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07 Hydrogen From SMR

This document summarizes the process of hydrogen production from natural gas via steam methane reforming (SMR). It discusses the basic stoichiometry and thermodynamics of SMR, outlines a typical SMR process design including reforming, water-gas shift reactions, and hydrogen purification steps. It provides energy balances for the process and discusses options for improving efficiency, such as integrating heat recovery and feed preheating. Alternative hydrogen purification methods like pressure swing adsorption are also briefly mentioned.
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0% found this document useful (0 votes)
171 views21 pages

07 Hydrogen From SMR

This document summarizes the process of hydrogen production from natural gas via steam methane reforming (SMR). It discusses the basic stoichiometry and thermodynamics of SMR, outlines a typical SMR process design including reforming, water-gas shift reactions, and hydrogen purification steps. It provides energy balances for the process and discusses options for improving efficiency, such as integrating heat recovery and feed preheating. Alternative hydrogen purification methods like pressure swing adsorption are also briefly mentioned.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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HydrogenfromNaturalGasviaSteamMethaneReforming(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):

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

21

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