Hydrogen 

from Natural Gas via Steam Methane Reforming (SMR)

John Jechura – [email protected]
Updated: January 4, 2015
Energy efficiency of hydrogen from natural gas
• Definition of energy efficiency
• From basic stoichiometry
 CH4 + 2 H2O → CO2 + 4 H2
 Fuel to satisfy the heat requirements
• From “real” processes
 SMR – Steam methane reforming
 Water shift reactions
 Heat integration
 CO2 removal or PSA?

2
Energy Efficiency
• Usable energy out of a process compared to all energy inputs
Eout

  Ein i
• Energy values could be heat, work, or chemical potential (heating value)
 HHV (Gross): Fuel + O2 → CO2 + H2O (liquid)
 LHV (Net): Fuel + O2 → CO2 + H2O (vapor)
GPSA Data Book Derived from Aspen Plus 2006.5
Compound HHV LHV HHV LHV
Btu/scf Btu/scf kcal/g.mol Btu/scf kcal/g.mol Btu/scf
Hydrogen 324.2 273.8 68.7 325.9 57.7 273.9
Methane 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

• Energy values may have to be discounted when combining different types
 Should the HHV be discounted when combining with heat values?

3
Basic Stoichiometery – CH4 + 2 H2O → CO2 + 4 H2
• Production: NH2 mol
4
NCH4 mol
• Apparent efficiency (HHV basis)
 Just from stoichiometry: 4  68.7
  1.29
1  213.6
 Include heat of reaction: 4  68.7
  1.00
1  213.6  61.3

METHANE

MAKE-H2

WATER
H2-CO2

Q
Q-RXN

4
How do we provide the heat of reaction?
• Could use additional methane – 0.29 mol fuel/mol reactant (HHV basis)

NH2 4 mol
• Production:   3.1
NCH4 1  0.29 mol

• Efficiency including fuel (HHV basis) METHANE

MAKE-H2

4  68.7 WATER

  1.0
H2-CO2

1.29  213.6
Q-RXN

FUEL

BURNER

AIR

FLUE-GAS

5
Steam Methane Reforming & Water Gas Shift
Reforming High Temperature Low Temperature Hydrogen Methanation
Reactor Shift Reactor Shift Reactor Purification Reactor

Natural Gas Flue Gas

Steam

Fuel Gas

Hydrogen

CO2

• Reforming.  Endothermic catalytic reaction,  • Gas Purification.  Absorb CO2 (amine) or separate 

typically 20‐30 atm & 800‐880°C (1470‐ into pure H2 stream (PSA or membrane).
1615°F) outlet.
• Methanation.  Convert residual CO & CO2 back 
CH4 + H2O  CO + 3 H2 to methane. Exothermic fixed‐bed catalytic 
• Shift conversion.  Exothermic fixed‐bed catalytic  reactions at 370‐425°C (700 – 800F).
reaction, possibly in two steps. 
CO + 3 H2  CH4 + H2O
CO + H2O  CO2 + H2
CO2 + 4 H2  CH4 + 2 H2O
HTS: 345‐370°C (650 – 700F)
LTS: 230°C (450F)

6
SMR Alternate Designs
• Traditional with 2 stages shift 
reactors – 95% to 98% purity

• Newer designs with PSA 
(Pressure Swing Adsorption) –
lower capital costs, lower 
conversion, but very high purity 
(99%+) 

7
Process Considerations
Kaes [2000] Molburg & Doctor [2003] Nexant Report [2006] Other
Desulfurization Model as conversion reactor Model as equilibrium reactor.
Reactors Sulfur compounds converted to H2S &
adsorbed in ZnO bed.
Small temperature increase 500 - 800°F depending on technology.
700°F most typical.
Typically up to 725 psi (50 bar)
Reformer 1450 - 1650°F exit 1500°F 20 - 30 atm (295 - 440 psia)
Equilibirium Gibbs reactor with 20°F Model as equilibrium reactor. 850-1000°F (455-540°C) inlet
approach (for design). 1470-1615°F (800-880°C) outlet
High Temperature 650 - 700°F entrance for HTS + LTS 660°F entrance 940°F (504°C) inlet
Shift Reactor 500 - 535°F entrance when no LTS
Equilibirium Gibbs reactor Fixed 90% CO conversion
All components inert except CO, H2O,
CO2, & H2.
Low Temperature 400 - 450°F entrance 400°F entrance
Shift Reactor Equilibirium Gibbs reactor 480-525°F (249-274°C) outlet
All components inert except CO, H2O, Fixed 90% CO conversion
CO2, & H2.
Methanation 500 - 550°F entrance
Equilibirium Gibbs reactor
All components inert except CH4, CO,
H2O, CO2, & H2.
Amine Purification Model as component splitter Model as component splitter MDEA circulation, duty, & work estimates
from GPSA Data Book
Treated gas 10 - 15°F increase, 5 - 10 Treated gas 100°F & 230 psi (16 bar) Rejected CO2 atmospheric pressure &
psi decrease, water saturated exit water saturated
95% CO2 recovery
PSA Model as component splitter Model as component splitter
100°F entrance 90% H2 recovered 75 - 85% recovery for "reasonable"
capital costs (higher requires more beds)

H2 purity as high as 99.999% 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.

8
Basic SMR Process
W Q
Remember, direction of arrow indicates whether AspenPlus has calculated, 
NOT whether it is heat in/out 
15 16 231
1 28 28

Q
WATER 273 815
377 28 19
STEAMGEN REFORMER
28
WATPUMP

349
18
Q HTS

15 W
1

GASCOMP
38
HVAL-1 1
FEED 427
HIERARCHY 18

CO2
Q
Q-HEAT1

Q 204
17
LTS
33 260
15 14

AMINE
Temperature (C) HIERARCHY
213
Pressure (atm) 16 38
15
COND1 METHANTR

335
HOTPROD 14
Q

38
Q
14

HVAL-2
PRODUCT
HIERARCHY

9
SMR Basic Process Energy Requirements
W Q

Q
WATER

STEAMGEN REFORMER TREATED TREATED2

WATPUMP

HTS

GASCOMP

HVAL-1
FEED
HIERARCHY
HOTPROD
CO2
Energy Inputs Energy Removal
kcal/hr kW kcal/hr
Steam Boiler 3,742,371 Post Reformer Cooler 2,238,933 Q

Reformer 6,332,965 Post HTS Cooler 1,026,525 LTS

Q

Amine Duty 5,680,514 Post LTS Cooler 2,305,814

Methanator Reheat 553,190 Amine Coolers 3,550,321
Sub-total 16,309,040 Product Cooler 800,533 AMINE
Total 9,922,126 HIERARCHY
BFW Pump 10,959 12.7
Gas Compressor 385,571 448.4
METHANTR
Amine Power 125,716 146.2 COND1

Sub-total 522,246

Total 16,831,286 Q
Q

Heating Values (HHV) HVAL-2

PRODUCT
kcal/hr kmol/hr kcal/mol HIERARCHY

Natural Gas In 21,363,070 100 213.6

Product Out 25,938,163 328.6 78.9
H2 Out 292.7
H2 Purity: 89%
H2 Production: 2.9

Total Product 25,938,163

Total Inputs 38,194,356
Efficiency 68%

10
SMR – Heat Recovery for Steam Generation
W Q

Q
WATER

STEAMGEN REFORMER TREATED TREATED2

WATPUMP

HTS

GASCOMP

HVAL-1
FEED
HIERARCHY
HOTPROD
CO2
Energy Inputs Energy Removal
kcal/hr kW kcal/hr
Steam Boiler 3,742,371 Post Reformer Cooler 2,238,933 Q

Methanator Reheat 553,190 Post HTS Cooler 1,026,525 LTS

Q

Heat Sub-total 4,295,561 Post LTS Cooler 2,305,814

Sub-total 5,571,272
Reformer 6,332,965 AMINE
Amine Duty 5,680,514 Amine Coolers 3,550,321 HIERARCHY
Sub-total 16,309,040 Product Cooler 800,533
Total 9,922,126
METHANTR
BFW Pump 10,959 12.7 COND1

Gas Compressor 385,571 448.4

Amine Power 125,716 146.2
Sub-total 522,246 Q
Q

Total 16,831,286 HVAL-2

PRODUCT
HIERARCHY

Heating Values (HHV)

kcal/hr kmol/hr kcal/mol
Natural Gas In 21,363,070 100 213.6
Product Out 25,938,163 328.6 78.9
H2 Out 292.7
H2 Purity: 89%
H2 Production: 2.9

Total Product 25,938,163

Net Inputs 33,898,795
Efficiency 77%

11
Reformer Furnace Design

“Hydrogen Production by Steam Reforming”
Ray Elshout, Chemical Engineering, May 2010

12
Direct Fired Heaters for Reformer & Amine Unit

Energy Inputs Energy Removal

kcal/hr kW kcal/hr
Steam Boiler 3,742,371 Post Reformer Cooler 2,238,933
Methanator Reheat 553,190 Post HTS Cooler 1,026,525
Heat Sub-total 4,295,561 Post LTS Cooler 2,305,814
Reformer Flue Gas 648,651
Reformer 6,332,965 Sub-total 6,219,923
Amine Duty 5,680,514
Sub-total 16,309,040 Amine Coolers 3,550,321
Product Cooler 800,533
BFW Pump 10,959 12.7 Total 10,570,777
Gas Compressor 385,571 448.4 HIERARCHY

Amine Power 125,716 146.2

Sub-total 522,246

Total 16,831,286

Heating Values (HHV)

kcal/hr kmol/hr kcal/mol Efficiency
Natural Gas In 21,363,070 100 213.6
Reformer Fuel Gas 8,184,406 38.3 213.6 77%
Amine Unit Fuel Gas 6,659,083 31.2 213.6 85%
Total 36,206,559 169.5

Product Out 25,938,163 328.6 78.9

H2 Out 292.7
H2 Purity: 89%
H2 Production: 1.7

Total Product 25,938,163

Net Inputs 36,728,805
Efficiency 71%

13
Pre‐Heat the Reformer Feed?

Energy Inputs Energy Removal

kcal/hr kW kcal/hr
Steam Boiler 3,742,371 Post Reformer Cooler 2,238,933
Methanator Reheat 553,190 For Feed Preheat -1,200,000
Heat Sub-total 4,295,561 Post HTS Cooler 1,026,525
Post LTS Cooler 2,305,814
Reformer 5,132,965 Reformer Flue Gas 1,673,228
Feed Preheat 1,200,000 Sub-total 6,044,500
Amine Duty 5,680,514
Sub-total 16,309,040 Amine Coolers 3,550,321
Product Cooler 800,533 HIERARCHY

BFW Pump 10,959 12.7 Total 10,395,354

Gas Compressor 385,571 448.4
Amine Power 125,716 146.2
Sub-total 522,246

Total 16,831,286

Heating Values (HHV)

kcal/hr kmol/hr kcal/mol Efficiency
Natural Gas In 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%
Total 36,000,833 168.5

Product Out 25,938,163 328.6 78.9

H2 Out 292.7
H2 Purity: 89%
H2 Production: 1.7

Total Product 25,938,163

Net Inputs 36,523,078
Efficiency 71%

14
SMR Alternate Designs
• Traditional with 2 stages shift 
reactors – 95% to 98% purity

• Newer designs with PSA 
(Pressure Swing Adsorption) –
lower capital costs, lower 
conversion, but very high purity 
(99%+) 

15
Alternate Hydrogen Purification Processes

“Hydrogen Production by Steam Reforming”
Ray Elshout, Chemical Engineering, May 2010

16
Use of PSA for Product Purification
W Q

Energy Inputs Energy Removal

kcal/hr kW kcal/hr
Steam 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-total 10,075,336 Post LTS Cooler 1,776,046
Reformer Flue Gas 1,674,739
BFW Pump 10,959 12.7 Total 5,516,243 Q
Gas Compressor 385,571 448.4
Sub-total 396,529

Total 10,471,865

Heating Values (HHV)

kcal/hr kmol/hr kcal/mol Efficiency
SEP

Natural Gas In 21,363,070 100.0 213.6

Reformer Fuel Gas 7,984,234 37.4 213.6 64%
Total 29,347,304 137.4

Tail Gas Out 8,075,157 165.9 48.7

Product Out 18,074,861 263.0 68.7 Q
H2 Out 263.0
H2 Purity: 100%
H2 Production: 1.9

Total Product 18,074,861

Total Inputs 29,743,834
Efficiency 61%

17
Use of PSA for Product Purification
W Q

Energy Inputs Energy Removal

kcal/hr kW kcal/hr
Steam 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-total 10,075,336 Post LTS Cooler 1,776,046 HIERARCHY

Reformer Flue Gas 2,250,289 Q

BFW Pump 10,959 12.7 Total 6,091,793

Gas Compressor 385,571 448.4
Sub-total 396,529

Total 10,471,865 SEP

Heating Values (HHV)

kcal/hr kmol/hr kcal/mol Efficiency
Natural Gas In 21,363,070 100.0 213.6
Reformer Fuel Gas 951,511 4.5 213.6
Sub-total 22,314,582 104.5 Q

Tail Gas Out 8,075,157 165.9 48.7 57%

Total 30,389,739

Product Out 18,074,861 263.0 68.7

H2 Out 263.0
H2 Purity: 100%
H2 Production: 2.5

Total Product 18,074,861

Total Inputs 22,711,111
Efficiency 80%

18
Integrated Process

“Hydrogen Production by Steam Reforming”
Ray Elshout, Chemical Engineering, May 2010

19
What should be the price of hydrogen?
• Hydrogen sales should cover all costs plus  • Example
profit
 Natural gas $4.36 per million BTU (as of 
 Raw material costs (primarily natural  March 30, 2011) = $3.68 per kmol CH4
gas)
 Electricity 6.79 ¢/kW‐hr (for 2010 per 
 Electricity EIA for Industrial customers)
 Other operating expenses (staff, …)  PSA production scenario
 Recovery of capital invested • 104.5 kmol/hr CH4  $385 per hr
• Minimum is to cover cost of natural gas &  • 461.1 kW  $31 per hr
power
• 263 kmol/hr H2  $0.79 per kg
 Electrolysis comparison – 80% 
electrolysis efficiency & 90% 
compression efficiency
• $3.80 per kg 
o $6.80 per kg with capital costs 
included

A Realistic Look at Hydrogen Price Projections, F. David Doty
Mar. 11, 2004 (updated Sept 21, 2004)

20
Other References
• Refinery Process Modeling, 1st ed.
Gerald L. Kaes
Kaes Enterprises, Inc., 2000
• “Hydrogen from Steam‐Methane Reforming with CO2 Capture”
John C. Molburg & Richard D. Doctor
Paper for 20th Annual International Pittsburgh Coal Conference, September 15‐19, 2003
http://www.netl.doe.gov/technologies/hydrogen_clean_fuels/refshelf/papers/pgh/hydrogen%20from%
20steam%20methane%20reforming%20for%20carbon%20dioxide%20cap.pdf
• Equipment Design and Cost Estimation for Small Modular Biomass Systems, Synthesis Gas 
Cleanup, and Oxygen Separation Equipment; Task 1: Cost Estimates of Small Modular 
Systems
NREL Subcontract Report, work performed by Nexant Inc., San Francisco, CA
May 2006
http://www.nrel.gov/docs/fy06osti/39943.pdf

21