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---Lower Pressure Ammonia Synthesis
Mahdi Malmali, Joshua Prince, Mike Reese, Alon McCormick, Ed Cussler
Chemical Engineering and Materials Science
University of Minnesota
1
h$p://www.gapinsaat.com/
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ASimplifiedCH4-BasedProcess
Jennings,J.R.,Cataly&cAmmoniaSynthesis,Springer,1991
2
RequirementsforDistributedProduc&on:1-CheapEnergy/FeedResources2-SimplerProcessatModerateCondiEons
Source:CatalyEcAmmoniaSynthesis
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Wind Offers Sustainable EnergyStranded Wind Resources Equals Ammonia Need
3
Na%onal Renewable Energy Laboratory, United States Department of Energy. Wind Resource Map (2014).
hJp://www.nrel.gov/gis/wind.html
Na%onal Agricultural Sta%s%cs Service, United States Department of Agriculture. Planted Corn Acreage by County (2014). hJp://www.nass.usda.gov/Charts_and_Maps/Crops_County/#cr
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4
WeareMakingRenewableAmmoniaOutofThinAir
Source:UMN.edu/
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5
AbsorpDon(staged)ReplacesCondensaDon(mixed)
100atm
Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.
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MetalHalideswithRemarkableAmmoniaUptakeCapacity
100gMgCl2blockholds135LSTPNH3
CaCl2 + NH3⎯→⎯←⎯⎯ Ca(NH3)Cl2Ca(NH3)Cl2 + NH3⎯→⎯←⎯⎯ Ca(NH3)2Cl2
3 2 2 3 3 4 2( ) 2 ( )Ca NH Cl NH Ca NH Cl⎯⎯→+ ←⎯⎯
3 4 2 3 3 8 2( ) 4 ( )Ca NH Cl NH Ca NH Cl⎯⎯→+ ←⎯⎯
2 3 3 2( )MgCl NH Mg NH Cl⎯⎯→+ ←⎯⎯
3 2 3 3 2 2( ) ( )Mg NH Cl NH Mg NH Cl⎯⎯→+ ←⎯⎯
3 2 2 3 3 6 2( ) 4 ( )Mg NH Cl NH Mg NH Cl⎯⎯→+ ←⎯⎯
6
Cl
Cl Cl
Cl
Johnsen, R. E., Jensen, P. B., Norby, P., & Vegge, T. (2014).The Journal of Physical Chemistry C, 118(42), 24349-24356.
Sr(NH3)8Cl2
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1-Be$erCatalysis(NotKeyHere)LowerPressureandLowerTemperature
2-LowerPressure
-UnravelingMechanismofReacDon-AbsorpDonProcess-ImplicaDonofaLowerPressureProcess
3-Be$erSeparaEon/Be$erSorbents
7
StrategiestoImproveHaber-BoschProcess
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PreheaterReactor
OutletInlet
ReacDon-AbsorpDonApparatus
Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.
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9
𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝑹𝒂𝒕𝒆= 𝐶↑∗ − 𝐶↓0 /1/𝑘↓𝑅 𝑀↓𝑅 + 1/𝑘↓𝑎𝑏𝑠 𝐴↓𝑎𝑏𝑠 + 1− 𝐶↑∗ ⁄𝐶 /𝑚
InReacDon-AbsorpDon,ReacDonTemperaturehasBigLiQleEffectontheProducDonRate
Malmali, M., Wei, Y., McCormick, A., & Cussler, E. L. (2016) Industrial & Engineering Chemistry Research, 55(33), 8922-8932. Malmali, M., Wei, Y., McCormick, A., & Cussler, E. L., Accepted.
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Proof:FedbatchatConstantPressure
10Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.
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SynthesisMoreAffectedbyRecycle
11
𝑹𝒂𝒕𝒆= 𝐶↑∗ − 𝐶↓0 /1/𝑘↓𝑅 𝑀↓𝑅 + 1/𝑘↓𝑎𝑏𝑠 𝐴↓𝑎𝑏𝑠 + 1− 𝐶↑∗ ⁄𝐶 /𝑚
Malmali, M., Wei, Y., McCormick, A., & Cussler, E. L. (2016) Industrial & Engineering Chemistry Research, 55(33), 8922-8932. Malmali, M., Wei, Y., McCormick, A., & Cussler, E. L., Accepted.
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StrategiestoImproveHaber-BoschProcess
1-Be$erCatalysis–NotKeyHereLowerPressureandLowerTemperature
2-LowerPressure3-BeQerSeparaDon/BeQerConversion
ImprovingtheRXN-ABSwithBeQerAbsorbents
12
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BulkMetalHalidesNotStable
13Wagner,K.,Malmali,M.,Smith,C.,McCormick,A.,Cussler,E.L.,Zhu,M.Seaton,N.C.A.(2017)AIChEJ.,63(7),3058–3068. Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.
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Second Generation Absorbents Even Better
14
0
40
80
120
160
150°C,3bar 200°C,3bar 300°C,3bar
SorpDo
nCa
pacity(m
g NH3g
salt-1)
CaBr2-Support1
CaBr2-Support2
CaBr2-Support3
CaBr2-Support4
CaBr2-Support5
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0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
150,1 150,2 150,3 200,1 200,2 200,3 300,1 300,2 300,3
Sorben
tCap
acity
[m
oleNH 3/molesorben
t]
AbsorpDonCondiDon:Temperature[oC],Pressure[bar]
MgCl2-Support 5
CaCl2-Support 5
SrCl2-Support 5
MgBr2-Support 5
CaBr2-Support 5
SrBr2-Support 5
Second Generation Sorbent Are Separate Ammonia Efficiently
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BeQerAbsorbent:Improvedby10X
16
10gSaltPackedinColumnBET:lessthan1m2/g
10gSorbent(5%and40%loading)Packedin
ColumnBET:lessthan400m2/g
Wagner,K.,Malmali,M.,Smith,C.,McCormick,A.,Cussler,E.L.,Zhu,M.Seaton,N.C.A.(2017)AIChEJ.,63(7),3058–3068. Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.
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17
DesorpEonTemperature
(°C)%Recovery
Salt1-Support5
150 14
200 31
300 70
400 93
Salt2-Support5
150 25
200 68
300 82
400 96
DesorpEonTemperature
(°C)%Recovery
Salt3-Support5
150 22
200 37
300 55
400 66
Salt4-Support5
150 15
200 57
300 82
400 91
20 Min Vacuum Regeneration
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18
Proposed Process Flow Diagram (PFD)
N2
H2
Absorber1uptake200C20bar
Absorber2regeneraEon
400C
Absorber3regeneraEon
400CReactor400C,20bar
Compressor Compressor
Storage
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Conclusions:DistributedSustainableAmmonia
1. ReplacingEconomyofScalewithEconomyofNumber
2. ReacEve-SeparaEonPromisesFasterRates3. AbsorpEonisPromising,weimprovedabsorbents
by10X4. DistributedRenewableAmmoniaPossiblewith
LowerCapEx5. RegeneraEonsEllUnderInvesEgaEon
19
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ArmyofUndergrads:• GiangLe(Dreyfus)• JenniferHendrickson(UROP)• JoshuaPrince(UROP)• CollinSmith• MichaelHo(UROP)
20
Supervisors:EdCusslerAlonMcCormick
Acknowledgments
Funding• AdvancedResearchProjectsAgency–Energy(REFUEL)• StateofMinnesota(LCCMR,MnDRIVE,IREE,CornGrowers)• DreyfusFoundaEon• UMNUROP
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BatchProcessTABS=460KAbsorbent:BulkCaCl2
21
InReacDon-AbsorpDon,Pressure…..
Malmali, M., Wei, Y., McCormick, A., & Cussler, E. L. (2016) Industrial & Engineering Chemistry Research, 55(33), 8922-8932.
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BeQerAbsorbent:BulkAbsorbentarenotStable
SupportedAbsorbentsareStablewithSuperiorPerformance
22
Wagner,K.,Zhu,M.,Malmali,M.,Smith,C.,Seaton,N.C.,McCormick,A.,&Cussler,E.L.(2017)AIChEJournal,doi:10.1002/aic.15685(2017).Cussler,E.,McCormick,A.,Reese,M.&Malmali,M.JoVE,(2017)Accepted.Malmali,M.,McCormick,A.,&Cussler,E.L.,Submi$ed.
T(C)P(bar)
N2:NH35:1Loading(mg/g)
150 1 130.90150 2 147.92150 3 173.12200 1 120.46200 2 138.56200 3 147.50300 1 65.74300 2 75.34300 3 83.18
SupportedAbsorbentX
0 1/3 t 2/3 t t
0 5 t 10 t 15 t
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AmmoniaSynthesizedbyHaberProcess20thCentury–“GreenRevoluDon”
23
1918NobelPrizeinChemistry
1931NoblePrizeinChemistry
Source:h$ps://www.BASF.com/
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21stCentury–2ndAmmoniaRevoluDon?Energy-DenseCarbon-FreeLiquidFuel
24
Gasoline Hydrogen Ammonia Methanol ElectricityEnergy Density, kWh/L 8.76 0.8 4.25 6.4 -
Fuel Cost, ¢/kWh 4.7 5.8 6.3 4.85 6.5Conversion Efficiency, % 30 55 55 60 92
Source-to-use Energy Cost, $/kWh 0.16 0.29 0.13 - 0.28
EnergyStorage?
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25
FutureHaberProcessRequireLowerCapitalandOperaDngCosts
300atm
400̊C
Compressor
N2&H2
ReacDon
HeatExchanger
NH3N2,H 2,N
H 3
300atm40̊C
300atm-20̊C
ReacDon-Then-SeparaDon
N2,H2,NH3
Compressor
N2&H2
ReacDon
30atm300̊C
30atm
400̊ C
N2&H2
ReacDon-AbsorpDon
400̊C
N2,H2&NH3
AbsorpDon
30atm
400̊ C
Component CapitalCostShare*
HeatExchangers 25%
Compressors 50%
Drivers 15%
Reactor 30%
Pump 5%
*Morgan,E.Techno-EconomicFeasibilityStudyofAmmoniaPlantsPoweredbyOffshoreWind,UniversityofMassachuse$sAmherst,2013.
Morgan, Eric, James Manwell, and Jon McGowan. "Wind-powered ammonia fuel production for remote islands: A case study." Renewable Energy 72 (2014): 51-61.
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26
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Compression ASPEN Simulation
27
§ Multi-stage compressors with intercooling used for feed gases
§ Single-stage compressor compensates for pressure drop in loop
§ Valve represents total pressure drop throughout system
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Compression Initial design (2/2)
28
§ Early results indicate multi-stage compression will be required
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Economic Considerations
29
The economic viability of the synthesis looks doubtful
§ Price per 180 acre farm per year on average for 8 years, $27,8551
§ Other energy conversions, such as ethanol, flow batteries, or fuel cells may be more viable2
§ There are already over 120,000 residential fuel cells in Japan for example
http://marketrealist.com/2016/09/ammonia-prices-continue-movement-last-week/
1. http://farmdocdaily.illinois.edu/2015/12/current-fertilizer-prices-and-projected-2016-costs.html 2. https://www.h2-international.com/2015/09/21/ene-farm-installed-120000-residential-fuel-cell-units/
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Back up
• SMRvs.Electrolysis
30
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Ammonia:PathtoSustainableEconomy?
31
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StrategiestoImproveHaber-BoschProcess
1-BeQerCatalysisLowerPressureandLowerTemperature
2-Be$erConversion/Be$erSeparaEon3-LowerPressure
Be$erAbsorber
32
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ABeQerCatalyst?
33
a
b
Malmali,M.,Wei,Y.,McCormick,A.,&Cussler,E.L.(2016).Industrial&EngineeringChemistryResearch,55(33),8922-8932.
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ClimateisChanging
34
CO2level450ppm:1.2-2.3°C550ppm:1.5-2.9°C650ppm:1.7-3.2°C
EffectoftemperatureIncrease1°C:Loosingreefs(foodchain)2°C:IcesheetsmelEng3°C:WeakeningofoceancirculaEon
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Safety: West Fer%lizer, Texas
35
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ReacDonRateConstantsDon’tVaryMuchwithPressure
36
Malmali,M.,Wei,Y.,McCormick,A.,&Cussler,E.L.(2016).Industrial&EngineeringChemistryResearch,55(33),8922-8932.
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Energy Density
37
=X400
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Reese, M.; Marquart, C.; Malmali, M.; Wagner, K.; Buchanan, E.; McCormick, A. Cussler E.; Ind. Eng. Chem. Res. 2016, 55 (13), 3742.
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𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝑹𝒂𝒕𝒆 = 𝐶↑∗ − 𝐶↓0 /1/𝑘↓𝑅 𝑀↓𝑅 + 1/𝑘↓𝐶 𝐴↓𝐶 + 1− 𝐶↑∗ ⁄𝐶 /𝑚
𝑘↓𝑅 Temkin-PyzhevEquaEon𝑟= 𝑘↓1 𝑃↓𝑁2 𝑃↓𝐻2↑1.5 /𝑃↓𝑁𝐻3 − 𝑘↓2 𝑃↓𝑁𝐻3 /𝑃↓𝐻2↑1.5 LinearizaEon
Calculatedfromdataforinternal/externalheattransfer
coefficients
CalculatedfromMFCreadings
SimplifiedPilotPlantFlowDiagram(ConvenDonal)
a/2N23a/2H2
aNH3
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InReacDon-AbsorpDon,ReacDonTemperaturehasBigLiQleEffectontheProducDonRate
TABS=460KAbsorbent:70gCaCl2
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𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝑹𝒂𝒕𝒆= 𝐶↑∗ − 𝐶↓0 /1/𝑘↓𝑅 𝑀↓𝑅 + 1/𝑘↓𝑎𝑏𝑠 𝐴↓𝑎𝑏𝑠 + 1− 𝐶↑∗ ⁄𝐶 /𝑚
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InReacDon-AbsorpDon,ReacDonRecycleFlowisControllingEffectofAbsorbentHistoryonProducDonRates
TRXN=700KTABS=460KAbsorbent:70gCaCl2
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𝑷𝒓𝒐𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝑹𝒂𝒕𝒆= 𝐶↑∗ − 𝐶↓0 /1/𝑘↓𝑅 𝑀↓𝑅 + 1/𝑘↓𝑎𝑏𝑠 𝐴↓𝑎𝑏𝑠 + 1− 𝐶↑∗ ⁄𝐶 /𝑚
0
200
400
0 1 2 3 4
1/r'(sec/bar)
1/PumpFlowRate(sec/mL)
1/2 𝑁↓2 + 3/2 𝐻↓2 ⇔┬𝑁𝐻↓3 𝑟= 𝑘↓1 𝑃↓𝑁↓2 𝑃↓𝐻↓2 ↑1.5 /𝑃↓𝐴 − 𝑘↓2 𝑃↓𝐴 /𝑃↓𝐻↓2 ↑1.5
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Tiffany – Effect of Scale
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EsEmatedplantcapitalcostpertonofcapacityofammonia–includingelectrolysis,excludingwindturbine
©2015,RegentsoftheUniversityofMinnesota.Allrightsreserved
EffectofScalefortheSmallAmmoniaPlant
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43
Alumina MgCl2/Alumina
MgCl2 CaCl2
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ConvenDonalCapitalCostsfora12ton/hAmmoniaSynthesisProcess
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0
20
40
60
80
100
0 2000 4000 6000 8000 10000
Pressure(a
tm)
Time
10atm 20atm 27atm 35atm 41atm
55atm 69atm 84atm 95atm
HigherIniDalChargeEnhancesProducDonRates
©2016,RegentsoftheUniversityofMinnesota.Allrightsreserved
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PerfectSeparaDonofAbsorberBeforeBreakthrough
P=18barTRXN=400CTABS=180C
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MgCl2 as liquid fuel storage • ControlledRelease• LowVolaElity• HighCapacity• Cheap• ReversibleStorage
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ConstantPressureProducDon
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AbsorpDon-EnhancedSynthesis
2.ReacEonandAbsorpEon
1.Feedthereactor
3.NH3DesorpEon
Catalyst
48
N2
H2
Absorbent(MgCl2)
Reaction
NH3
N2+3H2⇌2NH3Typicalconversion:15%
Malmali,M.;Wei,Y.;McCormick,A.;Cussler,E.L.;Ind.Eng.Chem.Res.2016,DOI:10.1021/acs.iecr.6b01880.
Huberty,M.S.;Wagner,A.L.;McCormick,A.;Cussler,E.;AIChEJ.2012,58(11),3526.
Himstedt,H.H.;Huberty,M.S.;McCormick,A.V.;Schmidt,L.D.;Cussler,E.L.;AIChEJ.2015,61(4),1364.
©2016,RegentsoftheUniversityofMinnesota.Allrightsreserved
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Group
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EdCusslerITDisEnguishedProfessor,CEMSFocus:AbsorpEon,ProcessDesign
AlonMcCormickProfessor,CEMSFocus:ReacEonEngineering
PaulDauenhauerAssociateProfessor,CEMSFocus:ReacEon-SeparaEonIntegraEon
ProdromosDaouEdisProfessor,CEMSFocus:Modeling&OpEmizaEon
MikeReeseDirector,RenewableEnergy,WCROCFocus:AmmoniaPilotPlant
RogerRuanProfessor,BBSFocus:Non-thermalPlasma
KennethValentasProfessor,BBSFocus:AmmoniaStorageinHydrochar
DougTiffanyAssistantExtensionProfessor,AppliedEconomicsFocus:EconomicAnalysis
StephenKelleySeniorFellow,HumphreySchoolofPublicAffairsFocus:PublicPolicy
©2016,RegentsoftheUniversityofMinnesota.Allrightsreserved
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KuraviProgEnergyCobustSci201339(4)285
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