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Overview of Hydrogen Production
Thomas NietschExpert
HELION
“HyFC” Hydrogen and Fuel Cell Academy
European Summer School
1 - 4 October 2007, Svendborg, DK
Expert
Feedstock for hydrogen production
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références2 2HELION
Hydrogen production
Petroleum
Steam Reforming
Petroleum7%
Electrolysis4%
Coal4%
Hydropower
Renewables
Nuclear
Electrolysis
Heating Fuel35%
Transportation Fuel40%
Chemical Feedstock 7%
(Olefins, Aromatics)
Miscellaneous8%
Power Generation
10%Electrolysis0,5%
WORLD HYDROGEN PRODUCTION VS
ENERGY PRODUCTION
3504 Mt
230 Mtoe
64 Mtoe
Gasification
« On-purpose »Hydrogen
Sources: IEA, IGU; 2002 data
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références3 3HELION
MerchantHydrogen2.6 Mtoe 85% from natural gas
Coal
(Tar, Aromatics, CO-H2)
Gasification
Nuclear
Natural GasSteamReforming
Chemical Feedstock 2%
Iron & Steel20%
Power Generation
60%
Miscellaneous18%
Heating Fuel
PowerGeneration20%
ChemicalFeedstock
7% NH3, CH3OHRefineries2236 Mtoe
593 Mtoe
2135 Mtoe
73 Mtoe/10,000 Mtoe = 0.8 % of world energyconsumption
By-productHydrogen57 Mtoe
Electricity: 12% of world energy consumption
73%
Hydrogen production and conversion chain
Natural gas Uranium Crude oilCO2 from
athmospherBio plants
Organicwasts
Sun, wind,watter
Wood
renewable Non renewable
Primeryenergy
Transformation Reformation RefineryGasificationSynthesis /electrolysis
Vermentation Vergärung Electrolysis Gasification
Natural gas Gas / dieselMethanol
Electricityproductiobn
Ethanol Bio gas HydrogenSecondaryEnergy
Coal
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références4 4HELION
Reformer Reformer Reformer Reformer Reformer
Hydrogen
CombustionFuel cell /
ICEIC / turbine
Heat andpower
Heat Heat andpower
Transformation
SecondaryEnergy
Transformation
UsfulEnergy
Hydrogen production by primary energy sources
� Natural gas: 85 %
� Coal: 4 %
� Crude oil: 7 %
� Hydropower: 4 %
� Renewables
� Nuclear power
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références5 5HELION
� Hydrogen production represents 0,8 % of the worlds energy consumption
85 % from NG0,8 % of world wide energy consumption
Hydrogen production by technologies
� Steam reforming (NG, coal, oil, biomass…)
� Gasification (NG, coal, oil, biomass…)
� Electrolysis (hydro, renewables, nuclear)
w Low temperature
� “New technologies”
w Photo-electrolysis (photolysis)
w Photo-biological production (bio photolysis)
w High temperature thermo-chemical water slitting
iodine / sulphur cycle (IS
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références6 6HELION
w Low temperature electrolysis
w High temperature electrolysis
l iodine / sulphur cycle (IS cycle)
Most H2 is produced by
large steam reforming plants
US DOE Goals for Hydrogen Production Costs 2005 *)
Production technology Goal Target Year
H2 from NG and oil 1,5 $/kg 1) 2010
Electrolysis < 250 kg/day 3) 2,5 $/kg 2) 2010
Electrolysis > 250 kg/day 2,0 $/kg 2) 2010
Biomass 4) 2,6 $/kg 2015
Biological systems 10 $/kg 2015
Photo electrochemical water splitting 5) 5,0 $/kg 2015
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références7 7HELION
Thermo-chemical cycles using nuclear heat
Demonstration of technical capability at price competitive with gasoline
2015
OthersEvaluate new production
technologies and fund R&D
1) no CO2 taxes
2) plant gate costs
3) cap costs 300 $/kW, 73 % efficiency, 350 bar
4) 75 000 kg/day, suitable for PEM FC
5) projected to commercial scale
*) US DOE, Energy Efficiency and Renewable Energy, 2003, Annual Progress Report: H2, FCs etc.
Production technology efficiency $/GJ $/kgSteam methane reforming 1), 2) 83% 5,54 0,75Hydrocarbon partial oxidation 1) 70 - 80 % 7 - 11NG Auto thermal reforming 1) 71 - 74 % 16,88 1,93Coal gasification 1) 63% 6,83 0,92Today's electrolysis 1) 10 - 45 1 - 6Steam reforming of bio oil produced by pyrolysis 1), 3)
56% 9,4 - 16,3 1,26 - 2,19
Direct biomass gasification 1), 3) 40 - 56 % 9 - 18 1,21 - 2,42
2003 Hydrogen Production Costs
Tod
ay's
te
chno
logi
esN
ew te
chno
logi
es
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références8 8HELION
Direct biomass gasification 1), 3) 40 - 56 % 9 - 18 1,21 - 2,42High temperature electrolysis 1, 4) 45 - 55 % 14,5 1,95SI cycle 1), 4) 42 - 52 % 1,8 to 2Photo biologic 1,) 4) 24% 41 5,5Photocatalysis 1, 4) 10 - 14 % 37 5
1) based on HHV2) NG at 3,15 $/GJ3) prediction based on lab scale results4) predictions
*) Hydrogen Production Methods, Feb 2005, prepared for MPR Associates, INC, MPR-WP-0001 revision 0, Kathleen McHugh
New
tech
nolo
gies
Why do we need hydrogen today?
� Self production 96 %
w Ammonia 60 %
l Fertilisers
l Washing powders, etc
w Refineries 29 %
� Merchant 4 %
w On site
w Pipelines
w Tube trailer
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références9 9HELION
w Refineries 29 %
w Chemicals 10 %
w Others 1 %
w Bulk
w Cylinders
Ammonia production and refineries
Why do we need (more) hydrogen tomorrow?
� Transportation
wFuel cell cars
� Increase demand in refineries
� Synthetic fuels
� New power generation
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références10 10HELION
� New power generation
w IGCC for CO2 free power generation
CO2 free
transportation and power generation
Hydrogen production today
� Today hydrogen production consumes finite primary energy
� Today hydrogen production contributes to pollution (CO2, global warming)
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références11 11HELION
H2 production consumes finite resources
and contributes to CO2 emissions
Hydrogen from fossil fuels
� By steam reforming (steam methane reforming –« SMR »)
� By partial oxidation (POX)
� By autothermal reforming (ATR)
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références12 12HELION
Reforming of fossil fuels
Steam reforming
steam
CH4, coal,
oil bio masse
Syn gas
H2, ~10 to 20 % CO
T = 700 to 900 °C
P = 1 to 50 barCH4 + H2O => CO + H2 / ∆h = 206 kJ/mol
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références13 13HELION
Sketch steam reforming
oil bio masseheat
� Steam reforming:
w CH4 + H2O = CO + 3 H2 ∆∆∆∆H = 206 kJ/mole
w CO + H2O = CO2 + H2 ∆∆∆∆H = -41 kJ/mole
w 700 to 850 °C
w 3 to 25 bar
Steam reforming
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références14 14HELION
w 3 to 25 bar
w Important CO content
w External heat source / heat supplied by steam
w Catalysts are Ni on Alumina, Alkali promoted, optimised for long-term stability (>3 years) at high temperatures
Equilibrium CO Content for Steam Reforming
0.1
0.15
0.2
0.25
CO in effluent [mole fr]
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références15 15HELION
Feed = Methane
1 2 3 4
600700
800900
10001100
0
0.05
0.1
Steam to Carbon Ratio
Outlet temperature
[°C]
High steam to carbon ration, low T
For reducing CO
Partial oxidation (POX) /autothermal reforming (ATR)
air
CH4, coal,
oil bio masse
Syn gas
H2, ~10 to 20 % CO
N2, NOx
T = 700 to 900 °C
P = 1 to 50 bar
CH4 + ½ O2 => CO + 2H2 / ∆h = -36 kJ/mol
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références16 16HELION
Sketch POX / ATR
oil bio masseHeat : POX
Heat = 0 : ATR
� Partial oxidation (POX)
w CH4 + ½ O2 => CO + 2H2 ∆h = -36 kJ/mol
w Combustion intern of a part of CH4
w CO purification
w Temperature range typically 750-1100 °C
Partial oxidation (POX) and autothermal reforming
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références17 17HELION
w Temperature range typically 750-1100 °C
w Partial oxidation is catalytic or non-catalytic
w Catalysts are Ni or noble metal on refractory oxides
� Autothermal reforming (ATR)
w Combination of steam reforming and partial oxidation
Equilibrium CO Content for Autothermal Reforming, No Steam Addition
0.08
0.1
0.12
0.14
0.16CO m
ole fraction [-]
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références18 18HELION
0
0.02
0.04
0.06
0.08
600 650 700 750 800 900 1000 1100
Outlet Temperature [°C]
CO m
ole fraction [-]
Hydrogen clean up
steam
High temperature
shift reaction
Heat
Syn gas
H2,
~10 to 20 % CO
T = 700 °C
P = 1 to 50 bar
CO +H2O <=> CO2 + 2 H2
/∆h = - 41 kJ/mol
T = 200 to 400 °C
P = 1 to 50 bar
CO +H2O <=> CO2 + 2 H2
/∆h = - 41 kJ/mol
H2,
~ 5 to 10 % CO
Low temperature
shift reaction
Preferential oxidation
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références19 19HELION
Heat
Heat
/∆h = - 41 kJ/mol
Heat
T < 200 °C
CO +O2 <=> CO2
/∆h
Preferential oxidation
H2,
~ 1 to 5 % CO
H2,
~ 0,1 to 5 ppm CO
3 steps for H2 clean up
Water Gas Shift Reaction
� CO + H2O = CO2 + H2 ∆∆∆∆H = - 42 kJ/mole
w Temperature range 600 -> 200 °C
l 400-600 °C : Fe-oxides, Chromia
l 300-400 °C : Fe-oxides, Chromia, Copper
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références20 20HELION
l 200-280 °C : Cu/ZnO systems
Equilibrated WGS Effluent, from SR at 800 °C
0.15
0.2
0.25
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références21 21HELION
1 23
4
500
400
300250
200
0
0.05
0.1
Mole fraction CO
Steam to Carbon Ratio
Temperature [°C]
3000 ppmv1000 ppmv
High steam to carbon ration, low T
For reducing CO
Fuel Processing Schemes: WGS Conclusions
� CO content is strong function of temperature and steam to carbon ratio
� Catalyst volumes become excessive at low temperature
Ô Strong need for high activity LTS catalyst
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références22 22HELION
Ô Strong need for high activity LTS catalyst
� Option of cutting off conversion
w Limitations of clean-up process
w Efficiency considerations
� Steam reforming
w Slow start-up
w Up to C6
w Radiant heat transfer
w Higher efficiency
Commonly Made Observations
� Autothermal
w Fast start-up
w Fuel flexible
w No heat transfer issues
w Lower efficiency
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références23 23HELION
w Higher efficiency
w Higher H2 concentration
w No oxygen/HC mixtures
w Lower efficiency
w N2 dilution
w Explosive mixtures
in contained space
Fuel Processing Schemes:CO Clean-Up Methods
� Preferential oxidation
� Selective methanation
� H2 selective membranes
� Pressure or temperature swing adsorption
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références24 24HELION
Ø The latter two are not catalytic and require higher pressure operation
Preferential Oxidation Catalysis
� CO + 0,5 O2 = CO2 ∆∆∆∆H = -280 kJ/mole
� H2 + 0,5 O2 = H2O ∆∆∆∆H = -240 kJ/mole
w Temperature range 80-200 °Cl At fuel cell or WGS conditions
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références25 25HELION
w Noble metals on oxide carrier (Ru, Pt, Au)l Kahlich et al. , Ulm University
l Oh et al., GM R&D
w Selectivity appears to be strongly dependent on temperature and pO2 ÔÔÔÔ engineering solutions
l Heil et al., Daimler Benz, US 5874051
Summary Reforming
� By steam reforming (steam methane reforming – « SMR »)w CH4 + H2O => CO + H2 ∆h = 206 kJ/mol
w CO +H2O => CO2 + 2 H2 + heat ∆h = - 41 kJ/mol
w 700 to 850 °C / 3 to 25 bar / CO content
w External heat source / heat supplied by steam
w Catalysts are Ni on Alumina, Alkali promoted, optimised for long-term stability (>3 years) at high temperatures
� By partial oxidation (POX)w CH4 + ½ O2 => CO + 2H2 ∆h = -36 kJ/mol
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références26 26HELION
w CH4 + ½ O2 => CO + 2H2 ∆h = -36 kJ/mol
w Combustion intern of a part of CH4
w CO purification
� By autothermal reforming (ATR)w Combination of steam reforming and partial oxidation
Summary CO clean up
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références27 27HELION
Texte de conclusion sur 1 ligne… sur 2 lignes
Modèle de titre sur 1 ligne
GAZNAT
5EAU
EAUVAPGAZCHAUD PRODPRIM
AIR
AIRCHAUD
ATRIN
PRODATR
SHIFTINSHIFT12SHIFT2IN
V1
HEAT1
MIX1
HEAT2RPRIM
V2
MIX2
ATR
HEAT4
HEAT5SHIFT1
SHIFT2
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références28 28HELION
Complex system
PROXINPROXOUT
SHIFTOUT
GAZMIXIN
AIRPROX
SEPIN
GAZSEP
EAUSEP
PROX
HEAT6
MIX3
HEAT7
SEPARA
Comparaison
Benefits high efficiency smaller size
emissions costs for small units
costs for large units simple system
Technology SMR ATR / POX
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références29 29HELION
costs for large units simple system
Challenges complex system lower efficiency
Sensitive to natural gas qualities H2 purification
Hydrogen from water splitting
»Natural gas
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références30 30HELION
Texte de conclusion sur 1 ligne… sur 2 lignes
High temperature water vapour electrolysis
1,5
2,0
2,5
3,0
3,5
4,0
4,5
5,0
Ene
rgy
E/k
wh/
m3 H
2
theoretical stack total enery demand= heat demand + electrical energy demand: ∆hr
theoretical stack electrical energy demand: ∆gr
liquid water
steam
theoretical and real energy imput to electrolyser
real PEM Esystem
"real" SOECsystem
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références31 31HELION
0,0
0,5
1,0
0 100 200 300 400 500 600 700 800 900 1000
Temperature T/°C
theoretical stack heat demand: T∆sr
liquid water
p = 1 bar
T (°C) 25 600 800 1000
E0T(V) 1.23 1.035 1 0.977
10.918 1
Cs0(kWh/Nm3) 2.94 2.47 2.38 2.19
Operation at higher temperature
enables lower theoretical electrical consumption
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références32 32HELION
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références33 33HELION
Technologie alcaline Technologie PEM Electrolyse haute température
Principaux avantages • Technologie éprouvée
depuis des années• Simplicité• Technologie la moins
coûteuse
• Pas d’électrolyte corrosif• Bonne stabilité chimique• Faible perte ohmique à
l’électrolyte• Bonne conductivité
protonique• Bonne résistance mécanique• Technologie très modulaire
• Possibilité de rendement élevé
• Pas d’électrolyte corrosif• Pas de problèmes de
distribution de liquide et d’écoulement
• Technologie très modulaire• Surtension d’électrodes
réduites
Principaux inconvénients • Rendement plus faible
(pertes ohmiques • Prix élevé de la membrane• Utilisation de catalyseurs à
• Besoin de chaleur haute température
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références34 34HELION
(pertes ohmiques élevées, surtension aux électrodes
• Densité de courant faible• Electrolyte corrosif
• Utilisation de catalyseurs à partir de matériaux précieux
température• Matériaux doivent être
résistants à la chaleur• Coût des procédés de
fabrication des matériaux élevé
• Durée de vie de la cellule actuellement très faible
Remarques De grandes unités d’électrolyse alcalines ont été construites dans le passé.
Le développement de catalyseurs et membranes bon marchés sont les clés pour la commercialisation à un prix abordable de cette technologie.
Procédé encore à l’échelle du laboratoire.
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références35 35HELION
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références36 36HELION
Comparison table of Water Electrolysis technologies
Technique Alkaline PEMHigh Temperature
(O2- conduction)
High Temperature
(H+ conduction)
Common electrolyte
uAqueous KOH solution
uAcidic Polymer membrane
u Solid Oxide (ceramic compound)
u Proton Conducting Ceramics
Expected application
s
u Industrial applications
u Stationary applications
u Stationary and mobile applications
u Stationary. To be coupled with high T solar or nuclear
Advantages
uMature technology
u Significant operating record in industrial
uQuick start-up
u Significant higher electrical efficiencies
u Freedom of architecture
uGood resistance to poisoning
u Softer conditions for structure and
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références37 37HELION
Texte de conclusion sur 1 ligne… sur 2 lignes
industrial applications poisoning
for structure and sealants
DrawbacksuKOH caustic
u “Low” operating pressures
u Limited lifetime of membranes
uHigh costs
u Low capacity
uNot mature
u Long start-up time
uNot mature
u Limited lifetime of structure and sealants due to thermo mechanical stress
u Less resistance to catalyst poisoning
Major R&D challenge
uDecrease capital costs
uHigher pressure and temperature for increased efficiency
uMaterial developments
uReduce price of catalysts
uMaterial development including structure and sealants…
u Stack design
u Identification and development of a suitable electrolyte
uDemonstrate feasibility
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références38 38HELION
Electrolysis versus SMR
� 1970 -1980: SMR supplants electrolysis. Numerous players (GE, ABB?) get out the electrolyzer’s business
� Today, the major market is for industrial application, mainly in the 3rd world, in aeras where natural gas is not available or expensive, for the markets below.
� In Europe, Japan and USA, use of electrolyzers is mainly for cooling and corrosion control in nuclear reactors.
� Electrolyzers for producing hydrogen as an energy carrier are a small niche market.
Key figures
Norsk Hydro Large scale electrolyzer (30,000 m3/h, i.e. 65t/day) used in the past (1948 -1990) for ammonia production
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références39 39HELION
� Most of the time the electrolyzer outflow is under 500 Nm3/h, i.e. 1,08 t/day
El Segundo SMR plant, California. 98,000 Nm3/hi.e. 212 t/day, for a Chevron Texaco’s refineryMain types of markets for H2 produced by electrolysis today
Corrosion control
CoolingHydrogenatio
nProtective atmosphere
Nuclear reactors
Power generators
H2 peroxide
Organic chemicals
Edible oil,
fatty acids
Metallurgy
Electronics
Float Glass
Source: interviews (Norsk Hydro, Accagen, Hydrogenics)
Three H2 production technologies through water electrolysis
Technique Alkaline electrolysisPolymer Electrolyte Membrane (PEM)
electrolysis
High temperature electrolysis
Electrolyte Aqueous KOH solution Acidic Polymer membraneSolid Oxide = hard, non
porous ceramic compou
Reactions
Electrolyte:
Cathode:
Anode:
Anode:
Cathode:
Anode:
Cathode
Total
4 H20 à 4 H+ + 4 OH-
4 H+ + 4 e- à 2 H2
4 OH- à O2 + 2 H20 + 4 e-
4 H20 à 1/2 O2 + 2H+ + 2e-
2 H+ + 2e- à H2
O2- à 1/2 O2 + 2e-
H2O(g) + 2e- à H2 + O2-
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références40 40HELION
Total Reaction
2 H20 à 02 + 2 H2
Characteristics
Operating pressures 3 - 30 bar
Commercial electrolyzers = a number of electrolytic cells arranged in a cell stack
Operating pressures: several 100 bars
Typical technology: SOF
operating at 700 – 1000
Applications Stationary applications Stationary and mobile applications
Stationary. To be coupled whigh T solar or nuclear
AdvantagesMature technology
Significant operating record in industrial applications
Higher turndown ratio
Increased safety (no KOH electrolytes)
More compact design
Significant higher overaprocess efficiencies
KOH caustic
Limited lifetime of the membranes
High costs
H distribution Clients
Renewable
Energies
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références41 41HELION
H2 distribution
Electrical Grid
H2 storageWindmills Fuel cellElectrolysis
Conversion
Clients
O2
Biomass
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références42 42HELION
Photo-electrolysis (photolysis)
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références43 43HELION
Photo-biological production (biophotolysis)
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références44 44HELION
High temperature thermo-chemical water slitting / iodine / sulphur cycle (IS cycle)
� H2SO4 => SO2 + H2O + ½ O2 850 °C
� I2 + SO2 + 2H2O => H2SO4 + 2 HI 120 °C
� 2 HI => I2 + H2 450 °C
� H O => H + ½ O
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références45 45HELION
� H2O => H2 + ½ O2
Production technologies from natural gas
Technique Steam Methane Reforming (SMR) Partial Oxidation (POX) Autothermal Reforming (ATR)
Heat
endothermic
Heat often supplied from the combustion of some of the CH4 feed-
gas
exothermic exothermic
Inputs WaterO2
Water for water gas shift reaction
Water + O2
Water for water gas shift reaction
ReactionCH4 + H2O + heat àààà CO + 3 H2
Product gas: 12% of COCH4 + ½ O2 àààà CO + 2 H2 + heat
CH4 + ½ O2 àààà CO + 2 H2 + heat
CH4 + H2O + heat àààà CO + 3 H2
Conversion of CO converted to CO and H through the Water-gas shift reaction
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références46 46HELION
Conversion of CO
CO converted to CO2 and H2. through the Water-gas shift reaction
CO + H2O àààà CO2 + H2 + heat
Characteristics 700 – 850°C, pressures 3 – 25 bars. Outlet T: 950 – 1100 °C
Combination of SMR and POX
Outlet T: 950 – 1100 °C
Gas pressure up to 100 bars
Benefits High efficiency Smaller size (No need for any external heating of the reactor)
Challenges
Costs for large units
Complex system
Sensitive to natural gas qualities
Cost for small units
Simple system
Lower efficiency
H2 purification
Emissions/flaring
� Fixed or fluidized bed. At industrial development stage
w Fluidized bed: more flexibility, better performances
w Other tech like “circulating bed”
w Texaco: fluidized bed
� Limited capacity of production because of price and availability (500,000 t/year = 50,000 hect)
� Erratic fuels: inconsistent quality, poor quality
� Maybe the oldest method of producing H2
� Source of city gas
� Variety of gasification processes
� Main processes: Texaco (70 atm, 1200°C, entrained bed)
& Kopper Totzek
Gasification of coal Gasification of biomass
Production technologies from coal: commercially mature, but more complex than the production of
H2 from natural gas
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références47 47HELION
� Erratic fuels: inconsistent quality, poor quality control
� Large scale systems: cheaper and lower quality fuels
� Smaller plants: high level of quality better fuel homogeneity
� Biomass gasification is an R&D area shared between H2 production and biofuels production. Gasification & pyrolysis are considered the most promising medium term technos for the commercialization of H2 prod from biomasse
& Kopper Totzek
w Fixed bed
w Fluidized bed
w Entrained flow
� Favorites: high T entrained flow processes
� Typical reaction (endothermic)
� C(s) + H20 + heat àààà CO + H2
� Then water gas shift reaction
� CO + H2O àààà CO2 + H2 + heat
� Higher cost
Production technologies from natural gasTechnique Steam Methane Reforming (SMR) Partial Oxidation (POX) Autothermal Reforming (ATR)
Heat
endothermic
Heat often supplied from the combustion of some of the CH4
feed-gas
exothermic exothermic
Inputs Water
O2
Water for water gas shift reaction
Water + O2
Water for water gas shift reaction
ReactionCH4 + H2O + heat àààà CO + 3 H2
Product gas: 12% of COCH4 + ½ O2 àààà CO + 2 H2 + heat
CH4 + ½ O2 àààà CO + 2 H2 + heat
CH4 + H2O + heat àààà CO + 3 H2
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références48 48HELION
Conversion of CO
CO converted to CO2 and H2. through the Water-gas shift reaction
CO + H2O àààà CO2 + H2 + heat
Characteristics
700 – 1000°C, pressures 3 – 25 bars.
Outlet T: 950 – 1100 °C
Combination of SMR and POX
Outlet T: 950 – 1100 °C
Gas pressure up to 100 bars
BenefitsHigh efficiency
Good costs for large units
Smaller size (No need for any external heating of the reactor)
Good costs for small units
ChallengesComplex system
Sensitive to natural gas qualities
Simple system
Lower efficiency
H2 purification
Emissions/flaring
Hydrogen and intermittent renewable sources2 projects, illustrating 2 different problematic
2 kWh
100 kWh
40 MWh
»Remote site
Remote energy – site electrification Renewable sources integration on electric grids
»Peak shaving
PEPITEdemo
MYRTEdemo
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références49 49HELION
1 – 10 kW 10 – 100 kW 500 kW
2 demonstration systems forecasted
Development of a techno-economic sizing tool for hydrogen hybrid systems
+
qPépite project (south of France) is under ANR sponsorship
qMyrte project (Corsica) is associated to an industrial program, encompassing a 3 MW PV power plant
Hydrogen cost depending on the energy source
15
20
25
30
/GJ produce
d hyd
rogen
H2 electrolytic
H2 ex natural gas0.03 €/KWh
0.05 €/KWh
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références50 50HELION
5
10
15
0 5 10 15 20
€/GJ source
€/GJ produce
d hyd
rogen
H2 ex biomass
H2 ex coal
Future energy production
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références51 51HELION
Annex
� Biogas gasification
wExamples for hydrogen production
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références52 52HELION
Gasification plant Texaco
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références53 53HELION
Gasification plant Marik
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références54 54HELION
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EM Group Gasifier
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références57 57HELION
> FyFC Overview of Hydrogen Production – 1-4 Oct 07, Svendborg, DK - Références58 58HELION
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