mahdi malmali, joshua prince, mike reese, alon mccormick ......---lower pressure ammonia synthesis...

---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/

ASimplifiedCH4-BasedProcess

Jennings,J.R.,Cataly&cAmmoniaSynthesis,Springer,1991

2

RequirementsforDistributedProduc&on:1-CheapEnergy/FeedResources2-SimplerProcessatModerateCondiEons

Source:CatalyEcAmmoniaSynthesis

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

4

WeareMakingRenewableAmmoniaOutofThinAir

Source:UMN.edu/

5

AbsorpDon(staged)ReplacesCondensaDon(mixed)

100atm

Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.

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

1-Be$erCatalysis(NotKeyHere)LowerPressureandLowerTemperature

2-LowerPressure

-UnravelingMechanismofReacDon-AbsorpDonProcess-ImplicaDonofaLowerPressureProcess

3-Be$erSeparaEon/Be$erSorbents

7

StrategiestoImproveHaber-BoschProcess

PreheaterReactor

OutletInlet

ReacDon-AbsorpDonApparatus

Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.

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.

Proof:FedbatchatConstantPressure

10Malmali, M., Reese, M., McCormick, A., & Cussler, E. L. (2017) ACS Sustainable Chemistry & Engineering, Accepted.

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.


1-Be$erCatalysis–NotKeyHereLowerPressureandLowerTemperature

2-LowerPressure3-BeQerSeparaDon/BeQerConversion

ImprovingtheRXN-ABSwithBeQerAbsorbents

12

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.

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

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

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.

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

18

Proposed Process Flow Diagram (PFD)

N2

H2

Absorber1uptake200C20bar

Absorber2regeneraEon

400C

Absorber3regeneraEon

400CReactor400C,20bar

Compressor Compressor

Storage

Conclusions:DistributedSustainableAmmonia

1.  ReplacingEconomyofScalewithEconomyofNumber

2.  ReacEve-SeparaEonPromisesFasterRates3.  AbsorpEonisPromising,weimprovedabsorbents

by10X4.  DistributedRenewableAmmoniaPossiblewith

LowerCapEx5.  RegeneraEonsEllUnderInvesEgaEon

19

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

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.

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

AmmoniaSynthesizedbyHaberProcess20thCentury–“GreenRevoluDon”

23

1918NobelPrizeinChemistry

1931NoblePrizeinChemistry

Source:h$ps://www.BASF.com/

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?

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.

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

Compression Initial design (2/2)

28

§  Early results indicate multi-stage compression will be required

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/

Back up

•  SMRvs.Electrolysis

30

Ammonia:PathtoSustainableEconomy?

31


1-BeQerCatalysisLowerPressureandLowerTemperature

2-Be$erConversion/Be$erSeparaEon3-LowerPressure

Be$erAbsorber

32

ABeQerCatalyst?

33

a

b

Malmali,M.,Wei,Y.,McCormick,A.,&Cussler,E.L.(2016).Industrial&EngineeringChemistryResearch,55(33),8922-8932.

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

Safety: West Fer%lizer, Texas

35

ReacDonRateConstantsDon’tVaryMuchwithPressure

36

Malmali,M.,Wei,Y.,McCormick,A.,&Cussler,E.L.(2016).Industrial&EngineeringChemistryResearch,55(33),8922-8932.

Energy Density

37

=X400

Reese, M.; Marquart, C.; Malmali, M.; Wagner, K.; Buchanan, E.; McCormick, A. Cussler E.; Ind. Eng. Chem. Res. 2016, 55 (13), 3742.

39

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

InReacDon-AbsorpDon,ReacDonTemperaturehasBigLiQleEffectontheProducDonRate

TABS=460KAbsorbent:70gCaCl2

40


InReacDon-AbsorpDon,ReacDonRecycleFlowisControllingEffectofAbsorbentHistoryonProducDonRates

TRXN=700KTABS=460KAbsorbent:70gCaCl2

41


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  

Tiffany – Effect of Scale

42

EsEmatedplantcapitalcostpertonofcapacityofammonia–includingelectrolysis,excludingwindturbine

©2015,RegentsoftheUniversityofMinnesota.Allrightsreserved

EffectofScalefortheSmallAmmoniaPlant

43

Alumina MgCl2/Alumina

MgCl2 CaCl2

ConvenDonalCapitalCostsfora12ton/hAmmoniaSynthesisProcess

44

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


45

PerfectSeparaDonofAbsorberBeforeBreakthrough

P=18barTRXN=400CTABS=180C

46

MgCl2 as liquid fuel storage • ControlledRelease•  LowVolaElity• HighCapacity• Cheap• ReversibleStorage

47

ConstantPressureProducDon

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.


Group

49

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


KuraviProgEnergyCobustSci201339(4)285

50

mahdi malmali, joshua prince, mike reese, alon mccormick ......---lower pressure ammonia synthesis...

Documents