HydrogenfromNaturalGasviaSteam

MethaneReforming(SMR)
Energyefficiencyofhydrogenfromnaturalgas
Definitionofenergyefficiency
Frombasicstoichiometry
- CH
4
+2H
2
OCO
2
+4H
2
- Fueltosatisfytheheatrequirements
Fromrealprocesses
- SMR Steammethanereforming
- Watershiftreactions
- Heatintegration
- CO
2
removalorPSA?
EnergyEfficiency
Usable energyout ofaprocesscomparedtoall energyinputs
Energyvaluescouldbeheat,work,orchemicalpotential(heatingvalue)
- HHV(Gross): Fuel+O
2
CO
2
+H
2
O(liquid)
- LHV(Net): Fuel+O
2
CO
2
+H
2
O(vapor)
Energyvaluesmayhavetobediscountedwhencombiningdifferenttypes
- ShouldtheHHVbediscountedwhencombiningwithheatvalues?
( )
out
in
i
E
E
q=

HHV LHV
Bt u/ scf Bt u/ scf kcal / g. mol Bt u/ scf kcal / g. mol Bt u/ scf
Hydrogen 324. 2 273. 8 68. 7 325. 9 57. 7 273. 9
Met hane 1010. 0 909. 4 213. 6 1013. 1 191. 7 909. 1
Carbon Monoxide 320. 5 320. 5 67. 6 320. 6 67. 6 320. 6
Carbon Dioxide 0. 0 0. 0 0. 0 0. 0 0. 0 0. 0
Compound
GPSA Dat a Book
HHV LHV
Der i v ed f r om Aspen Pl us 2006. 5
BasicStoichiometery CH
4
+2H
2
OCO
2
+4H
2
Production:
Apparentefficiency(HHVbasis)
- Justfromstoichiometry:
- Includeheatofreaction:
2
4
H
CH
mol
4
mol
N
N
=
4 68.7
1.29
1 213.6

q= =

4 68.7
1.00
1 213.6 61.3

q= =
+
METHANE
WATER
H2-CO2
Q-RXN
Q
MAKE-H2
Howdoweprovidetheheatofreaction?
Coulduseadditionalmethane 0.29molfuel/molreactant(HHVbasis)
Production:
Efficiencyincludingfuel(HHVbasis)
2
4
H
CH
4 mol
3.1
1 0.29 mol
N
N
= =
+
4 68.7
1.0
1.29 213.6

q= =

METHANE
WATER
H2-CO2
Q-RXN
FUEL
AIR
FLUE-GAS
MAKE-H2
BURNER
RealProcess SteamMethaneReforming&WaterShift
Reforming.Endothermiccatalyticreaction,
typically2030atm&800880C(1470
1615F)outlet.
CH
4
+H
2
O CO+3H
2
Shiftconversion.Exothermicfixedbed
catalyticreaction,possiblyintwosteps.
CO+H
2
O CO
2
+H
2
HTS:345370C(650 700F)
LTS:230C(450F)
GasPurification.AbsorbCO
2
(amine)or
separateintopureH
2
stream(PSAor
membrane).
Methanation.ConvertresidualCO&CO2back
tomethane.Exothermicfixedbedcatalytic
reactionsat370425C(700 800F).
CO+3H
2
CH
4
+H
2
O
CO
2
+4H
2
CH
4
+2H
2
O
Steam
Natural Gas
Reforming
Reactor
High Temperature
Shift Reactor
Low Temperature
Shift Reactor
Hydrogen
Purification
Fuel Gas
Flue Gas
Hydrogen
Methanation
Reactor
CO2
SMRAlternateDesigns
Traditionalwith2stagesshift
reactors 95%to98%purity
NewerdesignswithPSA
(PressureSwingAdsorption)
lowercapitalcosts,lower
conversion,butveryhighpurity
(99%+)
ProcessConsiderations
Kaes [ 2000] Mol bur g & Doct or [ 2003] Nex ant Repor t [ 2006] Ot her
Model as conversi on react or Model as equil ibri um react or.
Sul fur compounds convert ed t o H2S &
adsorbed in ZnO bed.
Small t emperat ure i ncrease 500 - 800F dependi ng on t echnology.
700F most t ypi cal .
Typi call y up t o 725 psi ( 50 bar)
Reformer 1450 - 1650F exi t 1500F 20 - 30 at m ( 295 - 440 psia)
Equi li bi ri um Gi bbs react or wit h 20F
approach ( for design) .
Model as equil ibri um react or. 850- 1000F ( 455- 540C) inlet
1470- 1615F ( 800- 880C) out let
650 - 700F ent rance for HTS + LTS 660F ent rance 940F ( 504C) i nl et
500 - 535F ent rance when no LTS
Equi li bi ri um Gi bbs react or Fi xed 90% CO conversi on
All component s inert except CO, H2O,
CO2, & H2.
400 - 450F ent rance 400F ent rance
Equi li bi ri um Gi bbs react or 480- 525F ( 249- 274C) out let
All component s inert except CO, H2O,
CO2, & H2.
Fi xed 90% CO conversi on
Met hanat i on 500 - 550F ent rance
Equi li bi ri um Gi bbs react or
All component s inert except CH4, CO,
H2O, CO2, & H2.
Ami ne Puri ficat i on Model as component spl it t er Model as component spli t t er MDEA ci rcul at i on, dut y, & work est imat es
from GPSA Dat a Book
Treat ed gas 10 - 15F i ncrease, 5 - 10
psi decrease, wat er sat urat ed
Treat ed gas 100F & 230 psi ( 16 bar)
exit
Rej ect ed CO2 at mospheric pressure &
wat er sat urat ed
95% CO2 recovery
PSA Model as component spl it t er Model as component spli t t er
100F ent rance 90% H2 recovered 75 - 85% recovery for "reasonable"
capit al cost s ( higher requi res more beds)
H2 puri t y as hi gh as 99. 999% H2 cont ai ns 0. 001% product st ream as
cont aminant
200 - 400 psig feed pressure for refi nery
appl icat i ons
4: 1 minimum feed: purge gas rat i o. Purge
gas t ypicall y 2 - 5 psig.
Desul furi zat i on
React ors
Hi gh Temperat ure
Shi ft React or
Low Temperat ure
Shi ft React or
HIERARCHY
AMINE
HIERARCHY
HVAL-1
HIERARCHY
HVAL-2
38
1
CO2
33
15
15
1
FEED
PRODUCT
38
14
273
28
Q
815
19
15
1
WATER
16
28
W Q
231
28
377
28
349
18
Q
427
18
204
17
213
16
Q
38
15
Q
W
260
14
Q-HEAT1
Q
335
14 HOTPROD
Q
REFORMER
WATPUMP
STEAMGEN
HTS
LTS
COND1
GASCOMP
METHANTR
BasicSMRProcess
Temperature (C)
Pressure (atm)
Remember,directionofarrowindicateswhetherAspenhascalculated,
NOTwhetheritisheatin/out
SMRBasicProcessEnergyRequirements
HIERARCHY
HVAL-1
HIERARCHY
HVAL-2
FEED
PRODUCT
Q
WATER
W Q
Q
Q
Q
CO2
W
REFORMER
WATPUMP
STEAMGEN
HTS
LTS
COND1
GASCOMP
HIERARCHY
AMINE
METHANTR
TREATED TREATED2
HOTPROD
Q
Q
Ener gy I nput s Ener gy Rem oval
kcal/ hr kW kcal/ hr
St eam Boi ler 3,742,371 Post Reformer Cool er 2,238,933
Reformer 6,332,965 Post HTS Cool er 1,026,525
Amine Dut y 5,680,514 Post LTS Cooler 2,305,814
Met hanat or Reheat 553,190 Amine Cool ers 3,550,321
Sub- t ot al 16,309,040 Product Cooler 800,533
Tot al 9,922,126
BFW Pump 10,959 12.7
Gas Compressor 385,571 448.4
Amine Power 125,716 146.2
Sub- t ot al 522,246
Tot al 16,831,286
Heat i ng Val ues ( HHV)
kcal/ hr kmol/ hr kcal/ mol
Nat ural Gas I n 21,363,070 100 213.6
Product Out 25,938,163 328.6 78.9
H2 Out 292.7
H2 Pur i t y : 89%
H2 Pr oduct i on: 2. 9
Tot al Pr oduct 25,938, 163
Tot al I nput s 38,194, 356
Ef f i ci ency 68%
HIERARCHY
HVAL-1
HIERARCHY
HVAL-2
FEED
PRODUCT
Q
WATER
W Q
Q
Q
Q
CO2
W
REFORMER
WATPUMP
STEAMGEN
HTS
LTS
COND1
GASCOMP
HIERARCHY
AMINE
METHANTR
TREATED TREATED2
HOTPROD
Q
Q
SMR HeatRecoveryforSteamGeneration
Ener gy I nput s Ener gy Rem oval
kcal/ hr kW kcal/ hr
St eam Boi ler 3,742, 371 Post Reformer Cool er 2,238,933
Met hanat or Reheat 553, 190 Post HTS Cool er 1,026,525
Heat Sub- t ot al 4,295, 561 Post LTS Cooler 2,305,814
Sub- t ot al 5, 571,272
Reformer 6,332,965
Amine Dut y 5,680,514 Amine Cool ers 3,550,321
Sub- t ot al 16,309,040 Product Cooler 800,533
Tot al 9,922,126
BFW Pump 10,959 12.7
Gas Compressor 385,571 448.4
Amine Power 125,716 146.2
Sub- t ot al 522,246
Tot al 16,831,286
Heat i ng Val ues ( HHV)
kcal/ hr kmol/ hr kcal/ mol
Nat ural Gas I n 21,363,070 100 213.6
Product Out 25,938,163 328.6 78.9
H2 Out 292.7
H2 Pur i t y : 89%
H2 Pr oduct i on: 2. 9
Tot al Pr oduct 25,938, 163
Net I nput s 33,898, 795
Ef f i ci ency 77%
ReformerFurnaceDesign
HydrogenProductionbySteamReforming
RayElshout,ChemicalEngineering,May2010
HIERARCHY
SMR DirectFiredHeatersforReformer&AmineUnit
Ener gy I nput s Ener gy Rem oval
kcal/ hr kW kcal/ hr
St eam Boi ler 3,742, 371 Post Reformer Cool er 2,238,933
Met hanat or Reheat 553, 190 Post HTS Cooler 1,026,525
Heat Sub- t ot al 4,295, 561 Post LTS Cooler 2,305,814
Reformer Flue Gas 648,651
Reformer 6,332, 965 Sub- t ot al 6, 219,923
Amine Dut y 5,680, 514
Sub- t ot al 16,309,040 Amine Coolers 3,550,321
Product Cooler 800,533
BFW Pump 10,959 12.7 Tot al 10,570,777
Gas Compressor 385,571 448.4
Amine Power 125,716 146.2
Sub- t ot al 522,246
Tot al 16,831,286
Heat i ng Val ues ( HHV)
kcal/ hr kmol/ hr kcal/ mol Efficiency
Nat ural Gas I n 21,363,070 100 213.6
Reformer Fuel Gas 8,184, 406 38.3 213.6 77%
Amine Uni t Fuel Gas 6,659, 083 31.2 213.6 85%
Tot al 36,206,559 169.5
Product Out 25,938,163 328.6 78.9
H2 Out 292.7
H2 Pur i t y : 89%
H2 Pr oduct i on: 1. 7
Tot al Pr oduct 25,938, 163
Net I nput s 36,728, 805
Ef f i ci ency 71%
HIERARCHY
SMR PreHeattheReformerFeed?
Ener gy I nput s Ener gy Rem ov al
kcal/ hr kW kcal/ hr
St eam Boil er 3,742,371 Post Reformer Cooler 2, 238, 933
Met hanat or Reheat 553,190 For Feed Preheat - 1,200,000
Heat Sub- t ot al 4,295,561 Post HTS Cooler 1, 026, 525
Post LTS Cooler 2, 305, 814
Reformer 5,132,965 Reformer Fl ue Gas 1,673,228
Feed Preheat 1,200,000 Sub- t ot al 6,044,500
Amine Dut y 5,680,514
Sub- t ot al 16, 309, 040 Amine Coolers 3, 550, 321
Product Cool er 800, 533
BFW Pump 10, 959 12.7 Tot al 10, 395, 354
Gas Compressor 385, 571 448.4
Amine Power 125, 716 146.2
Sub- t ot al 522, 246
Tot al 16, 831, 286
Heat i ng Val ues ( HHV)
kcal/ hr kmol/ hr kcal/ mol Efficiency
Nat ural Gas I n 21, 363, 070 100 213.6
Reformer Fuel Gas 7,978,680 37.3 213.6 64%
Amine Unit Fuel Gas 6,659,083 31.2 213.6 85%
Tot al 36, 000, 833 168.5
Product Out 25, 938, 163 328.6 78.9
H2 Out 292.7
H2 Pur i t y: 89%
H2 Pr oduct i on: 1.7
Tot al Pr oduct 25,938,163
Net I nput s 36,523,078
Ef f i ci ency 71%
SMRAlternateDesigns
Traditionalwith2stagesshift
reactors 95%to98%purity
NewerdesignswithPSA
(PressureSwingAdsorption)
lowercapitalcosts,lower
conversion,butveryhighpurity
(99%+)
AlternateHydrogenPurificationProcesses
HydrogenProductionbySteamReforming
RayElshout,ChemicalEngineering,May2010
W Q
Q
Q
Q
W
Q
Q
SEP
SMR UseofPSAforProductPurification
Ener gy I nput s Ener gy Rem ov al
kcal/ hr kW kcal/ hr
St eam Boiler 3, 742, 371 Post Reformer Cooler 2,238, 933
Feed Preheat 1, 200, 000 For Feed Pre- Heat - 1,200,000
Reformer 5, 132, 965 Post HTS Cooler 1,026, 525
Sub- t ot al 10,075, 336 Post LTS Cooler 1,776, 046
Reformer Fl ue Gas 1,674,739
BFW Pump 10, 959 12. 7 Tot al 5,516,243
Gas Compressor 385, 571 448. 4
Sub- t ot al 396, 529
Tot al 10,471, 865
Heat i ng Val ues ( HHV)
kcal/ hr kmol/ hr kcal/ mol Efficiency
Nat ural Gas I n 21, 363, 070 100. 0 213. 6
Reformer Fuel Gas 7, 984, 234 37. 4 213.6 64%
Tot al 29,347, 304 137. 4
Tail Gas Out 8,075, 157 165. 9 48.7
Product Out 18, 074, 861 263. 0 68.7
H2 Out 263. 0
H2 Pur i t y: 100%
H2 Pr oduct i on: 1. 9
Tot al Pr oduct 18,074,861
Tot al I nput s 29,743,834
Ef f i ci ency 61%
HIERARCHY
W Q
Q
Q
Q
W
Q
Q
SEP
SMR UseofPSAforProductPurification
Ener gy I nput s Ener gy Rem oval
kcal/ hr kW kcal/ hr
St eam Boiler 3,742, 371 Post Reformer Cooler 2,238,933
Feed Preheat 1,200, 000 For Feed Pre- Heat - 1,200, 000
Reformer 5, 132,965 Post HTS Cooler 1,026,525
Sub- t ot al 10, 075,336 Post LTS Cooler 1,776,046
Refor mer Flue Gas 2,250,289
BFW Pump 10,959 12. 7 Tot al 6,091, 793
Gas Compressor 385,571 448. 4
Sub- t ot al 396,529
Tot al 10, 471,865
Heat i ng Val ues ( HHV)
kcal/ hr kmol/ hr kcal/ mol Efficiency
Nat ural Gas I n 21, 363,070 100. 0 213.6
Reformer Fuel Gas 951, 511 4. 5 213.6
Sub- t ot al 22, 314,582 104. 5
Tai l Gas Out 8,075, 157 165. 9 48.7 57%
Tot al 30, 389,739
Product Out 18, 074,861 263. 0 68.7
H2 Out 263. 0
H2 Pur i t y : 100%
H2 Pr oduct i on: 2.5
Tot al Pr oduct 18,074, 861
Tot al I nput s 22,711, 111
Ef f i ci ency 80%
IntegratedProcess
HydrogenProductionbySteamReforming
RayElshout,ChemicalEngineering,May2010
Whatshouldbethepriceofhydrogen?
Hydrogensalesshouldcoverallcostsplus
profit
- Rawmaterialcosts(primarilynatural
gas)
- Electricity
- Otheroperatingexpenses(staff,)
- Recoveryofcapitalinvested
Minimumistocovercostofnaturalgas&
power
Example
- Naturalgas$4.36permillionBTU(asof
March30,2011)=$3.68perkmolCH
4
- Electricity6.79/kWhr(for2010per
EIAforIndustrialcustomers)
- PSAproductionscenario
104.5kmol/hrCH
4
$385perhr
461.1kW$31perhr
263kmol/hrH
2
$0.79perkg
- Electrolysiscomparison 80%
electrolysisefficiency&90%
compressionefficiency
$3.80perkg
- $6.80perkgwithcapitalcosts
included
ARealisticLookatHydrogenPriceProjections,F.DavidDoty
Mar.11,2004(updatedSept21,2004)
OtherReferences
RefineryProcessModeling,1
st
ed.
GeraldL.Kaes
KaesEnterprises,Inc.,2000
HydrogenfromSteamMethaneReformingwithCO2Capture
JohnC.Molburg&RichardD.Doctor
Paperfor20
th
AnnualInternationalPittsburghCoalConference,September1519,2003
http://www.netl.doe.gov/technologies/hydrogen_clean_fuels/refshelf/papers/pgh/hydrogen%20from
%20steam%20methane%20reforming%20for%20carbon%20dioxide%20cap.pdf
EquipmentDesignandCostEstimationforSmallModularBiomassSystems,SynthesisGas
Cleanup,andOxygenSeparationEquipment;Task1:CostEstimatesofSmallModular
Systems
NRELSubcontractReport,workperformedbyNexantInc.,SanFrancisco,CA
May2006
http://www.nrel.gov/docs/fy06osti/39943.pdf