HydrogenfromNaturalGasviaSteamMethaneReforming(SMR)

JohnJechura jjechura@mines.edu
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):

Fuel+O2 CO2 +H2O(liquid)

Fuel+O2 CO2 +H2O(vapor)

Compound
Hydrogen
Methane
Carbon Monoxide
Carbon Dioxide

GPSA Data Book

Derived from Aspen Plus 2006.5
HHV
LHV
HHV
LHV
Btu/scf Btu/scf kcal/g.mol Btu/scf kcal/g.mol Btu/scf
324.2
273.8
68.7
325.9
57.7
273.9
1010.0
909.4
213.6
1013.1
191.7
909.1
320.5
320.5
67.6
320.6
67.6
320.6
0.0
0.0
0.0
0.0
0.0
0.0

Energyvaluesmayhavetobediscountedwhencombiningdifferenttypes
ShouldtheHHVbediscountedwhencombiningwithheatvalues?

BasicStoichiometery CH4 +2H2OCO2 +4H2

Production:

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

Small temperature increase

Reformer

High Temperature
Shift Reactor

Low Temperature
Shift Reactor

Methanation

Amine Purification

1450 - 1650F exit

Equilibirium Gibbs reactor with 20F
approach (for design).
650 - 700F entrance for HTS + LTS
500 - 535F entrance when no LTS
Equilibirium Gibbs reactor
All components inert except CO, H2O,
CO2, & H2.
400 - 450F entrance
Equilibirium Gibbs reactor
All components inert except CO, H2O,
CO2, & H2.
500 - 550F entrance
Equilibirium Gibbs reactor
All components inert except CH4, CO,
H2O, CO2, & H2.
Model as component splitter
Treated gas 10 - 15F increase, 5 - 10
psi decrease, water saturated

PSA

Model as component splitter

100F entrance

H2 purity as high as 99.999%

Molburg & Doctor [2003]

Model as equilibrium reactor.
Sulfur compounds converted to H2S &
adsorbed in ZnO bed.
500 - 800F depending on technology.
700F most typical.
Typically up to 725 psi (50 bar)
1500F
Model as equilibrium reactor.
660F entrance

Nexant Report [2006]

Other

20 - 30 atm (295 - 440 psia)

850-1000F (455-540C) inlet
1470-1615F (800-880C) outlet
940F (504C) inlet

Fixed 90% CO conversion

400F entrance
480-525F (249-274C) outlet
Fixed 90% CO conversion

Model as component splitter

Treated gas 100F & 230 psi (16 bar)
exit
95% CO2 recovery
Model as component splitter
90% H2 recovered

MDEA circulation, duty, & work estimates

from GPSA Data Book
Rejected CO2 atmospheric pressure &
water saturated

75 - 85% recovery for "reasonable"

capital costs (higher requires more beds)

H2 contains 0.001% product stream as

contaminant
200 - 400 psig feed pressure for refinery
applications
4:1 minimum feed:purge gas ratio. Purge
gas typically 2 - 5 psig.

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

Heating Values (HHV)

Natural Gas In
Product Out
H2 Out

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

Heating Values (HHV)

kmol/hr
kcal/mol
100
213.6
328.6
78.9
292.7
89%
2.9

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

Heating Values (HHV)

Natural Gas In
Reformer Fuel Gas
Amine Unit Fuel Gas
Total
Product Out
H2 Out

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

Heating Values (HHV)

Natural Gas In
Reformer Fuel Gas
Amine Unit Fuel Gas
Total
Product Out
H2 Out

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

Heating Values (HHV)

Natural Gas In
Reformer Fuel Gas
Total
Tail Gas Out
Product Out
H2 Out

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

Heating Values (HHV)

Natural Gas In
Reformer Fuel Gas
Sub-total
Tail Gas Out
Total
Product Out
H2 Out

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

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