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Naturgass til fremstilling av hydrogen - Naturgass-kjeden fra reservoar til bruker -

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. Outline

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Naturgass til fremstilling av hydrogen - Naturgass-kjeden fra reservoar til bruker -

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  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 CCS carbon capture and storage CMG compressed methane gas CNG compressed natural gas CO carbon monoxide CO2 carbon dioxide DG-TREN Direction Generale Transport and Energy DME di-methylester EL electricity EU European Union FAME fatty acid methyl ester FC fuel cell FT Fischer Tropsch GHG greenhouse gas (emissions) GH2 gaseous hydrogen HFP Hydrogen and Fuel Cell Technology Platform H2 hydrogen HT-FC high temperature fuel cell ICE internal combustion engine LH2 liquid hydrogen NG natural gas RME rape seed methyl ester PE primary energy PEMFC proton exchange membrane fuel cell POX partial oxidation PSA pressure swing adsorption SMR steam methane reformer TES Transport Energy Strategy WGS water gas shift reactor

  4. Lesson “One”

  5. Seasonal energy load levelling N Daily energy load levelling E W S Canada • HVDC power transport • H2 – pipeline • LH2 tanker routes Early hydrogen vision Seasonal and daily distribution of renewable forms of energy and import to the industrial world (here: Germany) Source: Ludwig Bölkow, 1988 A global energy distribution system Source: GermanHy, 2008

  6. Supply gap! LBST, AWEO 2006 Hydrogen‘s short term role – today‘s challenge Source: LBST, Alternative World Energy Outlook, 2006

  7. Sankey diagram Scotland 2002 [TWh] Transport heavily depends on oil.What can replace dwindling oil in transport?

  8. Natural gas CO2 from air/ concentr. sources 2 Coal Min. oil Elec.-mix* fossil Also nuclear energy No primary energy carrier Synthesis/ electrolyis Reformer Gasificat. Refinery NG Methanol Gasol. also internal reforming Reformer Reformer Reformer Why hydrogen from natural gas? Primary energy Organic residuals (w(o wood) Sun, hydro-/wind power Replenish. raw mat. Wood renewable Fermen- Fermen- tation Conversion Elektrolys. Gasification tation Secondary energy I Hydrogen Ethanol Biogas Reformer Reformer Secondary energy II Hydrogen/ CO (HT-FC) *Also contains all forms of primary energy, such as nuclear energy Fuel cell End-energy Large variety of sources and pathways! Heat Refrig. Electr. Usable energy Cooling/ Processes Power/ light Heating/ Processes

  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 publicallyand widely proven to be safe and economic

  10. EU Hydrogen Energy Roadmap HyWays* (2004 - 2008) Transition and long-term pathways Prospect 2030 with forward looking assumptions * HyWays – The European Hydrogen Energy Roadmap Project (2004-2008) • EU-wide analysis to understand regionally different approaches & options for H2 in transport • Back- and forecasting with wide stakeholder involvement (industry, institutes, politics) • Application of toolbox for technical, economic, emissions and policyimpact 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 NG reforming Synthesis gas clean-up Hydrogen purification Synthesis gas (H2, CO, CO2, CH4) H2 + CO (e.g. <10ppm) Raw NG NG Pure H2 • Catalytic processes • Adsorption • Diaphragm processes • Purification by • metal-hydrides • Proton-/ion conductors • Iron-redox filter • (Iron sponge process) • Dust separation • De-sulphurisation • Steam reforming • Partial oxidation • Autothermal reforming • Plasma reforming • CO conversion • (CO-shift) Large NG reformer Haldor Topsoe Cleaning by staged adsorption Reformer reactor Off-gas tank Burner

  14. Steam Reforming of Natural Gas (SMR) • Steam reforming reaction for NG: • Endothermic (catalytic) process with heating (700 - 800°C) • Partial Oxidation of NG (POX) • Partial oxidation reaction for NG: • 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 NG to hydrogen process technology

  15. NG to hydrogen process technology Comparison of reforming processes for NG ATR Combined SMR/POX SMR POX 700 - 800°C 1,300°C 850 - 1,000°C Operating temperature 65 - 70% (small) 81% (large) 69% (large) 65% (PE = 100%) 37% (PE  EL = 33%) Efficiency Low (endothermic) High (exothermic) High (exothermic) Dynamics

  16. NG to hydrogen process technology Major processes for hydrogen production from NG – gas clean-up Feed gas clean-up NG reforming Synthesis gas clean-up Hydrogen purification Synthesis gas (H2, CO, CO2, CH4) H2 + CO (e.g. <10ppm) Raw NG NG Pure H2 • Catalytic processes • Adsorption • Diaphragm processes • Purification by • metal-hydrides • Proton-/ion conductors • Iron-redox filter • (Iron sponge process) • Dust separation • De-sulphurisation • Steam reforming • Partial oxidation • Autothermal reforming • Plasma reforming • CO conversion • (CO-shift)

  17. NG to hydrogen process technology Synthesis gas clean-up: CO – conversion • Conversion reaction to oxidise CO (CO-Shift): • 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 NG reforming Synthesis gas clean-up Hydrogen purification Synthesis gas (H2, CO, CO2, CH4) H2 + CO (e.g. <10ppm) Raw NG NG Pure H2 • Catalytic processes • Adsorption • Diaphragm processes • Purification by • metal-hydrides • Proton-/ion conductors • Iron-redox filter • (Iron sponge process) • Dust separation • De-sulphurisation • Steam reforming • Partial oxidation • Autothermal reforming • Plasma reforming • CO conversion • (CO-shift)

  19. NG to hydrogen process technology Hydrogen purification: adsorption Scheme of 4-stage PSA process Product hydrogen Control Unit Instrument Adsorber air Vent stack Feed gas Flushing gas I - Adsorption II, V - Pressure balance III - Pressure relaxation IV - Flush VI - Pressure rise Phigh Plow

  20. NG to hydrogen process technology Comparison of hydrogen purification processes Catalytic processes Membrane technology PSA Low (e.g. 3 bar) High (20 bar) High (10 bar) Pressure High (catalyst) High (system complexity) High (Pd/Ag membrane) Costs High High (exothermic) Low Dynamics

  21. H O 2 De-ion Osmosis NG Synthesis gas De-sulph. Bypass Heat NG to burner SMR Air ~ 250°C PSA-offgas ~ 1.000°C Offgas ~ 350°C Heat Offgas buffer (start-up N ) 2 WGS H to storage 2 ~15 bar tank (~ 30 bar) PSA H buffer 2 H O 2 Flowsheet of Carbotech SMR at ARGEMUC (100 Nm3H2/hr) Source: Bünger, Haukedal, 2003

  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 Steam-drum Steam-reformer 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) 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 Sources: CONCAWE/EUCAR/JRC, WtW calculations by LBST http://ies.jrc.cec.eu.int/wtw.html

  30. Typical hydrogen energy chainHydrogen from NG (EU-mix)

  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! MTA: Manual Transmission Automatic DI-ICE: Direct injection ICE Source: GM-WtW Study, LBST, 2003

  32. Hydrogen production costs from SMRfor on-site and large plant [€/Nm³H2] Source: LBST

  33. Specific investment costs of SMRsas function of capacity [Nm³H2/hr] HyGear (500 Nm³/h): ~3,000 €/(Nm³/h) with CCS without CCS onsite SMR large electrolysis unit & HP electrolysis in-situ gasification with CCS central SMR with CCS Source: HyWays, 2006 Investment scales strongly with plant size!

  34. Hydrogen production costsInternational data compilation [€/kg] Source: NextHyLights, 2010

  35. 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 Two key documents“Strategic Research Agenda” and “Deployment Strategy”Endorsed at HFP General Assembly March 2005 Strategic combination of both reportsJune/October 2005 “Operations Review Days”December 2005 HFP General AssemblyImplementation Plan endorsedOctober 2006 High Level Group H2 and FC (2002-2003) HyWays EU-H2-RoadmapJoint TechnologyInitiative kicked off Evolution and selected milestones of EU‘s H2/FC-strategy 2006 2007 2002 2004 2005 2003

  36. Hydrogen production mix Germany GermanHy - German Hydrogen Energy Roadmap Shares of primary energy carriers in hydrogen production political imperative: share of renewable energies at least 50% 100 PJ ‘Moderate’ 480 PJ 100 PJ ‘Climate’ 470 PJ 90 PJ ‘Resources’ 440 PJ 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

  40. Key data of fuel cells for transport Source: Daimler, 2010 Massive technical learning! Remaining challenges: FC system costs and H2-infrastructure

  41. Japan – Hydrogen and Fuel Cells Strategy Source: Ishitani 2010

  42. Japan - H2- fueling stations in field test Source: Monde 2010

  43. New EU Lighthouse cluster Oslo 500 km major trunk roads 5 vanHool FC buses 2 70 MPa and 1 35 MPa fuelling stations in Oslo Økern, West Oslo, Lillestrøm 10 Daimler B-class F-CELL 2 Alfa Romeo MiTo FC 5 Th!nk (FCrange extender) 1st fuelling station at Grenland HyNor – (Extendable) Norwegian H2 Corridor Stavanger fuelling station 15 Mazda RX8 H2 Wankel 15 Quantum Toyota H2 hybrid

  44. % Possible hydrogen production mix Norway NorWays – Norwegian Hydrogen Energy Roadmap project • >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 CCSdo 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 www.h2stations.org Source: LBST

  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 Umwelt-problematik. 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.

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