Solar Hydrogen Stellenbosch University, September 2 , 2010 · Solar Gasification and Reforming of...
Transcript of Solar Hydrogen Stellenbosch University, September 2 , 2010 · Solar Gasification and Reforming of...
Stellenbosch University > 2 Sept. 2010
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Solar Hydrogen
Stellenbosch University, September 2nd, 2010
Dr. Christian Sattler
DLR – German Aerospace Center - Solar Research
e-mail: [email protected]
Stellenbosch University > 2 Sept. 2010
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Overview
Introduction of DLREnergy
Solar HydrogenFrom Fossil RecoursesThermochemicalCycles
HYDROSOL, HYDROSOL 2, HYDRSOOL 3-DSummary and Outlook
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DLRGerman Aerospace Center
Research InstitutionSpace AgencyProject Management Agency
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Research Areas
AeronauticsSpaceTransportEnergySpace AgencyProject Management Agency
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Locations and employees
6500 employees across 29 research institutes and facilities at
13 sites.
Offices in Brussels, Paris, Washington, and Almería(plus permanent Delegation on the Plataforma Solar de Almería)
Koeln
Oberpfaffenhofen
Braunschweig
Goettingen
Berlin
Bonn
Neustrelitz
Weilheim
Bremen Trauen
Dortmund
Lampoldshausen
Hamburg
Stuttgart
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Energy
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DLR Energy Research Area
DLR Energy Research concentrates on:
CO2 avoidance through efficiency and renewable energiessynergies within the DLRmajor research specific themes that are relevant to the energy economySecond largest research centre in Germany for non-nuclear energyApprox. 400 employees
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Energy Research Program Themes
Efficient and environmentally compatible fossil-fuel power stations(turbo machines, combustion chambers, heat exchangers)Solar thermal power plant technology, solar materials conversionThermal and chemical energy storageHigh and low temperature fuel cellsSystems analysis and technology assessment
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Portfolio of Competences – Energy
Simulation/modelling
Fuel cells Power plant technology
Concentratingsolar systems
Combustion
Turbo-machines
Hybrid power plants
Heat storage
Gas turbines with alternativefuels
Fuel cells with alternative fuels
Solar power plants
Solar hydrogen production
Heat exchangers
Heat management
Solar process heat
Manufacturing techniques
Gas turbine systems
Materials
Efficientenergyconversion
Renewableenergies
Solar gas turbines
Syst
ems
anal
ysis
and
tech
nolo
gy a
sses
smen
t
Solar gas turbines
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Solar Hydrogen
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Vision
Producing hydrogen for mass markets means implementing as efficient processes as possible to convert available energy sources like renewables or nuclear into the chemical energy vector.(De Beni G. 1970; Marchetti 1973; Winter 2000)
Hydrogen should be produced from water to reduce dependencies on fossil fuelsTo reduces environmental impact
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Technical and Economic Efficiency
Technical: In which process is the most energy stored in the hydrogenIs the process technical feasible?Are there any knock-out criteria?
Economic: Is the product (hydrogen) cost competitive?Are there any other economic reasons that make the process not competitive?
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Hydrogen Production Today
Steam Methane ReformingThermal efficiency 78%1 kg H2 by means of SMR yields to 9.42 kg of CO2The production cost of hydrogen is estimated at 0.04 €/kWh (1.33 €/kg)
Coal GasificationThe Lurgi Process (Fixed-Bed) 500 – 1000 °CThe Winkler Process (Fluidized-Bed) 800 - 1100 °C The Koppers-Totzek/Texaco Process (Entrained-Bed) 1040 – 1540 °C
Thermal efficiency 58 - 63%23 kg CO2 / kg H2
Hydrogen costs from coal gasification are 1.21 to 1.79 €/kg H2(coal price not reported)
Partial Oxidation1300 - 1500 °C 1.45 – 1.67 €/kg
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Solar Thermal Processes for Hydrogen Production
Today:Industrial-scaleCheapNot renewable
Future:RenewableExpensive
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Production-, Storage- and Infrastructure topics of the European Hydrogen and Fuel Cell JTI
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Solar Hydrogen from Hybrid Fossil Processes
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Carbon Based Transition ProcessesStarting from applied technologiesReduced risk compared to water splitting technologiesSolar Reforming of Natural Gas
Development by a number of groups since at least 25 yearsCost are estimated to 1.4 €/kg H2
Solar Gasification and Reforming of PetcokeDevelopment by ETH Zurich, CIEMAT, and PDVSA Cost are estimated to about 2.1 €/kg H2
SOLZINC – Carbothermal reduction of ZnOPilot reactor successfully testedZinc is produced not hydrogen!
Solar Cracking of MethaneNo CO2 emission but C, C might be a product toochallenging reactor design: solids and high temperatures
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Solar Steam Methane Reforming – Technologies
Reformer heated externally (700 to 850°C)Optional heat storage ( up to 24/7) E.g. DLR Project ASTERIX
Irradiated reformer tubes (up to 850°C), temperature gradient Approx. 70 % Reformer-Development: CSIRO, Australia and in Japan; Research in Germany and IsraelAustralian solar gas plant in preparation
Catalytic active direct irradiated absorberApprox. 90 % Reformer-High solar flux, works only by direct solar radiationDLR coordinated projects: SCR, Solasys, Solref; Research in Israel, Japan
decoupled/allothermal indirect (tube reactor) Integrated, direct, volumetric
Quelle: DLR
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Direct heated volumetric receiver:SOLASYS, SOLREF (EU FP4, FP6)
Pressurised solar receiver,Developed by DLRTested at the Weizmann
Institute of Science, IsraelPower coupled into the process gas: 220 kWth and 400 kWth
Reforming temperature: between 765°C and 1000°CPressure: SOLASYS 9 bar, SOLREF 15 barMethane Conversion:
max. 78 % (= theor. balance)DLR (D), WIS (IL), ETH (CH), Johnson Matthey (UK), APTL (GR), HYGEAR (NL), SHAP (I)
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Assessment of relevant H2 pathways until 2020including NG Solar-SMR for comparison issues
highhighnegative -neutral
modest -high
neutral -m
odest
Positive impact on GHG emission reduction
highhighhigh
modest -high
modest
Positive impact on security of energy supply
25-33 €/GJ50-67 €/GJ31 €/GJ12*
€/GJ8*
€/GJH2 production cost
BiomassWindelectrolysis
Grid Electricityelectrolysis
NGSolar-SMR
NGSMR
*assuming a NG price of 4€/GJ; NG Solar-SMR: expected costs for large scale, solar-only
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Project Perspectives
The consortium forces the realisation of the a prototype reforming plantLink with Australian CSIRO by an ongoing IPHE project Funding was assured in October 2009Development phase of the joint projectSOLREF receiver will run on a second tower at the CSIRO Solar Centre in Newcastle, NSW
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Thermochemical Cycles
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Thermochemical Water Splitting2500 °C
100 °C0 °C
- 273 °C
H H
O
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PROBLEMS!
Hydrogen + Oxygen = explosive gas!DangerousSeparation?
2500 °C MaterialsSpecial ceramics – difficult to handle, expensive
2500 °C TemperatureHow could such high temperatures be achieved?Efficiency?
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Sollution
H2O
H2 + O2
2500 °C
H2O
O2
1250 °C
H2
850 °CAre the problems solved now?
•Still high temperatures
•Materials
•Chemical reactions
•Efficiency
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Thermochemical Cycle
Firstly developed in the oil crises of the 1970sUse of nuclear energy to produce an energy carrierMainly in the USA (General Atamics, Westinghouse), but also in Europe (FZJ, JRC Ispra) and Japan (JAEA)Up to 900 different cycles are knownMain groups:
Sulphur cyclesVolatile metal oxide cyclesNon-volatile metal oxie cyclesLow temperature cycles
In the 1980s and 1990s the interst went down because of lower oil pricesCome back in the 2000s
Solar thermal more in the focusStudies to identify the most promising cycles (e.g. USA, France)
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Thermochemical vs. Electrochemical?
ThermochemicalNo conversion steps necessary = possibly very high efficiency
ElectrochemicalConversion steps necessary for power production = lowerefficiency
No contradiction: use energy forms as efficient as possible
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Promising and well researched Cycles
395304Hybrid Copper Chlorine
Low-Temperature Cycles
431100 – 18002Ferrites
6820002Cerium Oxide
4222002Iron Oxide
Non-volatile Metal Oxide Cycles
421600Hybrid Cadmium
4518002Zinc/Zinc Oxide
Volatile Metal Oxide Cycles
38900 (1150 without catalyst)
3Sulphur Iodine (General Atomics, ISPRA Mark 16)
43900 (1150 without catalyst)
2Hybrid Sulphur (Westinghouse, ISPRA Mark 11)
Sulphur Cycles
LHV Efficiency (%)
Maximum Temperature (°C)
Steps
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Temperature nuclear
71+%750+(Very) High TemperatureReactor
68%650Advanced Gas CooledReactor
64%550Breeder Reactor, Sodiumcooled
50%320Pressurised Water Reactor
48%300CANDU Reactor (Heavy Water Reactor)
47%285RBMK (Graphite moderated)
47%285Boiling Water Reactor
Carnot-EfficiencyTemperature(°C)Reactor Type
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Temperature – Concentrating Solar Power3500 °C
1500 °C
400 °C
150 °C50 °C
Paraboloid: Dish
Solar tower(Central Receiver System)
Parabolic trough
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Annual Efficiency of Solar Power TowersPower Tower 100MWth
Optical and thermal efficiency / Receiver-Temperature
0
5
10
15
20
25
30
35
40
45
50
600 700 800 900 1000 1100 1200 1300 1400
Receiver-Temperature [°C]
Opt
ical
effi
cien
cy a
nd th
erm
al a
nnua
l use
ef
ficie
ncy
[%]
R.Buck, A. Pfahl, DLR, 2007
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Solar Towers, “Central Receiver Systems”
Solar-TwoPSAPS10+20
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Efficiency comparison solar H2 production fromwater, SANDIA 2008
25%62%77%52%RotatingDisc < 1
Future Solar dish
1800Nickel ManganeseFerrit Process
23%83%57%49%MoltenSalt700
Future Solar tower
600Hybrid CopperChlorine-process
22%76%57%51%Particle700
Future Solar tower
850Hybrid Sulphur-process
20%76,2%57%45%Particle700
Future Solar tower
850High temperaturesteam electrolysis
14%83%57%30%MoltenSalt 700
ActualSolar tower
NAElctrolysis (+solar-thermal power)
ηAnnual
EfficiencySolar – H2
ηReceiver
η OpticalηT/C
(HHV)
Solar-receiver+ power [MWth]
Solar plantT[°C]
Process
G.J. Kolb, R.B. Diver SAND 2008-1900
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Water based processesLong term necessary for the de-carbonised H2 societyBenchmark: Renewable electricity + electrolysisChallenging technologiesMetal/Metal oxide thermo-chemical Cycles
Zn/ZnO (3,58 – 4,12 €/kg)Mixed Iron Oxides (Ferrites)Already shown in the HYDROSOL project Cost based on the small scale experiments are 7 €/kgCalculated improvements will lead to 3,5 €/kg
Sulphur Cycle Family Developed for use with nuclear heatHybrid Sulfur (ISPRA Mark 11) Cost calculation 0,8 €/kg H2 nuclearSulphur-Iodine Process (ISPRA Mark 16) Cost calculation 1,17 – 1,66 €/kg nuclear, 4,53 €/kg solar
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HYDROSOL, HYDROSOL 2, HYDROSOL 3D
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Thermochemical Cycle using Mixed Iron Oxides Process Operation
1200°C
800 – 1200 °C
2. Step: Regeneration
1. Step: Water Splitting
O2
H2O O2H2H2O + MOred MOox + H2
MOox MOred + ½ O2
Net reaction: H2O H2 + ½ O2
MOred
MOredMOox
MOox
Redox materials used in theHYDROSOL-2 project:ZnFeO, NiZnFeO
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1200° C
1200° C
Reactor for continuous hydrogen production:
Reactor with two modules 15 kW two-chamber system Two different alternating processes:
• Production: 800°C, water steam, nitrogen, exothermic
• Regeneration: 1200°C, nitrogen, endothermic
Transient steps like• Switching between half cycle• Start-up / Shutdown
Closed system: quartz window Four-way-valve
800° C
800° C
H2+N2
O2+N2
O2+N2
H2+N2
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HYDROSOL II Pilot Reactor in Operation
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Experiments – Process Control Software:
Regeneration
Production
Set parameterSolar Power
Process-Flow-Sheet
N2
N2H2O
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Experiments – Process Control Software:
Flux Measurement at test operation FluxMaxboth Modules= 115kW/m2
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Results: Thermal cycling
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Hydrogen production of 4th day of experimental series
0
1
2
3
4
5
6
7
8
9
10:1
4:25
:00
10:2
3:35
:20
10:3
2:44
:07
10:4
1:52
:96
10:5
1:02
:50
11:0
0:11
:62
11:0
9:20
:68
11:1
8:29
:71
11:2
7:39
:00
11:3
6:48
:32
11:4
6:05
:43
11:5
6:01
:18
12:0
5:54
:21
12:1
5:39
:75
12:2
5:34
:45
12:3
5:25
:87
12:4
5:16
:01
12:5
5:09
:93
13:0
5:27
:85
13:1
5:38
:89
13:2
5:49
:78
13:3
6:25
:34
13:4
6:39
:26
13:5
7:08
:35
14:0
7:44
:28
14:1
7:45
:50
14:2
8:13
:50
14:3
8:43
:34
14:4
8:38
:73
14:5
9:09
:28
15:0
9:48
:46
15:2
0:15
:14
15:3
0:54
:76
15:4
1:34
:09
15:5
2:11
:10
16:0
2:50
:15
16:1
3:29
:14
16:2
3:59
:71
16:3
4:38
:90
16:4
5:13
:87
16:5
4:56
:40
c(H
2) [%
]
Stellenbosch University > 2 Sept. 2010
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Summary and Outlook
• Technologies like solar steam reforming should be short term technologies to introduce solar technology into the chemical industry
• Thermochemical cycles will provide renewable hydrogen with very high efficiency compared to other renewable technologies
• The HYDROSOL reactor concept was scaled up in HYDROSOL 2 from the solar furnace to a 100 kW pilot plant on the tower of the PSA
• Topic of the ongoing HYDROSOL 3-D project is the design of a MW test plant
• Also sulfur cycles should be scaled-up since the development is already on a very advanced level and the temperature level is lower than of other TCCs
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Acknowledgement
The Projects HYDROSOL, HYDROSOL II; HYTHEC, HYCYCLES, Hi2H2, INNOHYP-CA, SOLHYCARB und SOLREF are co-funded bythe European CommissionHYDROSOL 3-D is co-funded by the European Joint Technology Initative on Hydrogen and Fuel Cells
HYDROSOL was awardedEco Tech Award Expo 2005, TokyoIPHE Technical Achievement Award2006 Descartes Research Price 2006
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Thank you very much for your attention!