Fundamentals of Gas Separations and CO2 Capture Technology / Developments in Membrane Separation

7/28/2019 Fundamentals of Gas Separations and CO2 Capture Technology / Developments in Membrane Separation

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FundamentalsofGasSepara2onandCOCaptureTechnology

DevelopmentsinMembraneSepara2on

JenniferWilcox

DepartmentofEnergyResourcesEngineering

RECSSummerSchoolJune19th,2013


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CleanEnergyConversionsTeam-013

BryceAnzelmo(PhD) PanithitaRochana(PhD) EkinOzdogan(PhD) JiajunHe(PhD) KyoungjinLee(PhD) AbbyKirchofer(PhD) AnaSuarezNegreira(PhD,ChemE) MengyaoYuan(PhD)

BeibeiWang(MS) TaoNarakornpijit(MS) JeremyHoffman(UG,Chem)RezaHaghpanah(Post-doc) Dong-HeeLim(Post-doc)

MahnazFirouzi(Post-doc) DawnGeatches(Post-doc) ErikRupp(ResearchAssistant)


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Agenda

ScaleofEmissionsWorkofCarbonCapture

N2-SelecveMembranes


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ToPreventCWarming

Between2000-2050ifcumulaveemissionsarelessthan: 1,000Gt25%probabilityglobal

warmingbeyond2C

1,440Gt50%probabilityglobalwarmingbeyond2C

Wherewereprojectedtogo(BAU):

Assumingannualincreases: Coal0.3% Oil0.9% NaturalGas2.3%

~29GtCO2emiedin2009 ~44GtCO

2projectedin2050

1790cum.GtCO2in2050!

BAU

009 050

Ref:Allenetal.,Nature,2009

Ref:BPStascalRev.ofWorldEnergy,2012


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ExpandingtheImpactofCCS

BAU-1790GtCO

1000GtCO5%probabilityofC

1440GtCO50%probabilityofC

Scenario AvoidedCum.GtCO

ReplaceCoalw/NG 1512

90%Capture(PointSourceElectricSector) 1288

90%Capture(PointSourceElectricSector)+50%

Transport(on-boardcapture;EV;DAC)

1083


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Apprecia2ngtheScale USpopulaon~311,591,000 CHpopulaon-~1,344,130,000 Annualemissionspercapita:

US~17.5tonsCO2 CH~5tonsCO2

FlightfromSFtoBirmingham(viaHouston)RT~0.7tonsCO2

DriveHondaAccord~1.5tonsCO2 DriveHondaCivicHybrid~0.74tonsCO2 Dependingonsorbentloadingand

performance(cycling)

17.5tonstotal150tonsmaterial

JusttheCOperpersoninUS!

Justthesorbent+COperpersoninUS!


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CaptureandRegenera2onareBothKey

CapturingCO2isonlythestory MUSTregenerate Oponsforusage:

Chemicalfeedstock? Challengemarketissmall

Enhancedoilrecovery(akaEOR) Seemstobebestnear-termopon

Storage Challengesincludepublicperceponandovercomingrisks

ofpotenalseismicevents

AmineScrubbing-CurrentState-of-the-Art

TechnologyforPoint-Source

CaptureofCO2


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Agenda


N2-SelecveMembranes


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MinimumWorkforSepara2oncombinedfirstandsecondlaws

Wmin =RT nBCO2 ln(yB

CO2 ) + nBB CO2 ln(yB

B CO2 )[ ] +RT nCCO2 ln(yC

CO2 ) + nCCCO2 ln(yC

CCO2 )[ ]RT nA

CO2 ln(yACO2 ) + nA

A CO2 ln(yAA CO2 )[ ]

Wilcox,CarbonCapture,Springer,2012


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MinimumWorkforSepara2on

APSReport,FeasibilityofDACwithChemicals,2011


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1

3

5

7

9

11

13

15

17

19

0 0.05 0.1 0.15 0. 0.5 0.3 0.35 0.4

Minimum

Work

(kJ/

mo

lCO

2Cap

ture

d)

COConcentra2on

50%capture;80%purity75%capture;80%purity90%capture;80%purity50%capture;95%purity75%capture;95%purity90%capture;95%purity

50%capture;99%purity75%capture;99%purity90%capture;99%purity

MinimumWork

CoalGasifica2on1-

4kJ/molCO

NaturalGasCombus2on6-9kJ/molCO

CoalCombus2on5-7kJ/molCO

DirectAirCapture191kJ/

molCO

DACisalways~20kJ/molCO2,regardlessof%captureand

purity

Reason:capturinglessofagiventotalgas

Addionalworkrequiredduetodensitychangesw/mixturesof

CO2andN2

95%CO2+5%N2:681kg/m3 80%CO2+20%N2:343kg/m3 ~0.5kJ/molCO2addional

compressionenergy!

Ref:Wilcox,CarbonCapture,2012


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SherwoodPlotforFlueGasScrubbing

CalculaonscarriedoutusingIECM,allcasesassume500-MWplantburningAppalachianbituminous,NGCC(477-MW)

O&M+annualizedcapitalcostsareincludedinthecostesmates


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CostandScale

Process Price[$/kg]

Concentra2on[molefrac2on]

Emissions[kg/day]

Cost[1000s$/day]

CO2-PCC 0.045 0.121 8.59x106 392

CO2-NGCC 0.059 0.0373 3.01x106 178

SOx(MS) 0.66 0.00127 8.94x104 59.6

SOx(LS) 2.1 0.000399(399ppm) 2.32x104 50.4NOx 1.1 0.000387(387ppm) 1.11x10

4 12.5

Hg 22000 5x10-9(ppb) 0.951 21.6

Valuesmaychangebaseduponcoal-typeburnedandscrubbingmethods;1ENLighoot,MCMCockrem,WhatAreDilute

Soluons,Sep.Sci.Technol.,(),165(1987)

the recovery of potentially valuable solutes from dilute solution is dominated by the costsof processing large masses of unwanted materials.1 -Edwin Lightfoot


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nd-LawEfficiencyDropswithConcentra2on

House,K.Z.etal.,Proc.Nat.Acad.Sci.,108(51),20428-20433(2011)

2nd

=

Wmin

Wreal


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BenefitsofMembraneProcesses

Focusisonthemoreconcentratedgas,i.e.,N2 DAC,NaturalGas,Coalapplicaons

Basedprimarilyuponphysicalseparaonprocesses,withCO2maintainingitslinearformthroughoutseparaon

Waterdoesnotneedtobeunnecessarilyheated;mostsolventsareaqueous-basedw/thechemical~30%

Regeneraonisnotrequiredinmembraneseparaon Ingeneral,thefootprintissmaller

MembraneProcess:

Majorchallengew/CO2-selecvepolymers:lackofdrivingforceinfluegasw/CO2concentraon~12%-considerN2-selecvemembraneinstead


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Agenda


N-Selec2veMembranes


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N-Selec2veMembraneforCarbonCapture

Flux:

Q=permeability=DiffusivitySolubility

L=membranethickness

InspiraonARPA-Ebrainstormsessionin2010 CaptureCO2onthehigh-pressuresideofthemembranemayleadtocostsavingsin

termsofcompressionenergy Canwedoit?Startw/aliteraturereview

Feed

Residue(retentate)

Permeate


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NandODiffusivityinVanadiumPermeability=DiffusivitySolubility

1Keinonenetal.Appl.Phys.A34,39(1984);2Nakajimaetal.PhilosophicalMagazineA67,557(1993).3Holleck,J.Phys.Chem.74,503(1970);4FukaiandSugimoto,Adv.InPhys.34,263(1985)


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NandOSolubilityinVanadium

1Henry,J.L.,etal.J.Less-CommonMetals5,39(1971);2Henry,J.L.,etal.J.Less-CommonMetals1,115(1970);3Tanaka,S.;Kimura,H.Trans.JIM0(1979).

Hydrogen solubility in vanadium3Decreasing()


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Theory,Experiments,andOp2miza2on-theteam-

TheoryandExperiments:

Opmizaon:

PhDstudents:NiRochana,EkinOzdogan,

KyoungjinLee

PhDstudents:MengyaoYuan,TaoNarakornpijit

Post-doc:RezaHaghpanah

2 l li 2 f S l 2 b


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N

Mem

brane

Step1

Adsorp2on StepDissocia2onN N

NStep3

BulkDiffusion

NNN

H NH3

Poten2alApplica2ons:

CarboncaptureAmmoniasynthesis

Methane/N2mixtures Airseparaon(selecveO2)(IGCC,oxy-combuson)

Goals: Use DFT to provide insight into tuning materials electronic structure for

enhancednitrogenreacvity

PerformpermeaontestsontheGroupVmaterials

Poten2alApplica2onsforN-Selec2veMembranes

PhDstudents:NiRochana,EkinOzdogan,

KyoungjinLee


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NDissocia2onisDifficult!

Bonddissociaonenergies N~225kcal/mol;944kJ/mol;9.7eV O~119kcal/mol;498kJ/mol;5.1eV H~104kcal/mol;435kJ/mol;4.4eV

CommonN2dissociaoncatalysts(H-B,ammoniasynthesis) Fe,Ru

d-bandcentermodel(HammerandNrskov)providesinsight


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Thedensityofstates(DOS)ofasystemdescribesthenumberofstatesat

eachenergylevelthatareavailabletobeoccupied.

DensityofStates

unoccupiedoccupied

Fermi level

Transionmetalreacvityisdisnguishedbyitsd-states,witheach

transionmetalhavingacharacteriscd-bandcenter


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d-bandCenterModel

Whenbondingandan-bondingstatesareformed,bondstrengthdependsontherelaveoccupancyofstates Bondingstatesfilledstrongbonds;an-bondingstatesfilledweakening

d-bandcenterincreasesfromRtoLofperiodictable(transionmetals) bothbondingandan-bondingstatesarehigherfromRtoL Strengthofadsorbate-metalbondincreases

WhyuseFeandRuforammoniasynthesis?WhynotGroupV? answervolcano

HammerandNrskov,Nature376238(1995);HammerandNrskov,Adv.Catal.4571-129(2000)


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MaterialScreeningandDFT

1.Surfaceac2vity N2adsorponmechanism N2dissociaonpathway Comparisontoothertypical

ammoniasynthesiscatalysts

.SolubilityandDiffusivity AtomicNbinding

mechanism

ComparisontoatomicHbinding

3.Effectofalloying

Ru Effectonbinding Implicaonsfor

permeability

Computa2onalMethodology

VASP(ViennaabinioSimulaonPackage)

Densityfunconaltheory(DFT)

Projector-augmentedwave(PAW)potenal

GGAPBEBulk vanadium Lattice constant

[]

This study 2.98

Previous calculation 2.93-2.941

3.0212

Experiment 3.0243

1MehlandPapaconstantopoulos,Phys.Rev.B54,4519(1996);2Vitosetal.,J.,Surf.Sci.411,186(1998);3OnlineCRCHandbookofChemistryandPhysics,91stedion,2010-2011


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MolecularNAdsorp2onEnergy

1Grunze,etal.,Appl.Phys.A44,19(1987);2Bozso,etal.J.Catal.49,18(1977);Ertletal.,Surf.Sci.114,515(1982);3Sheyetal.,J.Phys.Chem.C11,17768(2008)

strength of N2-metalbond increases

Eads (eV/molecule) = E(surf+N2) [E(surf)+E(N2)]n(N2)V(110)

1-top2-short-bridge (SB)3-long-bridge (LB)4-three-fold (TF)

V(111)

1-top, 2-hcp3-fcc, 4-bridge


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Absorp2onofAtomicNinBulkV

Intersal

binding

Vanadium:bccstructure 1)O-site 2)T-site

Configura2on Conc.(at.%)Ebinding(eV/N)

V16N(O) 6.25 -1.99

V16N(T) 6.25 -0.90

Ebinding (eV/atom) = E(bulk + n N atoms) [ E(bulk) + 0.5n*E(N2) ]


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Absorp2onofTwoNAtomsinBulkV

No. Configura2on Conc.(at.%) N-Ndist.()Ebinding(eV/N)

1 V16N2(T,T) 12.5 2.991 -1.55

2 V16N2(O,O) 12.5 2.499 -2.10

3 V16N2(O,O) 12.5 2.800 -2.70

4 V16N2(O,O) 12.5 4.240 -2.78

1 32 4


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BaderChargeAnalysisonV16N

-1.545 -1.545

+0.011 +0.016

+0.008

+0.008+0.008

+0.008

+0.016

+0.016

+0.381

+0.011

+0.011

+0.011

+0.011

+0.011

+0.011

+0.381

+0.381+0.381

+0.016

+0.016

+0.381

+0.381

+0.378+0.378

+0.379 +0.380

+0.001

+0.378

+0.376 +0.376 -0.00

+0.016+0.011

+0.006

+0.005

AsVdonatesitsd-electronstop-stateofN,chargeis

accumulatedonN

Chargeinterac2oncouldexplainthestrongbindingofN

inV,aswellastherepulsive

interaconbetweenNatoms

Strongbindingcouldenhancethesolubility.However,too

strongbindingcanleadtoa

slowdiffusionprocess

Pauling-ScaleElectronegavies:N=3.04;V=1.63;Ru=2.2


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EffectofRuAddi2on

Ru Ru

+2.836

-0.09

-0.254 -0.257

-0.255

-0.141

-0.255

Pure Vanadium Distance (N-Ru)= 0.5 Distance (N-Ru)= 0.71

+2.710

-0.292-0.292

-0.292

-0.374

-0.292+3.075

-0.235

-0.174

-0.372

-0.372

-0.214

+3.347 +3.075

Lattice Constant= 3.01

Eb= -2.132 eVLattice Expansion= 1.01%





HbindinginV:O-site=-0.076eV;T-site=-0.280eV

Aboud and Wilcox, J. Phys. Chem. C, 114(24) 10978-10985 (2010);Pauling-Scale Electronegativities: N = 3.04; V = 1.63; Ru = 2.2


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FluxMeasurements

Test Temperatures:500C -1000C

MembraneFoils

(GroupVmetals)DiffusionBarrier

(uniformlyrigidizedsheetof

aluminafiberandbinder)

PorousSupport

(HastelloyX)

Inside of Membrane Holder

SweepGas

Permeate

Retentate

FeedGas

Test Pressures:20 90 psi

M b D f t C 2


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Fluxmeasurements: Argongasusedtocorrectforpinholeandgeneralleaksinthemembranesystem Eachpurefoilistestedatatemperaturerangeof500C-1000C.Ateachtemperature,

feedpressureischangedbetween23.4-93.4psig.RetentatePressureiskeptat3.4psig

UseKnudsendiffusionforcorrecons:

MembraneDefectCorrec2ons

Nitrogen Permeability measurement


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NitrogenPermeabilitymeasurement

Nitrogenpermeabilitythroughvanadiumishigherbytwoordersofmagnitudethanitspermeabilitythroughniobium.

ComparetothehydrogenpermeabilitythroughPdmembrane(1.610-8mole/msPa0.5),enhancingthenitrogenpermeabilitybyalloyingorother

techniquesisnecessary.

Vhasala{ceconstantof2.98;Nbhasala{ceconstantof...


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COPermeabilitymeasurement

CO2permeabilityislowerthannitrogenpermeabilitybyfiveordersofmagnitudeinvanadium.CO2isexpectedtodiffusethroughthedefectsin

themetals,whichishighlylimited.


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FluxMeasurementsw/GasMixturesNiobium(P=90psi)

0.00E+00

5.00E-07

1.00E-06

1.50E-06

2.00E-06

2.50E-06

0.00E+00

5.00E-05

1.00E-04

1.50E-04

2.00E-04

2.50E-04

3.00E-04

0.001 0.0011 0.0012 0.0013 0.0014

CO2

Flux((mole/ms)

N2

Flux(mole/ms)

1/T (K-1)

4 mol% CO2-96 mol% N2

N2 CO2

0.00E+00

1.00E-06

2.00E-06

3.00E-06

4.00E-06

5.00E-06

6.00E-06

7.00E-06

8.00E-06

0.00E+00

5.00E-05

1.00E-04

1.50E-04

2.00E-04

2.50E-04

0.001 0.0011 0.0012 0.0013 0.0014

CO2

Flux((mole/ms)

N2

Flux(mole/ms)

1/T (K-1)

15 mol% CO2-85 mol % N2

N2 CO2

Naturalgasfluegas Coalfluegas


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MembraneSurfaceAerPermea2on

ScanningElectronMicroscopy(SEM)onVmembranes

ExposuretohighTinducesstructuralchangesassociatedwithdefectformaon Gasexposureenvironmentsaffectcrystallinestructures


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MembraneSurfaceAerPermea2on

X-rayPhotoelectronSpectroscopy(XPS)

Surfacenitrideisconfirmedbythetailofvanadium2pspectra

O1s

V2p

Nitride

V2p

V2p

Nitride


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MembraneBulkAerPermea2on

X-rayDiffrac2on(XRD)onVmembranes

!

Bulkvanadiumnitridephasesformeda}erexposuretoN 2athightemperature


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ModelingandOp2miza2on Scopeofresearch

Processmodeling:Modelingofpost-combusoncapturefromcoal-firedpowerplantsusingN2-selecvemembranesandtheircombinaonswithCO2-selecvemembrane

Bi-objec2veop2miza2on:AssessmentoftheengineeringfeasibilityofusingN2-selecvemembranesinlarge-scalecaptureapplicaonsby

simultaneouslyminimizingenergyandmembranesurfacearearequirements,twoimportantindicatorsofcapturecosts

SixmembraneconfiguraonshavebeenmodeledinMATLAB;Bi-objecveopmizaonwasperformedbythebuilt-ingenecalgorithminMATLAB

PhDstudents:MengyaoYuan,TaoNarakornpijit

Post-doc:RezaHaghpanah


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MembraneConfigura2ons:N-Selec2veMembranes

Feed Retentate1

Permeate1

Permeate

Retentate

(Product)N

N

Config.:2-stageN2-

selecvemembranes,with

pressurizaonon1st-stage

feed

Config.3:2-stageN2-selecvemembranes,nopressurizaonon1st-stage

feed

FeedRetentate1

Permeate1

Permeate

N

N

Retentate(Product)

Config.1:Single-stageN2

-

selecvemembraneFeedRetentate

(Product)Permeate N


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HybridConfigura2ons:N-+CO-Selec2veMembranesConfig.4:1st-stageN2-selecvemembranewithfeed

pressurizaon,2nd-stageCO2-

selecvemembrane

Retentate1

Permeate1 Permeate

(Product)

RetentateN

CO

Feed

Config.5:1st-stageN2-selecvemembranewithnofeedpressurizaon,2nd-stageCO2-

selecvemembrane

FeedRetentate1

Permeate1Permeate(Product)

RetentateN

CO

Config.6:1st-stageCO2-selecvemembranewithfeed

pressurizaon,2nd-stageN2-

selecvemembrane

Retentate1

Permeate1Permeate

Retentate(Product)CO

N

Feed

Pareto Curves of N Selec2ve Membrane


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ParetoCurvesofN-Selec2veMembraneConfigura2ons(100%Capture,95%Purity)

0%

20%

40%

60%

80%

100%

120%

0

1

2

3

4

5

6

0 50,000100,000150,000200,000250,000300,000

Membranesurfacearea(m)

Config.1

Config.2

Config.3

En

ergyuse(GJ/tC

O2

captured)

Energ

ypenalty

CO-selec2vemembranes

Absorp2on

Pareto Curves of Hybrid Membrane Configura2ons


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ParetoCurvesofHybridMembraneConfigura2ons(90%Capture,95%Purity)

0%

20%

40%

60%

80%

100%

0

1

2

3

4

5

6

0 50,000100,000150,000200,000250,000300,000

Membranesurfacearea(m)

Config.4

Config.5

Config.6

Energypenalty

En

ergyuse(GJ/tC

O2

captured)

CO-selec2vemembranes

Absorp2on


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FootprintComparison

500MWplantemits11,000tonsCO2/dayandassumecapture90%(10,000tons)

Plantsizeis0.15km2 CurrentSOAaminescrubbingtocaptureis

0.02km2or13%oftheplantslandarea

Membranesurfacearea 250,000m2=0.025km2 Butitstypicallyshell-in-tubeconfiguraon Surfaceareawilllikelybelessthanthatofatradionalaminescrubbingsystem

0

4

6

8

10

0 1 3 4 5 6 7 8 9 10

0

4

6

8

10

0 1 3 4 5 6 7 8 9 10

0

4

6

8

10

0 1 3 4 5 6 7 8 9 10


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InSummary ProofofConcept:nitrogenpermeatesGroupVmetals,selecvelyoverCO2

viaasoluon-diffusionmechanism

FromDFT,atomicNdrawssignificantchargefromVleadingtostabilizaonandbondinginthela{ce

AllyingwithRusignificantlyreducesatomicNstabilityinV N

2-selecvemembranesarelikelytohaveasmallerfootprintthanCO

2-

selecvemembranes.Thefinalsize,however,alsodependsonthesurfaceareato-volumera2osofthemembranemodules.

Energyinefficiencycomesinpartfromhea2ngandcoolinguse,whichisdictatedbythehighoperangtemperaturesrequiredbythemembrane

materials.

N2-selecvemembraneshaveshowngreatpotenalasfeedCOenrichersforCO2-selecvemembranes.


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NextSteps

ConnueDFTcalculaonstopredictalloysforenhancedN2separaon WorkwithSwRItospuerdepositalloysofVRuandNbRuonporous

stainlesssteelsupports

WorkwithDrStevePaglieri(TDA)toassistintubularreactordesigntomakematerialstesngeasier

MeasureN2andCO2fluxesofalloysandcomparetopure Carryoutopmizaoncalculaonsonnaturalgassystems;consider

applyingmembranebeforetheexpansioninthegasturbine


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Acknowledgements

Funding:

Experiments:NSFEager,CatalysisDivision;EPAP3(high-Tfurnace);ArmyResearchOffice

DFT:NSFTeragrid,UTAusn

HelpfulDiscussions: DrStevePaglieri,TDAResearch

NAMS,013


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Addi2onalInforma2on:

FromSpringersite:

hp://www.springer.com/chemistry/book/

978-1-4614-2214-3

CleanEnergyConversionsWebsite:

hp://cec-lab.stanford.edu/


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GigatonChallengeThinkOutsidetheBox!dontworry..YoullsTllgraduateandfindajob

EkinOzdogan,PhD013Shell,ResearchEngineer,ProcessEvaluaons

Houston,TX

NiRochana,PhD013PTT,ResearchEngineer,BusinessDevelopment

Bangkok,Thailand


50/50

Ques2ons?

Fundamentals of Gas Separations and CO2 Capture Technology / Developments in Membrane Separation

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