Overview on the work carried out at the German Aerospace Center

Transcription

1 Chart 1 Solar Fuels Overview on the work carried out at the German Aerospace Center Dr. Christian Sattler christian.sattler@dlr.de

2 Chart 2 Contents - Short Introduction of the DLR - Energy Program - Institute of Solar Research - Department of Solar Chemical Engineering - Solar Fuels - Short-term CO 2 -Reduction: Solar Reforming - Long-term: Water splitting processes - Thermochemical Cycles - High Temperature Electrolysis - Conclusion

3 Chart 3 German Aerospace Center (DLR)

4 Chart 4 DLR German Aerospace Center Research Institution Space Agency Project Management Agency

5 Chart 5 Research Areas - Aeronautics - Space Research and Technology - Transport - Energy - Space Administration - Project Management Agency

6 Chart 6 Locations and employees 7000 employees across 32 institutes and facilities at 16 sites. Offices in Brussels, Paris, Washington, Singapore, and Almería. Permanent delegation on the European Solar Test Centre Plataforma Solar de Almería, Spain Juelich Cologne Bonn Bremen Trauen Braunschweig Lampoldshausen Stade Hamburg Goettingen Neustrelitz Berlin Stuttgart Augsburg Oberpfaffenhofen Weilheim

7 Chart 7 > Standard presentation > Jan Total income 2010 Research, operations and management tasks (excluding trustee funding from the Space Administration / DLR Project Management Agency): 745 Mio. ( 74 bn) 44 All values in million 104 Space Research and Technology Aeronautics Transport Energy Space Administration / DLR Project Management Agency Other income / earnings 205

8 Chart 8 National and International Networking Customers and partners: Governments and ministries, agencies and organisations, industry and commerce, science and research World Europe Germany

9 Chart 9 Energy

10 Chart 10 DLR Energy DLR Energy Research concentrates on: -CO 2 avoidance by efficiency optimisation and renewable energies - synergies within the DLR - major research specific themes that are relevant to the energy economy

11 Chart 11 Energy Program Themes - Efficient and environmentally compatible fossil-fuel power stations (turbo machines, combustion chambers, heat exchangers) - Solar thermal power plant technology, solar fuels - Thermal and chemical energy storage - High and low temperature fuel cells - Systems analysis and technology assessment

12 Chart 12 Institute of Solar Research Department of Solar Chemical Engineering

13 Chart 13 DLR Institute of Solar Research Main Topic: Solar Thermal Power Plants 140 Persons 5 Departments, 4 Sites Köln-Porz, Jülich Stuttgart Jülich Plataforma Solar de Almería (Permanent Delegation) and Office in Almería, Spain Köln-Porz Stuttgart

14 Folie 14 Department of Solar Chemical Engineering Head Organisation Strategy Representation in boards Group High temperature CE Solar tower >500 C Group Low temperature CE Reactors up to Parabolic troughs < 500 C Solar Fuels Solar Materials Heat transfer fluids Solar fuels Water treatment SOWΛRLΛ GmbH 25 Persons + Students, 65% external funding

15 Q Temp erature (K) Pressure (N/sq m) Mass Flow Rate (kg/sec) Duty (Watt) DEA Folie 15 Competences Development of components and processes 850 mm and 530 mm 1000 mm RECDEA scientific, technologic and economic evaluation CO MIX2 DEA RECSPLT MIX CO2TOT 25 LOSS1 COOL1 CO 1 CO-O2 Q= Q= Q= O RECREG MIX4 REGOUT N2 N2TOT Q= CO-OUT CO CO2-OUT DEATOT FLASH ABSOR BER STRIPPER 205 Q= QC=0 189 QR=0 WATER 4 MIX3 QC= QR= SEP COOL3 LOSS2 O2, CO2 O2,CO Q= Q= Q= N2REC COOL4 D EAREC Q=

16 Folie 16 Solar Fuels H 2 > 20 years experience and international cooperation Processes Reforming of NG Thermo-chemical cycles Sulfur metal oxides Solar HT electrolysis Cracking of methane Photo-catalysis Products H 2, syn-gas, methanol, FT-Synfuels H 2 O -MO - OH 2 ox -MO red C -MO- O 2ox -MO red ½ O C (Roeb, Müller-Steinhagen, Science, Aug ) Contact DLR: Dr. Martin Roeb, (martin.roeb@dlr.de Tel.: +49(0) )

17 Folie 17 Solar Materials - High temperature recycling of waste materials (e.g. aluminium, sulfuric acid) - Development of solar heated reactors solar heated rotary kilns - Development and demonstration of production processes Contact DLR: Dr. Martin Roeb, martin.roeb@dlr.de Tel.: +49(0)

18 Folie 18 Heat Transfer Fluids for CSP - Accelerated Aging Degradation rates, and kinetics of gas, water, and other degradation products formation - Physico-chemical parameter at high temperatures Vapor pressure, density, heat capacity, heat conductivity, viscosity, gas soluability - Interaction with power plant components Hydrogen diffusion, influence of material contacts and impuritieson the aging of the heat transfer fluids - Field tests Authentic and representative samples of heat transfer fluids during power plant operation, inline- / atline- / offline-analysis Contact DLR: Dr. Christian Jung (christian.jung@dlr.de; Tel. +49 (0) )

19 Folie 19 Photocatalytic Synthesis of Solar Fuels - Qualification of new photo-catalysts for hydrogen production or the reduction of CO 2 Determination of spectral quantum yields by special lamp technologies, Determination of the solar efficiency in our solar test fascilities, Evaluation of long term stability, and product quality, optimisation of the produktivity - Chemical Engineering Development of solar receiver-reactors, design of concentrator technologies, scaleup, and economic evaluation Contact DLR: Dr. Christian Jung (christian.jung@dlr.de; Tel. +49 (0) )

20 Folie 20 Photochemical Water Treatment - Untersuchung photochemischer Verfahren (VUV bis solar) Actinometry of light sources, degradation tetst by photolytic and photo-catalytic processes; water analytics - Development of photo-reactors Solar receiver-reactor technology and photo-reactors for nnovative light sources - Development of photo-chemical plants Plants for water treatment with photo-chemical key steps up to demonstration scale, research on the combination of treatment technology, automation, recycling of photo-catalysts, energetic optimisation Contact DLR: Dr. Christian Jung (christian.jung@dlr.de; Tel. +49 (0) )

21 Chart 21 Solar Fuels

22 Slide 22 Solar Chemistry - Basics - Role models - photosynthesis - use of photons for photochemistry - burning glass use of heat for thermochemistry - Principle in chemical reactions: - photochemistry thermochemistry - However in some cases there are synergies in chemical processes, especially if not only one reaction takes place - Example: degradation of wastes

23 Slide 23 Solar Chemistry instead of Solar Power - Solar Thermochemistry is efficient because energy conversion steps are reduced! - Example: Hydrogen production: H 2 O H 2 + ½ O 2 - Solarchemical: 2 conversions - Solar radiation heat Chemical reaction - Via solar power: 4 conversions - Solar radiation heat mechanical energy electrical energy chemical reaction - Solar photo-chemistry uses the light directly without any conversion. Photo-chemistry is economical if the reaction needs a large amount of photons - Example: Production of Caprolactam an intermediate for Nylon Annual production > 200,000 t (by artificial light)

24 Slide 24 Solar Fuels Production pathways Solar Energy Heat Radiation Solar-thermal Fossil Resources Biomass PV CO 2 Heat Synthetic Fuels Mechanical Energy Power Thermochemistry Electrolysis Photochemistry Hydrogen

25 Chart 25 Temperature Levels of CSP Technologies 3500 C -Paraboloid: Dish 1500 C 390 C -Solar Tower (Central Receiver System) 150 C 50 C -Parabolic Trough / Linear Fresnel

26 Chart 26 Solar Towers, Central Receiver Systems -PS10, PSA CESA-1, Torresol, Spain -Solar-Two, Daggett, USA -Solarturm Jülich, Germany

27 Chart 27 Annual Efficiency of Solar Power Towers Power Tower 100MW th Optical and thermal efficiency / Receiver-Temperature Optical efficiency and thermal annual use efficiency [%] Receiver-Temperature [ C] R.Buck, A. Pfahl, DLR, 2007

28 Chart 28 Solar Tower Jülich Receiver 22.7m² (Intratec, Saint-Gobain) Tower 60m (Züblin) 2150 Heliostats á 8.2 m² (SHP/AUSRA) Vessel 9t/h, 30 bar/500 C (VKK-Standardkessel) Thermal storage 1h Turbine 1.5 MWe (KKK-Siemens)

29 Chart 29 Principle of the solar thermal fuel production Recourses -Natural Gas -Water, CO 2 Heat Chemical Reactor Fuel -H 2 -CO + H 2 Solar Tower -Industry -Transportation Energy Converter -Fuel Cell -Transportation -Power Production

30 Chart 30 Short-term CO 2 -Reduction: Solar Reforming

31 Chart 31 CO 2 Reduction by solar heating of state of the art processes like steam methane reforming and coal gasification CG 20 kg/kg 15 SMR -CO 2 Reduction 20 50% SPCR 10 SSMR 5 0 SMR SSMR CG SPCR

32 Chart 32 Steam and CO 2 -Reforming of Natural Gas Steam reforming: H 2 O + CH 4 3 H CO CO 2 Reforming: CO 2 + CH 4 2 H CO Reforming of mixtures of CO 2 /H 2 O is possible and common Use of CO 2 for methanol production: e.g. 2H 2 + CO CH 3 COH (Methanol) Both technologies can be driven by solar energy as shown in the projects: CAESAR, ASTERIX, SOLASYS, SOLREF

33 Chart 33 Solar Methane Reforming Technologies decoupled/allothermal -indirect (tube reactor) Integrated, direct, volumetric - Reformer heated externally (700 to 850 C) - Optional heat storage (up to 24/7) - E.g. ASTERIX project - Irradiated reformer tubes (up to 850 C), temperature gradient - Approx. 70 % Reformer-h - Development: CSIRO, Australia and in Japan; Research in Germany and Israel - Australian solar gas plant in preparation Source: DLR - Catalytic active direct irradiated absorber - Approx. 90 % Reformer-h - High solar flux, works only by direct solar radiation - DLR coordinated projects: Solasys, Solref; Research in Israel, Japan

34 Chart 34 Project Asterix: Allothermal Steam Reforming of Methan - DLR, Steinmüller, CIEMAT kw plant at the Plataforma Solar de Almería, Spain (1990) - Convective heated tube cracker as reformer - Tubular receiver for air heating

35 Chart 35 Pilot Scale Solar Chemical Reactors - SolarGas Experimental set-up of the 200 kw SolarGas reactor Top view of DCORE reactor (right) layout of entire integrated reformer and HRU Source: R. McNaughton et al., CSIRO, Australia

36 Chart 36 Direct heated volumetric receivers: SOLASYS, SOLREF (EU FP4, FP6) - Pressurised solar receiver, - Developed by DLR - Tested at the Weizmann Institute of Science, Israel - Power coupled into the process gas: 220 kw th and 400 kw th - Reforming temperature: between 765 C and 1000 C - Pressure: SOLASYS 9 bar, SOLREF 15 bar - Methane Conversion: max. 78 % (= theor. balance)

37 Chart 37 Potential Solar sites

38 Chart 38 Suitable locations for CSP in Northern Africa

39 Chart 39 Natural Gas Pipeline Grid and Natural Gas Fields

40 Chart 40 Suitable locations for solar reforming - Example Algeria and Tunisia -Pipelines -Fields kwh/m²/y - 50 km distance to pipelines - Acceptable DNI - Available Land

41 Chart 41 Long-term: Water splitting processes

42 Chart 42 Solar Pathways from Water or CO 2 to Hydrogen Carbon Monoxide

43 Chart 43 Solar Pathways from Water or CO 2 to Hydrogen Carbon Monoxide

44 Chart 44 Promising and well researched Thermochemical Cycles Steps Maximum Temperature ( C) LHV Efficiency (%) Sulphur Cycles Hybrid Sulphur (Westinghouse, ISPRA Mark 11) (1150 without catalyst) Sulphur Iodine (General Atomics, ISPRA Mark 16) (1150 without catalyst) Volatile Metal Oxide Cycles Zinc/Zinc Oxide Hybrid Cadmium Non-volatile Metal Oxide Cycles Iron Oxide Cerium Oxide Ferrites Low-Temperature Cycles Hybrid Copper Chlorine

45 Chart 45 Efficiency comparison for solar hydrogen production from water (SANDIA, 2008)* Process T [ C] Solar plant Solarreceiver + power [MWth] η T/C (HHV) η Optical η Receiver η Annual Efficiency Solar H 2 Elctrolysis (+solarthermal power) NA Actual Solar tower Molten Salt % 57% 83% 14% High temperature steam electrolysis 850 Future Solar tower Particle % 57% 76,2% 20% Hybrid Sulfurprocess 850 Future Solar tower Particle % 57% 76% 22% Hybrid Copper Chlorine-process 600 Future Solar tower Molten Salt % 57% 83% 23% Nickel Manganese Ferrit Process 1800 Future Solar dish Rotating Disc < 1 52% 77% 62% 25% *G.J. Kolb, R.B. Diver SAND

46 Chart 46 Fuel Production from H 2 O and CO 2 by Solar Radiation C H CO 2 H 2 O H O H H O H MO reduced O MO oxidized H H H O H 2 CO O MO reduced MO oxidized O 1200 C DLR: Roeb, Müller-Steinhagen, Science, Aug. 2010

47 Chart 47 Hydrosol technology scale-up 2008: Pilot reactor (100 kw) PSA solar tower 2005: Continuous Η 2 production 2004: First solar thermochemical Η 2 production DLR solar furnace

48 Chart 48 Pilot-plant in operation since March 2008

49 Chart 49 Modelling of the pilot plant - Overview Modelling: Parameter Insulated Power (#1) Heliostatfield- Simulation Tool STRAL (C++) Modelling-Control Software (Labview ) Parameter Temperature (#2) Temperature Model (Matlab/Simulink ) Parameter Hydrogen Amount (#3) Hydrogen Production Model

50 Chart 50 Modelling Temperature model: Collecting formulas of the heat flows (simplified balance!) Q GaBa Q KGa Q GB Q ak Q KF Q Q KK ak Q af Q KF Q HS Q af Heat flows: heat radiation, heat conduction and convection

51 Chart 51 Modelling Temperature model: First Verification of open loop control system Regeneration Temperatures East ( ) Input: Simulated power East Sampling rate (Sim.): every second T [ C] Sampling rate (Exp.): Every second Average Deviation: 6.5% 200 Temperature Simulated Temperature Measured 0 10:15:00 10:30:00 10:45:00 11:00:00 11:15:00 11:30:00 11:45:00 12:00:00 12:15:00 12:30:00 12:45:00 13:00:00 13:15:00 13:30:00 13:45:00 14:00:00 14:15:00 14:30:00 14:45:00 15:00:00 Time Production

52 Chart 52 Pilot Plant arranged on the research platform of the ST Jülich (artist view)

53 Chart 53 Solar Pathways from Water or CO 2 to Hydrogen Carbon Monoxide

54 Chart 54 The thermochemical cycles covered in HycycleS Sulphur-Iodine Hybrid Process Cycle Heat Wärme Heat Oxygen 800 C 1200 C Water H 2 O O 2 Hydrogen C O 2 H 2 SO 4 H 2 SO 4 SO 3 H 2 O + SO 3 SO 2 + ½O 2 H 2 H 2 Electrolysis (90 C) H 2 SO 4 + H 2 SO H 2 O SO 2 H 2 O + H 2 O

55 Chart 55 H 2 SO 4 decomposition in 2 steps 1. Evaporation of liquid sulfuric acid (400 C) -Absorbers : -SiSiC foam -2. Dissociation of sulfur trioxide (850 C) -SiSiC honeycomb

56 Chart 56 Stability of construction materials High temperature tests (850 o C) Ebending (GPa) CEA Exposure time (hrs) SiO 2 layer Core material Performance of long-term corrosion campaigns (SO 2, SO 3 rich, boiling H 2 SO 4 ) and post-exposure mechanical testing and inspection mainstream materials SiC-based as well as brazed samples SiC based materials retained suitable for the intended application since they are not affected significantly by the SO2-rich, SO3-rich and boiling sulphuric acid exposures.

57 Chart 57 Advanced catalysts and coatings for H 2 SO 4 decomposition In-house synthesized materials (metal oxide based) with high catalytic activity in terms of SO 2 production from H 2 SO 4 : Coating of active materials in small- & large-scale SiSiC monoliths or fragments Satisfying stability of samples coated with in-house materials under long-term operation exp. 1 bar Derivation of an empirical kinetic model exp. 2 bar exp. 3 bar exp. 4 bar kin model 1-4 bar Evaluation of the employed materials chemical stability Extraction of an SO 3 dissociation mechanism CrFe oxide identified as the most suitable catalyst SO3 conversion (%) WHSV (h-1) Karagianakis et al, IJHE 2011/2012; Giaconia et al, IJHE 2011

58 Chart 58 SO3 conversion (%) Example of Catalyst qualification: CuAl 2 O C, WHSV= 290 h 1 SO3 conversion (%) equilibrium 40 h 1 63 h h h time on stream (hours) temperature ( C) Durability tests performed at high space velocity values After initial deactivation, catalyst shows < 5% loss of activity (100hrs on stream) Change of colour observed, due to phase separation phenomena CuAl 2 O 4 coated SiSiC fragments (kinetic model for decomposer design) Exp. campaign Ea (kj/mol) A (h 1 ) dn (mm)* No * ln(1 X ) k A e k WHSV Ea RT

59 Chart 59 Design of multi-chamber solar reactor foam SO 3 + H 2 O Solar radiation (focus 1) Solar radiation (focus 2) honeycomb H 2 SO 4 SO 2 + O 2 + H 2 O Front view of evaporator (left) and decomposer Rear view

60 Chart 60 Solar reactor for sulfuric acid decomposition H 2 SO 4 SO 3 + H 2 O 400 C 850 C 750 C 650 C SO 3 SO 2 + ½ O 2

61 Operation in our solar furnace in Cologne

62 Chart 62 Overview of test series in solar furnace Catalyst Fe 2 Cr 2 O 4 Evaporator solar Number of experiments 19 Sulfuric acid concentration w% 94 Sulfuric acid flow rate ml/min 1 8 Mean honeycomb temperature C Residence time s Weight hourly space velocity 1/h

63 Chart 63 Thermodynamic equilibrium of H 2 SO 4 decomposition H 2 SO 4 dissociation completed at about 550 C 80% of SO 3 decomposed at 850 C 40% of SO 3 decomposed at 650 C Source: Noglik et al., 2009

64 Chart 64 Conversion of SO 3 in honeycomb

65 Chart 65 Solar reactor as H 2 SO 4 decomposer [%] reactor (Fe 2 O 3 catalyst) net (Fe 2 O 3 catalyst) V acid [ml/min] - Development and operation of a scalable prototype - FEM analysis - trouble-free operational > 200 h - conversions > 80 % - reactor efficiency > 25 % - Continuum model of foam vaporiser - Computer tomography - Modelling of SO 3 decomposition - Validation with experimental data - Control procedure for scale-up solar tower system Thomey et al, IJHE 2012 Noglik et al, IJER 2010 Haussener et al, ASME-JHT 2009

66 Chart 66 Scale-up of the solar HyS process

67 Chart 67 Implementation into a Solar Tower

68 Chart 68 Techno-economics Electrolyser replacement 26% Equipment Equipment Electrolyser replacement 50% Contingencies General facilities Storage Periphery (Land & Piping) Interests Contingencies Start-up expenses 4% 2% Interests Start-up expenses General facilities Periphery 2% 5% Storage 2% 9% Lebros et et al, IJHE 2010 Electrolyser replacement Electricity cost Discount rate Electrolyser investment Plant life Decomposer investment By-product revenues Production cost of hydrogen [ /kg] Flowsheet for solar HyS process refined and completed All Components including the solar field were sized for a nuclear HyS and SI process and a solar HyS process Investment, O&M cost, production cost were analysed 6-7 /kg(h 2 ) for HyS optimistic scenarios lead to 3.5 /kg(h 2 ) 50 MW solar tower plant for hydrogen production by HyS cycle defined and depicted Thorough safety analysis was carried out for respective nuclear and solar power plants

69 Chart 69 Solar Pathways from Water or CO 2 to Hydrogen Carbon Monoxide

70 Chart 70 High temperature electrolysis process Temperature in the range of 600 C to 900 C are required to drive the electrolyser. Electricity and heat are supplied to the electrolyser to drive the electro-chemicals reactions. The waste heat from the H 2 and O 2 gas streams existing the cell is used to evaporate water. The H 2 O stream is further heated by the second Heat exchanger to raise the temperature of the electrolyser. H 2O 2e H 2 O 2 1 O O2 2e 2 1 H 2 O H 2 O 2 2 2

71 Chart 71 Economic analysis Key parameters of the hydrogen production cost with the a concentrating solar installation coupled to a high temperature electrolyser: Efficiency of the plant Efficiency of the solar installation Electricity consumption of the electrolyser Site of the plant (annual solar irradiation, availability of water, connection to the electricity and gas grit Investment Lifetime of the plant

72 Chart 72 Thermal conductivity of working fluids

73 Chart 73 Flow diagram of the coupling of the solar power tower with the electrolyser

74 Chart 74 Flow diagram of the coupling of the parabolic dish to the electrolyser

75 Chart 75 Flow Diagram of the coupling of the parabolic trough to the electrolyser Parabolic Trough Collectors Pre-heating Evaporation Super-heating Feed Water Sensible heat storage for pre-heating Latent heat storage for evaporation Power Block Sensible heat storage for super-heating Electrolyser Block

76 Chart 76 Conclusion and Outlook

77 Chart 77 Future Solar Thermal Plants more than power! Production of solar fuels (renewable H 2 and CH 4 / CH 3 OH), Recycling of CO 2, Power Production and Desalination (H 2 O) H 2 H 2 O Power CO 2 CH 4, CH 3 OH Heat Sea water Desalinated Water

78 Chart 78 Acknowledgement - Thanks to all our funding agencies especially the European Commission and our industrial partners. - Thanks to all colleagues and partners who provided various contributions to this work. DLR H 2 Aircraft ANTARES

79 Chart 79 Thank you very much for your attention!