

Ni

Inte

nsity (

a.u

.)

2Theta


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


SEM-EDX

Reduced

10 cycles

100 cycles

HiFUEL R110

Homogeneous surface distribution of elements


SEM-EDXParticle cut

HiFUEL R110

Homogeneous distribution of elements in the particle

20 mm100 cycles

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


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



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




HIGH ACTIVITY




HIGH ACTIVITY

PGM reduces at low temperaturesMaintains structure, phasesCrystallite size under detection limitsSurface morphology through oxidation/reduction cycles

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

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

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

Documents

Catalysts for sorption enhanced reforming with …ieaghg.org/docs/General_Docs/6_Sol_Looping/3_HTSLC-CSIC...CATALYSTS SER OXI/RED CYCLES: RESULTS PGM-based reforming catalyst Reactor