1
Naturgass til fremstilling av hydrogen
- Naturgass-kjeden fra reservoar til bruker THE PRODUCTION OF HYDROGEN FROM NATURAL GAS
TPG4140 NATURGASS
11 Oktober 2010
10:15-11:00 & 11:15-12:00
NTNU Energi- og Prosessteknikk (EPT)
Prof. Dr.-Ing. Ulrich Bünger
Ulrich.Bunger@ntnu.no
2
Outline
Lesson “One”
• Why hydrogen?
• Why hydrogen from natural gas?
• Hydrogen from natural gas
• NG to hydrogen process technology
Lesson “TWO”
• Hydrogen energy chains (= pathways)
• Emissions and costs in comparison to other pathways
• International strategies and projects
• Norwegian strategy
3
Glossary
ATR
auto-thermal reformer
HT-FC
CCS
carbon capture and storage
ICE
CMG
compressed methane gas
LH2
CNG
compressed natural gas
NG
CO
carbon monoxide
RME
CO2
carbon dioxide
PE
DG-TREN Direction Generale Transport and Energy PEMFC
DME
di-methylester
POX
EL
electricity
PSA
EU
European Union
SMR
FAME
fatty acid methyl ester
TES
FC
fuel cell
WGS
FT
Fischer Tropsch
GHG
greenhouse gas (emissions)
GH2
gaseous hydrogen
HFP
Hydrogen and Fuel Cell Technology Platform
H2
hydrogen
high temperature fuel cell
internal combustion engine
liquid hydrogen
natural gas
rape seed methyl ester
primary energy
proton exchange
membrane fuel cell
partial oxidation
pressure swing adsorption
steam methane reformer
Transport Energy Strategy
water gas shift reactor
4
Lesson “One”
5
Early hydrogen vision
Seasonal and daily distribution of renewable forms of energy
and import to the industrial world (here: Germany)
Source: Ludwig Bölkow, 1988
N Seasonal energy
load levelling
Daily energyA global
W
load levelling
energy
E
distribution system
S
HVDC power transport
H2 – pipeline
LH2 tanker routes
Source: GermanHy, 2008
6
Hydrogen‘s short term role – today‘s challenge
20,000
15,000
10,000
Legend
Geotherm al
Hydro
Wind
Biom ass
Solar colle ctors
SOT
PV
Uranium
Coal
Gas
Oil
2030
Geothermal
20,000
W EO 2006
Supply
gap!
Wind pow er
15,000
Biom ass
Hydropower
Uranium
Solar
collectors
SOT
Coal
PV
Gas
5,000
5,000
Oil
1930
1950
1970
1990
2010
10,000
LBST, AWEO 2006
Total primary energy supply in [Mtoe]
2006
2030
2050
Source: LBST, Alternative World Energy Outlook, 2006
2070
2090
7
Sankey diagram Scotland 2002 [TWh]
Transport heavily depends on oil.
What can replace dwindling oil in transport?
8
Why hydrogen from natural gas?
Primary
energy
Replenish.
raw mat.
Organic
residuals
(w(o wood)
Sun,
hydro-/wind
power
renewable
Natural
gas
Wood
fossil
Also
nuclear energy
Conversion
Fermentation
Fermen- Elektrolys. Gasification
tation
Secondary
energy I
Ethanol
Biogas
Hydrogen
Reformer Reformer
Secondary
energy II
NG
Reformer
Coal
Min. oil
2
CO2 from
air/
concentr.
sources
No primary
energy carrier
Reformer
Gasificat.
Refinery
Synthesis/
electrolyis
Methanol
Gasol.
Reformer
Reformer
also internal
reforming
Hydrogen/
CO (HT-FC)
*Also contains all forms of primary energy,
such as nuclear energy
Fuel cell
End-energy
Usable energy
Elec.-mix*
Electr.
Heat
Refrig.
Power/
light
Heating/
Processes
Cooling/
Processes
Large variety of sources
and pathways!
9
Why hydrogen from natural gas?
• In transition phase hydrogen from renewables is more expensive
• Specifically with fuel cells, hydrogen from NG has some GHG
emission reduction potentials versus oil and coal
• NG infrastructure widely available in Europe
• In comparison to oil, NG supply in Europe has a longer term
resource potential ( increased energy supply diversity)
• Today, hydrogen from NG is the least complex ( least expensive)
pathway; steam-reforming of NG (SMR) is the best-known process
but will become more costly over time
• SMR are scalable by size allowing potential transition to flexible
onsite hydrogen production
• Carbon sequestration and storage (CCS) allows nearly CO2 free
hydrogen production, if accepted publically
and widely proven to be safe and economic
10
EU
Hydrogen
Energy
Roadmap
HyWays*
(2004 - 2008)
Selected
hydrogen WTW
pathway
portfolio for 10
countries
(2030)
Transition
and long-term pathways
Spec. CO2 equivalent emissions [g/km]
200
HyWays
U.S. DoE goal:
2-3 $/gge (FC)
180
Untaxed
External costs added
160
Gasoline
EU taxed
140
120
EU taxed
Diesel
100
Onsite SMR
80
Central SMR
(with CCS)
60
By-product
40
20
Offshore wind
Coal gasification
(with CCS)
Boxes represent spread across 10
countries
Shaded areas denote costs with
uncertainty
All cars FC hybrid (2.6 lGE/100 km)
except gasoline/diesel ICE
Waste wood
Onshore wind
0
0,000
0,010
0,020
0,030
Prospect 2030
with forward
looking
assumptions
0,040
0,050
0,060
* HyWays – The European
Hydrogen Energy Roadmap Project
(2004-2008)
Spec. H2 supply costs [€/km]
•www.HyWays.de
EU-wide analysis to understand regionally different approaches & options for H2 in transport
Page 1
• Back- and forecasting with wide stakeholder involvement (industry, institutes, politics)
• Application of toolbox for technical, economic, emissions and policy
impact modelling
• No commercialization approach!
11
Natural gas grid in Europe
Source: NaturalHy 2008
12
Choice of most relevant hydrogen sources
Source: Daimler 2010
13
NG to hydrogen process technology
Major processes for hydrogen production from NG - reforming
Feed gas
clean-up
Raw NG
NG
reforming
NG
Synthesis
gas
clean-up
Synthesis gas
(H2, CO, CO2, CH4)
Hydrogen
purification
H2 + CO
(e.g. <10ppm)
• Dust separation • Steam reforming
• CO conversion
• De-sulphurisation • Partial oxidation
(CO-shift)
• Autothermal reforming
• Plasma reforming
Large NG reformer
Haldor Topsoe
Cleaning by
staged adsorption
•
•
•
•
Catalytic processes
Adsorption
Diaphragm processes
Purification by
metal-hydrides
• Proton-/ion conductors
• Iron-redox filter
(Iron sponge process)
Reformer reactor
Off-gas tank
Pure H2
Burner
14
NG to hydrogen process technology
Steam Reforming of Natural Gas (SMR)
• Steam reforming reaction for NG:
CH4  H 2O  CO  3 H 2
H   206kJ / mole
• Endothermic (catalytic) process with heating (700 - 800°C)
Partial Oxidation of NG (POX)
• Partial oxidation reaction for NG:
CH4  1/ 2 O2  CO  2 H 2
H   36 kJ / mole
• Exothermic (non-catalytic) process at 1,300°C and  9 MPa
with pre-heated O2 to 700 - 800°C, lower H2 efficiency and high
dynamics, O2 taken from air leads to N2 contents in product gas
15
NG to hydrogen process technology
Comparison of reforming processes for NG
SMR
Operating
temperature
700 - 800°C
POX
ATR
Combined SMR/POX
1,300°C
850 - 1,000°C
Efficiency
65 - 70% (small)
81% (large)
69% (large)
65% (PE = 100%)
37%
(PE  EL = 33%)
Dynamics
Low
(endothermic)
High
(exothermic)
High
(exothermic)
16
NG to hydrogen process technology
Major processes for hydrogen production from NG – gas clean-up
Feed gas
clean-up
Raw NG
NG
reforming
NG
Synthesis
gas
clean-up
Synthesis gas
(H2, CO, CO2, CH4)
Hydrogen
purification
H2 + CO
(e.g. <10ppm)
• Dust separation • Steam reforming
• CO conversion
• De-sulphurisation • Partial oxidation
(CO-shift)
• Autothermal reforming
• Plasma reforming
•
•
•
•
Pure H2
Catalytic processes
Adsorption
Diaphragm processes
Purification by
metal-hydrides
• Proton-/ion conductors
• Iron-redox filter
(Iron sponge process)
17
NG to hydrogen process technology
Synthesis gas clean-up: CO – conversion
• Conversion reaction to oxidise CO (CO-Shift):
CO  H 2O  CO2  H 2
H   41kJ / mole
• Exothermic process at 190 - 260°C independant from pressure
• Also dubbed water gas shift reaction (WGS)
18
NG to hydrogen process technology
Major processes for hydrogen production from NG - purification
Feed gas
clean-up
Raw NG
NG
reforming
NG
Synthesis
gas
clean-up
Synthesis gas
(H2, CO, CO2, CH4)
Hydrogen
purification
H2 + CO
(e.g. <10ppm)
• Dust separation • Steam reforming
• CO conversion
• De-sulphurisation • Partial oxidation
(CO-shift)
• Autothermal reforming
• Plasma reforming
•
•
•
•
Pure H2
Catalytic processes
Adsorption
Diaphragm processes
Purification by
metal-hydrides
• Proton-/ion conductors
• Iron-redox filter
(Iron sponge process)
19
NG to hydrogen process technology
Hydrogen purification: adsorption
Scheme of 4-stage PSA process
Product hydrogen
Adsorber
Control
Unit
Instrument
air
Vent stack
Feed gas
Flushing gas
Phigh
Plow
I
- Adsorption
II, V - Pressure balance
III - Pressure relaxation
IV - Flush
VI - Pressure rise
20
NG to hydrogen process technology
Comparison of hydrogen purification processes
Pressure
Costs
Dynamics
Catalytic
processes
PSA
Low
High
High
(e.g. 3 bar)
(20 bar)
(10 bar)
High
High
High
(catalyst)
High
Membrane
technology
(system complexity) (Pd/Ag membrane)
High
(exothermic)
Low
21
Flowsheet of Carbotech SMR at ARGEMUC
(100 Nm3H2/hr)
H2O
NG
De-ion
Osmosis
Synthesis gas
De-sulph.
Bypass
Heat
Air
NG to burner
SMR
PSA-offgas
~ 250°C
~ 1.000°C
Offgas
~ 350°C
Offgas buffer
Heat
(start-up N2)
WGS
H2to storage
tank (~ 30 bar)
~15 bar
H2 buffer
Source: Bünger, Haukedal, 2003
PSA
H2O
22
Large NG steam reformer Leuna/Bitterfeld
• 35,000 Nm3/h hydrogen
• 9-bed PSA (99.9 vol% purity)
Source: Linde
23
Aerial View of SMR
(330 Nm³/h)
Hydrogen product tanks
Reformer reactor
Offgas buffer tank (2 MPa)
4-stage PSA
Source: Caloric
24
Major Components of SMR
Off-gas container
Adsorber
Steamdrum
Steamreformer
Burner
Cooler
Air blower for burner
25
On-site SMR (100 Nm3 H2/h)
with CO-Shift and PSA
Source: Mahler IGS
26
Compact small scale SMR
with integrated desulphurisation for residential PEM-fuel cells (0.5 - 1 kWel)
Type
FPS-1000
Class
FPS-500
for net 1 kWel systems for net 500 Wel systems
CO removal process
Preferential oxidation
Burner fuel
Anode off gas + NG or NG only
CO in product gas
< 1 ppm (initial), < 10 ppm (after 90,000 hours)
Thermal efficiency (LHV) *1 at nominal output
77%
Life (without exchanging any catalysts)
90,000 hours (5 ppm-S in NG)
Size (including thermal insulation, without outer piping)
75%
280Wx440Lx395H
Start-up time
260Wx370Lx395H
ca. 1 hour
Turn down (net available H2 basis)
0% (self-sustainable) - 100%
Load change rate at increasing output
> 1 W/sec*2
Load change rate at decreasing output
Moment*2
Designed start-up and shut-down times
200 times
Pressure drop of fuel line
< 5 kPa
*3
Flow rate of natural gas for process at nominal output
4.2 NL/min
Steam/Carbon ratio at steam reformer
O2/CO Ratio at CO removal reactor
1.5
Flow rate of product gas at nominal output (dry)
Product gas (dry %)
2.1 NL/min
2.5
23 NL/min
11.5 NL/min
H2
> 75 vol.%
N2
< 3 vol.%
CH4
< 2 vol.%
CO
< 1 ppm
CO2
20 vol.%
*1 Thermal efficiency = Enthalpy of H2 consumed in cell stack / (Process natural gas + Burner natural gas)
*2 depends on control procedure.
*3 Composition of natural gas: CH4 = 88 vol.%, C2H6 = 6 vol.%, C3H8 = 3 vol.%, C4H10 = 3 vol.%
Source: Osaka Gas, 2004
27
Lesson “Two”
28
Outline
Lesson “One”
• Why hydrogen?
• Why hydrogen from natural gas?
• Hydrogen from natural gas
• NG to hydrogen process technology
Lesson “TWO”
• Hydrogen energy chains (= pathways)
• Emissions and costs in comparison to other pathways
• International strategies and projects
• Norwegian strategy
29
Fuel emissions and costs in comparison
Energy specific physical properties
CO2
LHV
Density
kg/l
MJ/kg
MJ/l
g/MJ
Gasoline
0.745
43.2
32.2
73.38
Diesel
0.832
43.1
35.9
73.25
Naphtha
0.720
43.7
31.5
71.22
Ethanol
0.794
26.8
21.3
71.38
FAME (biodiesel)
0.890
36.8
32.8
76.23
FT diesel
0.780
44.0
34.3
70.80
Methanol
0.793
19.95
15.8
69.1
DME
0.670
28.4
19.0
67.36
CNG
0.000790
45.1
0.0356
56.24
Hydrogen
0.000090
120.0
0.0108
0.0
Sources: CONCAWE/EUCAR/JRC, WtW calculations by LBST
http://ies.jrc.cec.eu.int/wtw.html
30
Typical hydrogen energy chain
Hydrogen from NG (EU-mix)
NOX CH4 CO2
NOX CH4 CO2
Energy loss
Natural gas
supply
(EU-mix)
NG
Reformer
(on site)
H2
Energy loss
H2 compression
Electricity
Electricity
Energy loss
Energy source
Energy source
NOX CH4 CO2
Electricity
supply
(EU-mix)
Electricity
Energy loss
CGH2
31
Emissions and costs in comparison
GHG emissions for various hydrogen (and reference) energy chains
Fuel production governs GHG emissions
End-use efficiency has a large impact on
WtW efficiency!
Source: GM-WtW Study, LBST, 2003
MTA: Manual Transmission Automatic
DI-ICE: Direct injection ICE
32
Hydrogen production costs from SMR
for on-site and large plant [€/Nm³H2]
Manufacturer
Haldor Topsoe 1998
Linde 1992
Units
Capacity
560
100.000
Nm3H2/h
NG input
1,4406
1,4167
kWh/kWhH2
LHV (NG)
10
10
LHV (H2)
3
3
kWh/Nm3
kWh/Nm3
LHV (H2)
33,33
33,33
kWh/kg
0,43
0,43
Nm3NG/(Nm3H2)
0,0161
2.172.990
-0,05
77.716.366
kWh/kWhH2
EUR
3.880
8.000
403
777
8.000
72.007
EUR/Nm3/h
h/a
tH2/a
Discount rate
Economic lifetime
Capital costs
8%
15
253.869
8%
15
9.079.568
a
EUR/a
NG costs
Electricity costs
Annual NG costs
Annual electricity costs
0,030
0,065
580.850
14.065
0,015
0,050
51.000.000
-6.000.000
EUR/kWh
EUR/kWh
EUR/a
EUR/a
Maintenance
Number of operators
Labour costs
Labour
O&M total
H2 costs
21.730
0
0
0
21.730
0,065
2.331.491
10
50.000
500000
2.881.501
0,024
EUR/a
H2 costs
0,194
0,071
NG input
Electricity input
Investment
Specific investment
Equivalent full load periods
Annual H2 production
EUR/a/operator
EURa
EUR/a
EUR/kWh
EUR/Nm3H2
Source: LBST
Specific investment costs of SMRs
as function of capacity [Nm³H2/hr]
8.000
HyGear (500 Nm³/h):
~3,000 €/(Nm³/h)
7.000
3
Specific investment [€/(Nm /h)]
33
SMR
Bio gasif
Electr.
6.000
with
CCS
Coal gasif
5.000
without
CCS
4.000
onsite SMR
large electrolysis
unit &
HP electrolysis
3.000
in-situ
gasification
with CCS
2.000
central SMR
1.000
0
1
10
100
Source: HyWays, 2006
1.000
10.000
3
Capacity [Nm /h]
Investment scales strongly with plant size!
100.000
1.000.000
with
CCS
34
Hydrogen production costs
International data compilation [€/kg]
Source: NextHyLights, 2010
35
Evolution and selected milestones of EU‘s H2/FC-strategy
Vision Report: “Hydrogen energy and Fuel Cells – A vision of our future”
June 2003
EU Hydrogen&Fuel Cell Technology Platform founded
January 2004 with participation of major stakeholders
High Level Group H2 and FC
(2002-2003)
Two key documents
“Strategic Research Agenda” and “Deployment Strategy”
Endorsed at HFP General Assembly March 2005
2002
Strategic combination of both reports
June/October 2005
“Operations Review Days”
December 2005
HFP General Assembly
Implementation Plan endorsed
October 2006
HyWays EU-H2-Roadmap
Joint Technology
Initiative kicked off
2003
2004
2005
2006
2007
36
Hydrogen production mix Germany
GermanHy - German Hydrogen Energy Roadmap
Shares of primary energy carriers in hydrogen production
100 PJ
480 PJ
100 PJ
470 PJ
90 PJ
440 PJ
political imperative:
share of renewable energies
at least 50%
‘Moderate’
‘Climate’
‘Resources’
Hydrogen to be produced from different primary energy sources
depending on scenario and respective share of individual sources
The future mix of energies for H2 production will
depend on political targets and support, as well
as technological achievements
37
Hydrogen admixture to natural gas grid
NaturalHy – European stakeholder study
(e.g into storage cavern)
Source: M.-B. Hägg, D. Grainger, J. A. Lie;
Dept. of Chem. Eng., NTNU; NaturalHy, 2004
38
Hydrogen admixture to natural gas grid
NaturalHy – European stakeholder study
Some results highlighted
• H2 does not separate from a layer of H2/NG in a confined room
• H2 has a significant impact on the laminar and turbulent flame
velocity
• Mixtures up to 50% H2 in NG are not critical for the crack
propagation in X52 steel pipes
• The permeability of H2 through PE pipes is about 8x the
permeability of NG
Admixture is option for „greening“ NG in public grids.
BUT:
H2-NG mixtures do not provide fuel for fuel cells.
Source: Onno Florisson, Gasunie, NaturalHy, 2007
39
Automotive manufacturers‘ FCEV strategies
2009
Daimler
Fiat
2010
64
A-class
2011
2012
200 B-class
20
H2CNG Panda
> 20
Panda
2013
2014
2015
1,000 B-class
2016
2017
2018
2019
10,000 p.a. B-class
Volkswagen
Ford
GM
Toyota
SAIC
Riversimple
100,000 p.a.
C-class
307 CC
FiSyPAC
20 X-Trail FCV
35
30 FCVs
110 Equinox
10,000 FCVs
100,000 FCVs
>100 FCHV-adv
> 100
250,000 FCVs
FCV Sedan
200 FCX Clarity
Honda
Hyundai
Kia
2021
< 10
FCVs
PSA
Nissan
Renault
2020
1,000
1,000
10,000
30,000
100,000
6
190
Rowe 750 Rowe 750
30
5,000
Source: GM, LBST compilation
40
Key data of fuel cells for transport
Source:
Daimler, 2010
Massive technical learning!
Remaining challenges: FC system costs and H2infrastructure
41
Japan – Hydrogen and Fuel Cells Strategy
Source: Ishitani 2010
42
Japan - H2- fueling stations in field test
Source: Monde 2010
43
HyNor – (Extendable) Norwegian H2 Corridor
New EU Lighthouse cluster Oslo
500 km major trunk roads
Stavanger fuelling station
5 vanHool
FC buses
2 70 MPa and 1 35 MPa
fuelling stations in Oslo
Økern, West Oslo, Lillestrøm
2 Alfa Romeo 10 Daimler 5 Th!nk (FC
B-class range extender)
MiTo FC
F-CELL
1st fuelling station at Grenland
15 Mazda RX8
H2 Wankel
15 Quantum Toyota
H2 hybrid
44
Possible hydrogen production mix Norway
NorWays – Norwegian Hydrogen Energy Roadmap project
200000
%
100%
180000
90%
80%
160000
70%
60%
t Hydrogen /a
140000
50%
40%
120000
Biomass gasification
30%
20%
100000
Byproduct hydrogen
10%
0%
2010
2015
2020
2025
2030
2035
2040
2045
2050
80000
NG-SMR
Electrolysis
60000
40000
20000
0
2010 2015 2020 2025 2030 2035 2040 2045 2050
 >2020, central NG SMR (without carbon capture) and onsite electrolysis
 >2035, more electrolysis (sparsely populated areas deployed; increasing NG prices)
 By-product hydrogen, biomass gasification and SMR with CCS
do not appear economic under current assumptions.
45
Hydrogen as future export opportunity
NorWays – Norwegian Hydrogen Energy Roadmap project
Source: NorWays 2008
Export of hydrogen from NG seems inferior to direct NG export
(given the feasibility of CO2 storage at the destination)
Export of hydrogen from renewable energy from Norway to central
Europe seems advantageous against HVDC in the future!
46
H2 cars and fuelling stations worldwide
290 entries worldwide
29 operated on NG ((de-)central+trucked LH2)
147 in operation (out of which 16+ public)
23 decommissioned, 7 under construction
95 planned, or plans given up (e.g. Mexico)
www.h2mobility.org
Source: LBST
www.h2stations.org
47
Selected Literature
Weindorf, Bünger: Verfahren zur Reinigung von Wasserstoff für den Einsatz in
kleinen Brennstoffzellen (in German), 1996.
Scholz: Verfahren zur großtechn. Erzeugung von Wasserstoff und ihre Umweltproblematik. Berichte aus Technik & Wissenschaft 67/1992, Linde, pp. 13-21.
Ullmann’s Encyclopedia of Industrial Chemistry, Vol. B3, unit operations II, VCH,
1988, pp. 9-1 - 0-52.
Meyer Steinberg: Modern and prospective technologies for hydrogen production
from fossil fuels, Int. J. Hydrogen Energy, Vol. 14, No. 11, pp. 797-820, 1989.
European High Level Group on Hydrogen&Fuel Cells: Hydrogen Energy and
Fuel Cells – A Vision of Our Future,
http://europa.eu.int/comm/research/rtdinfo_en.html, 2003.
The Hydrogen Economy – Opportunities and Challenges, Editors M. Ball, M.
Wietschel, Cambridge University Press, 2009, ISBN 978-0-521-88216-3.