hydrogen as a fuel made by electrolysis - zsw-bw.de · -19-advanced alkaline electrolysis...
TRANSCRIPT
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Energy Science & Technology IIINovember 12th 2015, Ulm
Andreas Brinner, Ludwig Jörissen
Zentrum für Sonnenenergie- und Wasserstoff-ForschungBaden-Württemberg (ZSW)
Hydrogen as a Fuel made by Electrolysis
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The Cycle of Energy and Materials
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Once there is abundant Electricity from Renewables we will need Energy Storage
Warum neue Energieträger ?
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What do we want / need?Unlimited Energy and Mobility with no harmfull impact to the environment.
We need coupled systems.
Solar
WindGSP / BCHP
CO2 Speicher
ElectricGrid GAS GRID
Electrolysis /H2 Storage
Methanization
H2
CO2
CH4
Electricity Generation
Electricity Storage
CO2
GASTANK
Electric Energy
Hydrogen Synthetih Methane
BEV FCEV CNG-V
Mobility
H2
CO2
Plug-In HEV Plug-In HEV
BEV: Battery Electric Vehicle
FCEV: Fuel Cell Electric Vehicle
CNG-V: Compressed Natural Gas Vehicle
Plug-In HEV: Plug-In Hybrid Electric Vehicle
GSP Gas and steam power plant
BCHP Block-type heating power station
Warum neue Energieträger ?
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Or just a Power Gap Filler?
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How to “Destroy” water
H2O ⇌ H2 + 1/2 O2∆G(l)25°C = -237,141 kJ/mol º 1,23 V∆H(l)25°C = -285,830 kJ/mol º 1,48 V
Alkaline Electrolysisconventional electrolysisadvanced electrolysis
Membrane electrolysisPolymer electrolyte
High temperature electrolysisSolid state electrolyte
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Electrolyzer Operation
Source: Stolten, FZJ
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Thermodynamics of Water SplitingH2O Heat of Evaporation
Source: Schnurnberger, DLR
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Thermodynamic efficiencies
In water electrolysis one needs to overcom ∆H
Higher heating value of hydrogen (water in liquid form)∆H0 = 285.6 kJmol-1 1.48 V∆G0 = 237.1 kWmol-1 1.23 VT∆S via heat or electricityWater spliting via electricity
Lower heating value of hydrogen (water in vapor form)∆H0 = 241.8 kJmol-1 1.25 V∆G0 = 228.6 kWmol-1 1.19 VT∆S via heat
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Water Electrolysis (Principles) -1
Verfahren zur Wasserstoffherstellung
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Water Electrolysis (Principles) -2
Quelle: T. Smolinka, M. Günther FhG-ISE, J.Garche, FCBAT
Quelle: ELT; www.elektrolyse.de Quelle: E-ON / SWB Quelle: R. Hino / JAERI - Japan (angepasst)
Verfahren zur Wasserstoffherstellung
Technology Temperature Cathode (HER) Charge carrier Anode (OER)
Half-cell reactions, Temperature Range and Charge Carriers of the dominant electrolysis processes
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Some Examples globallly
Quelle: M del Pilar, INTA, Spanien, B. Simonsen, IET, Norwegen, S. Schoenung, OA, USA
Projektbeispiele für globale Elektrolyseprojekte
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Some experimental / laboratory installations
Quelle: M del Pilar, INTA, Spanien, B. Simonsen, IET, Norwegen, S. Schoenung, OA, USA
Projektbeispiele für globale Elektrolyseprojekte
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Water Electrolysis is Known for quite some Timea few examples
ELT, 30bar, 2,4MW
Alkaline Electrolysis (AEL)
PEM-Elektrolysis(PEMEL)
Solid Oxide Electrolysis (SOEL)
Not yet commercially available
Power: 1 kW – 2,5 MWPressure: atmospheric – 100 bar
Power: 0,1 kW – 100 kWPressure: atmospheric – 100 bar
Hydrogenics, 10bar, 320kW
Hydrotechnik, 1bar, 0,6MW
ABB, 1bar, 100kW, bis 2000
Siemens, 50bar, 100kW, ab 2012
FUMATech, 10bar, 1,7kW
Idaho NL, 1bar, 17,5kW
Kommerzieller Stand der Elektrolysetechnik
But lots of promises
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Conventional Alkaline Electrolysis
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Separators for Water Electrolysis (I)
Source: Stolten, FZJ
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Separators for Water Electrolysis (II)
Source: Stolten, FZJ
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Electrode Materials
Source: Stolten, FZJ
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Reduction of Internal Resistance
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Advanced Alkaline Electrolysis
Minimization of electrode gap (zero gap)Electrodes are in direct contact with the separator
Electrode shapePerforated metal sheet as electrode with adapted diameter,
Cathode (Hydrogen evolution: 0,5 mm)Anode (Oxygen evolution: 1 mm)
Special shape of holes (conical shape)
Separator / DiaphragmWettability, thermal StabilityUsed to be asbestous, today oxide (Ni, Zr, …) powder in a microporous polymer
Catalytic electrodesCathode: Nickel (partially alloyed)Anode: Metal oxides (e.g. Ni Co2O4, LaNiO3, LaSrCoO3)
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Technologies
Pressurized Electrolysis
AdvantagesVery compact, low piping diameterRoom for further improvementDirect coupling to various industrial applications
DisadvantagesHigh investment costLarge control effortIncreased safety requirementsLower dynamic range (30-100% @ 10 bar)Increased maintenance effort
Atmospheric electrolyzers
AdvantagesSimple and robust systemsSimple controlLarge dynamic range (20% -100%)20%-30% lower capital investment compared to pressurized elecrolyzersReliable, long term experience
DisadvantagesLarger footprintMore effort for gas dryingAdditional cost for additinal compression stageLimited high load capabilioties
Source: Wenske, Enertrag
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Advanced Alkaline Electrolysis
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Alkaline Electrolysis Cell
Quelle: A. Brinner, DLR-TT, Stuttgart
Elektrolyse entscheidend für Erfolg !
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Advanced Pressurized Electrolyzer using vacuum-plasma-sprayed Electrodes (CLR-Konzept)
Quelle: Hysolar Final Report, Phase II 1992- 1995, Stuttgart
Comparison at 500 mA/cm2
1,7 kWN alkaline laboratory electrolyzer,atmospheric operation,
22 % energy saving as compared toblank metal electrodes
10 kWN alkaline pressurized electrolyzer,
5 bar operating pressure,18 % energy saving as compared to
im Vergleich zuBlank metal electrodes
Leistungsanpassungsprinzipien
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How to Connect Cells
Bipolar Design
CharacteristicCell Electrical series connectionVoltage is the sum of individual cell voltages
AdvantagesMinimization of voltage drop, better efficiencyCompactBetter adaptability to applications
DisadvantagesMore complicateddesignOne dect cellleads to a defect stack
Unipolar Design
CharacteristicCells connected in parallelLow voltage, high current
AdvantageRuggedLow investment costFaulty cells can be mothballed easily
DisatvanragesBukyLittle potential to improve energy efficiency
Source: Wenske, Enertrag
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Alkaline 0,5 MWN Pressurized Electrolyzer
N2-iner-tization
Elektrolysisstack
H2-Water-Separation
Waterseparator
Waterloop
Causticloop
Quelle: eigene Aufnahme
Elektrolyse entscheidend für Erfolg !
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Alkaline Electrolysis Plants with Long History
Source: Smolinka, ISE
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Large Units have been Realized in AEL
Source: Smolinka, ISE
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Electrolyte-cooler
Electrolysis-stack
Gas-Separation
Electrolyte-collection
Electrolyte-loop
Advanced Atmospheric, Alkaline Elektrolyzer having2400 kW Electric Power Input
Weiterentwicklung der Wasserstofferzeugung
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And AEL is (Re)-Entering the MW-Class
Source: Smolinka, ISE
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Membrane Eectrolysis
Polymer electrolyte membranePerflourinated sulfonic acide.g. Nafion
Cathode catalyst: PtAnode catalyst: Ir or Ru-OxideCurent collector: Titanium
[-CF-CF2-(CF2-CF2)n-]mO-CF2-CFO-CF2-CF2-SO3H
CF3
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Membrane electrolysis
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PEM Electrolyzers gradually Grow
Source: Smolinka, ISE
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Mainz Energy Park
Hydrogen production from wind-electricity
Pressurized PEM-electrolyzer upto 6 MW
Hydrogen use for vehicles and asfeed-in gas to the natural gas grid
- 33 -Source: Siemens
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Advantages Solid Oxide Electrolysis
Decreased amount of electrical energy requiredImproved reaction kineticsHeat from high temperature heat source or internal lossesAdiabatic operation possibleHeat utilizationReduced operating costTypical operating temperatures approximately 850°C.
Source: A. Friedrich, DLR
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Solid Oxide Electrolysis (Hot Elly)
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Modern SOEC
Source: A. Friedrich, DLR
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Comparison of Electrolysis Technologies
Source: Smolinka, ISE
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Water Electrolysis is a System Issue
Crucial ComponentsCaustic loop (KOH)Gas caustic separator, scrubberGas purification (oxygen removal, drying)Power electronicsHeat management
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Electrolyzer Efficiencies
Source: Smolinka, ISE
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Coupling of Energy ConvertersThe Hysolar-ProjectTechnology development, Investigation & Analysis of different ways to couple Photovoltaics and Electrolysis
Principle
Technical Realization
Quelle: A. Brinner, DLR-TT, Stuttgart
Elektrolyse entscheidend für Erfolg !
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350 kWN Photovoltaic-Field Solar Village bei Riyadh, Saudi Arabia
Quelle: eigene Aufnahme
Elektrolyse entscheidend für Erfolg !
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Dynamic Coupüling of Photovoltaics and Electrolysis
27.10.89
Optimum Operation
19.09.89
Minimum Operation
19.05.89
Dynamic Operation
Measurements were taken during the German-
Saudi-Arabian ProjectHYSOLAR
Quelle: A. Brinner, DLR-TT, Stuttgart
Leistungsanpassungsprinzipien
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Dynamic Wind Electrolysis Coupling
1997
Dynamic Electrolysis
Messungen im Rahmendes
Europäischen Joule II-Projektes
JOU2-CT93-0413
1996
Wind Turbine TestQuelle: W. Hug, H. Dienhart, DLR-TT, Stuttgart
Leistungsanpassungsprinzipien
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Coupling of Wind and Hydrogen Systems need Conditioning!
Übertragung der Ergebnisse auf Wind-Elektrolysesysteme
Electronisc Power Conditioning ELA
Electronic Voltage Conditioning ESA
Quelle: W. Hug, H. Dienhart, DLR-TT, Stuttgart
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Operation of Electrolyzers using Renewable Energies is efficient
Total electrolysis efficiency of 70%for an operating day using activated
electrodes
Total electrolysis fefficiency of 55%for an operating day using non
activated electrodes
10 kW Electrolyzer
350 kW Electrolyzer
Quelle: A. Brinner, DLR-FK, Stuttgart
Elektrolyse entscheidend für Erfolg !
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Thank You Very Much For Your Kind Attention