07 Hydrogen From SMR
07 Hydrogen From SMR
JohnJechura [email protected]
Updated:January4,2015
Energyefficiencyofhydrogenfromnaturalgas
Definitionofenergyefficiency
Frombasicstoichiometry
CH4 +2H2OCO2 +4H2
Fueltosatisfytheheatrequirements
Fromrealprocesses
SMR Steammethanereforming
Watershiftreactions
Heatintegration
CO2 removalorPSA?
EnergyEfficiency
Usable energyout ofaprocesscomparedtoall energyinputs
Eout
Ein i
Energyvaluescouldbeheat,work,orchemicalpotential(heatingvalue)
HHV(Gross):
LHV(Net):
Compound
Hydrogen
Methane
Carbon Monoxide
Carbon Dioxide
Energyvaluesmayhavetobediscountedwhencombiningdifferenttypes
ShouldtheHHVbediscountedwhencombiningwithheatvalues?
NH2
NCH4
mol
mol
Apparentefficiency(HHVbasis)
Justfromstoichiometry:
Includeheatofreaction:
4 68.7
1.29
1 213.6
4 68.7
1.00
1 213.6 61.3
METHANE
MAKE-H2
WATER
H2-CO2
Q-RXN
Howdoweprovidetheheatofreaction?
Coulduseadditionalmethane 0.29mol fuel/mol reactant(HHVbasis)
Production:
NH2
NCH4
4
mol
3.1
1 0.29
mol
Efficiencyincludingfuel(HHVbasis)
METHANE
MAKE-H2
4 68.7
1.0
1.29 213.6
WATER
H2-CO2
Q-RXN
FUEL
BURNER
AIR
FLUE-GAS
SteamMethaneReforming&WaterGasShift
Reforming
Reactor
Natural Gas
High Temperature
Shift Reactor
Low Temperature
Shift Reactor
Hydrogen
Purification
Methanation
Reactor
Flue Gas
Steam
Fuel Gas
Hydrogen
CO2
Reforming.Endothermiccatalyticreaction,
typically2030atm&800880C(1470
1615F)outlet.
CH4 +H2O CO+3H2
Shiftconversion.Exothermicfixedbedcatalytic
reaction,possiblyintwosteps.
CO+H2O CO2 +H2
HTS:345370C(650 700F)
LTS:230C(450F)
GasPurification.AbsorbCO2 (amine)orseparate
intopureH2 stream(PSAormembrane).
Methanation.ConvertresidualCO&CO2back
tomethane.Exothermicfixedbedcatalytic
reactionsat370425C(700 800F).
CO+3H2 CH4 +H2O
CO2 +4H2 CH4 +2H2O
SMRAlternateDesigns
Traditionalwith2stagesshift
reactors 95%to98%purity
NewerdesignswithPSA
(PressureSwingAdsorption)
lowercapitalcosts,lower
conversion,butveryhighpurity
(99%+)
ProcessConsiderations
Desulfurization
Reactors
Kaes [2000]
Model as conversion reactor
Reformer
High Temperature
Shift Reactor
Low Temperature
Shift Reactor
Methanation
Amine Purification
PSA
Other
400F entrance
480-525F (249-274C) outlet
Fixed 90% CO conversion
BasicSMRProcess
W
15
1
Remember,directionofarrowindicateswhetherAspenPlus hascalculated,
NOTwhetheritisheatin/out
16
231
28
28
Q
WATER
STEAMGEN
377
28
273
28
REFORMER
815
19
WATPUMP
15
1
349
18
HTS
W
GASCOMP
FEED
HVAL-1
HIERARCHY
38
1
427
18
CO2
Q-HEAT1
Q
204
17
LTS
33
15
AMINE
Temperature (C)
Pressure (atm)
260
14
HIERARCHY
213
16
38
15
METHANTR
COND1
HOTPROD
335
14
38
14
PRODUCT
HVAL-2
HIERARCHY
SMRBasicProcessEnergyRequirements
W
Q
WATER
STEAMGEN
REFORMER
TREATED
TREATED2
WATPUMP
HTS
W
GASCOMP
HVAL-1
FEED
HIERARCHY
HOTPROD
Energy Inputs
CO2
Energy Removal
Steam Boiler
Reformer
Amine Duty
Methanator Reheat
Sub-total
kcal/hr
3,742,371
6,332,965
5,680,514
553,190
16,309,040
BFW Pump
Gas Compressor
Amine Power
Sub-total
10,959
385,571
125,716
522,246
Total
16,831,286
kW
Post Reformer Cooler
Post HTS Cooler
Post LTS Cooler
Amine Coolers
Product Cooler
Total
kcal/hr
2,238,933
1,026,525
2,305,814
3,550,321
800,533
9,922,126
Q
Q
LTS
AMINE
HIERARCHY
12.7
448.4
146.2
METHANTR
COND1
kcal/hr
21,363,070
25,938,163
H2 Purity:
H2 Production:
Total Product
Total Inputs
Efficiency
kmol/hr
kcal/mol
100
213.6
328.6
78.9
292.7
89%
2.9
PRODUCT
HVAL-2
HIERARCHY
25,938,163
38,194,356
68%
10
SMR HeatRecoveryforSteamGeneration
W
Q
WATER
STEAMGEN
REFORMER
TREATED
TREATED2
WATPUMP
HTS
W
GASCOMP
HVAL-1
FEED
HIERARCHY
HOTPROD
Energy Inputs
CO2
Energy Removal
Steam Boiler
Methanator Reheat
Heat Sub-total
kcal/hr
3,742,371
553,190
4,295,561
Reformer
Amine Duty
Sub-total
6,332,965
5,680,514
16,309,040
BFW Pump
Gas Compressor
Amine Power
Sub-total
10,959
385,571
125,716
522,246
Total
16,831,286
kW
Post Reformer Cooler
Post HTS Cooler
Post LTS Cooler
Sub-total
Amine Coolers
Product Cooler
Total
kcal/hr
2,238,933
1,026,525
2,305,814
5,571,272
Q
Q
LTS
AMINE
3,550,321
800,533
9,922,126
HIERARCHY
12.7
448.4
146.2
METHANTR
COND1
PRODUCT
Natural Gas In
Product Out
H2 Out
kcal/hr
21,363,070
25,938,163
H2 Purity:
H2 Production:
Total Product
Net Inputs
Efficiency
HVAL-2
HIERARCHY
25,938,163
33,898,795
77%
11
ReformerFurnaceDesign
HydrogenProductionbySteamReforming
RayElshout,ChemicalEngineering,May2010
12
DirectFiredHeatersforReformer&AmineUnit
Energy Inputs
Energy Removal
Steam Boiler
Methanator Reheat
Heat Sub-total
kcal/hr
3,742,371
553,190
4,295,561
Reformer
Amine Duty
Sub-total
6,332,965
5,680,514
16,309,040
BFW Pump
Gas Compressor
Amine Power
Sub-total
10,959
385,571
125,716
522,246
Total
16,831,286
kW
Post Reformer Cooler
Post HTS Cooler
Post LTS Cooler
Reformer Flue Gas
Sub-total
Amine Coolers
Product Cooler
12.7
448.4
146.2
Total
kcal/hr
2,238,933
1,026,525
2,305,814
648,651
6,219,923
3,550,321
800,533
10,570,777
HIERARCHY
kcal/hr
21,363,070
8,184,406
6,659,083
36,206,559
25,938,163
H2 Purity:
H2 Production:
Total Product
Net Inputs
Efficiency
kmol/hr
kcal/mol Efficiency
100
213.6
38.3
213.6
77%
31.2
213.6
85%
169.5
328.6
292.7
89%
1.7
78.9
25,938,163
36,728,805
71%
13
PreHeattheReformerFeed?
Energy Inputs
Energy Removal
Steam Boiler
Methanator Reheat
Heat Sub-total
kcal/hr
3,742,371
553,190
4,295,561
Reformer
Feed Preheat
Amine Duty
Sub-total
5,132,965
1,200,000
5,680,514
16,309,040
BFW Pump
Gas Compressor
Amine Power
Sub-total
10,959
385,571
125,716
522,246
Total
16,831,286
kW
Post Reformer Cooler
For Feed Preheat
Post HTS Cooler
Post LTS Cooler
Reformer Flue Gas
Sub-total
Amine Coolers
Product Cooler
12.7
448.4
146.2
Total
kcal/hr
2,238,933
-1,200,000
1,026,525
2,305,814
1,673,228
6,044,500
3,550,321
800,533
10,395,354
HIERARCHY
kcal/hr
21,363,070
7,978,680
6,659,083
36,000,833
25,938,163
H2 Purity:
H2 Production:
Total Product
Net Inputs
Efficiency
kmol/hr
kcal/mol Efficiency
100
213.6
37.3
213.6
64%
31.2
213.6
85%
168.5
328.6
292.7
89%
1.7
78.9
25,938,163
36,523,078
71%
14
SMRAlternateDesigns
Traditionalwith2stagesshift
reactors 95%to98%purity
NewerdesignswithPSA
(PressureSwingAdsorption)
lowercapitalcosts,lower
conversion,butveryhighpurity
(99%+)
15
AlternateHydrogenPurificationProcesses
HydrogenProductionbySteamReforming
RayElshout,ChemicalEngineering,May2010
16
UseofPSAforProductPurification
W
Q
Q
Energy Inputs
Energy Removal
Steam Boiler
Feed Preheat
Reformer
Sub-total
kcal/hr
3,742,371
1,200,000
5,132,965
10,075,336
BFW Pump
Gas Compressor
Sub-total
10,959
385,571
396,529
Total
10,471,865
kW
Post Reformer Cooler
For Feed Pre-Heat
Post HTS Cooler
Post LTS Cooler
Reformer Flue Gas
Total
12.7
448.4
kcal/hr
2,238,933
-1,200,000
1,026,525
1,776,046
1,674,739
5,516,243
kcal/hr
21,363,070
7,984,234
29,347,304
8,075,157
18,074,861
H2 Purity:
H2 Production:
Total Product
Total Inputs
Efficiency
kcal/mol Efficiency
kmol/hr
100.0
213.6
37.4
213.6
64%
137.4
165.9
263.0
263.0
100%
1.9
48.7
68.7
SEP
18,074,861
29,743,834
61%
17
UseofPSAforProductPurification
W
Q
Q
Energy Inputs
Energy Removal
Steam Boiler
Feed Preheat
Reformer
Sub-total
kcal/hr
3,742,371
1,200,000
5,132,965
10,075,336
BFW Pump
Gas Compressor
Sub-total
10,959
385,571
396,529
Total
10,471,865
kW
Post Reformer Cooler
For Feed Pre-Heat
Post HTS Cooler
Post LTS Cooler
Reformer Flue Gas
Total
12.7
448.4
kcal/hr
2,238,933
-1,200,000
1,026,525
1,776,046
2,250,289
6,091,793
HIERARCHY
SEP
kcal/hr
21,363,070
951,511
22,314,582
8,075,157
30,389,739
165.9
48.7
18,074,861
263.0
263.0
100%
2.5
68.7
H2 Purity:
H2 Production:
Total Product
Total Inputs
Efficiency
kmol/hr
kcal/mol Efficiency
100.0
213.6
4.5
213.6
104.5
57%
18,074,861
22,711,111
80%
18
IntegratedProcess
HydrogenProductionbySteamReforming
RayElshout,ChemicalEngineering,May2010
19
Whatshouldbethepriceofhydrogen?
Hydrogensalesshouldcoverallcostsplus
profit
Rawmaterialcosts(primarilynatural
gas)
Example
Naturalgas$4.36permillionBTU(asof
March30,2011)=$3.68perkmolCH4
Electricity
Electricity6.79/kWhr(for2010per
EIAforIndustrialcustomers)
Otheroperatingexpenses(staff,)
PSAproductionscenario
Recoveryofcapitalinvested
Minimumistocovercostofnaturalgas&
power
104.5kmol/hrCH4 $385perhr
461.1kW $31perhr
263kmol/hrH2 $0.79perkg
Electrolysiscomparison 80%
electrolysisefficiency&90%
compressionefficiency
$3.80perkg
o
$6.80perkgwithcapitalcosts
included
ARealisticLookatHydrogenPriceProjections,F.DavidDoty
Mar.11,2004(updatedSept21,2004)
20
OtherReferences
RefineryProcessModeling,1st ed.
GeraldL.Kaes
KaesEnterprises,Inc.,2000
HydrogenfromSteamMethaneReformingwithCO2Capture
JohnC.Molburg&RichardD.Doctor
Paperfor20th 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
21