Hydrogen Potentials and Perspective. Dr. Manfred Klell HyCentA Research GmbH, Graz A3PS, Vienna, 18. November 2010

Transcription

1 Hydrogen Potentials and Perspective Dr. Manfred Klell HyCentA Research GmbH, Graz A3PS, Vienna, 18. November 010

2 Hydrogen Motivation Properties Production Storage Application Internal Combustion Engine Turbine Fuel Cell Slide

3 Hydrogen Economy Hydrogen provides a sustainable energy cycle with closed loop feedstock: Production from water through electrolysis with electricity from water power Storage as compressed gas, liquified or in compounds Combustion in fuel cells, turbines or internal combustion engines emitting water Motivation Source: Züttel 010 Slide 3

4 H(ydrogenium) Properties Hydrogen H is the most abundant element, more than 90 % of all atoms are hydrogen, main component and main energy source of stars, simplest atom, one proton and one electron only, very reactive, combines to the molecule H, in inorganic (H O, NH 3 ) and organic compounds (hydrocarbons, alcohols, acids, proteins). Hydrogen H is a colorless, odorless gas with no toxic effects, lowest density, high diffusion and heat transfer coefficients, low melting and boiling points, explosive atmosphere with air in a wide range of mixtures, high flame speed, high adiabatic combustion temperature. Slide 4

5 Production Annual production: 600 Mrd. Nm³, 6,5 EJ/year (1,5 % of primary energy consumptiuon) In chemistry (NH 3 ), refining & metallurgic processes Production 40 % by-product (Chlor-Alkali-Electrolysis) 50 % Reforming (η to 80 %) 10 % Electrolysis (η to 70 %) Gasification (η to 50 %) Chemical water splitting (lab scale) Biochemical methods (lab scale) - Anode e - e - Kathode - ½ O H - - OH e - H O e - OH H O ½ O e H O e H OH Slide 5

6 Compressed Gas CGH Compressed gaseous hydrogen CGH: compressed gas at ambient temperature and pressures of bar Storage compression consumes % of energy content H u issue: safety of storage system gravimetric storge capacity: pure: 33.3 kwh/kg system 700 bar: 1 kg H / 0 kg tank (5 mass%), 1.7 kwh/kg volumetric storge capacity 700 bar: pure 1.3 kwh/dm³ system 700 bar: 0.0 kg H /dm³, 0.7 kwh/dm³ Slide 6

7 Cryogenic Liquid LH Liquid hydrogen LH: cryogenic storage at ambient pressure at temperatures around 50 C Storage liquefaction consumes 0-30 % of energy content H u complex and open storage system boil off losses (1% to 3% per day) gravimetric storge capacity: pure: 33.3 kwh/kg system: 1 kg H / 18 kg tank (7 mass%), kwh/kg volumetric storge capacity: pure.3 kwh/dm³ system: 0.04 kg H /dm³, 1. kwh/dm³ Slide 7

8 Storage in compounds Physical adsorption and chemical absorption: H molecules are bound on the surface, e. g. of carbon (nanotubes, microspheres) or in are bound in the atomic lattice of metals (Mg, Al, Na, Li) or in liquids (alcohol, gasoline, oil, diesel, NH 3 ) Storage high theoretical energy densities practically difficult conditions for charging and decharching (high or low temperatures, high pressures, long time, irreversible) at lab scale Slide 8

9 Gravimetric Energy Density 1 kg gasoline 0,36 kg H, 1 kg H =,77 kg gasoline ,3 33,3 33,3 Storage Gravimetric Energy Density [kwh/kg] Gravimetric Energy Density Pure Gravimetric Energy Density System 13,9 13,9 7,4 8 11,5 0 1,6 GH (350 bar) 1,8 GH (700 bar) LH ( bar) 0,4 Solid Storage MH 0,15 Li Ion Battery 3,8 CNG (00 bar) LNG Gasoline Slide 9

10 Volumetric Energy Density 1 l (dm³) gasoline = 3,84 dm³ LH = 6,95 dm³ GH bei 700bar 10 Storage Volumetric Energy Density [kwh/dm 3 ] 0,8 0,5 1,3 0,9, 1, 0,8 8, GH (350 bar) Volumetric Energy Density Pure Volumetric Energy Density System GH (700 bar) LH ( bar) Solid Storage MH 0,7 Li Ion Battery, 1,5 CNG (00 bar) 5,8 3,3 LNG 7 Gasoline Slide 10

11 Internal Combustion Engine over 1 billion internal combustion engines worldwide Internal Combustion Engine Advantages: simple, robust and cheep ( 30/kW) high energy density (of engine and fuel) multy fuel ability (liquid, gaseous) Disadvantages: low efficiency (Carnot) emissions (pollutants and noise) Combustion engine with hydrogen: no emissions except NOx - no H Infrastrukture Slide 11

12 History Internal Combustion Engine 1807 Francois de Rivaz built the first vehicle with a simple internal combustion engine with hydrogen 1860 Etienne Lenoir built the first commercially available internal combustion engine with hydrogen that he also used in a vehicle Slide 1

13 Efficiency Internal Combustion Engine The efficiency of internal combustion engines is limited by the Carnot-efficiency for the conversion of heat into mechanical energy. Efficiency increases with combustion ratio and air/fuel ratio. Efficiency of hydrogen engines reaches values between gasoline and diesel engines Ottomotoren Dieselmotoren Laderm. Saugm. Großm. LKW PKW p max : 90 bar 00 bar 180 bar 160 bar a=1,8 a=1,4 1 a=3,0; λ=,0 0,9 0,8 a=,8; λ=1,7 Volllast a=1,9; λ=1, ,6 1,4 1, Verdichtungsverhältnis ε [ ] Slide 13

14 Ideal Combustion Internal Combustion Engine g CO/Wh, g HO/kWh y y Cx H y x O x CO HO 4 g CO/kWh g HO/kWh Kohle C C7H15 Propan C3H8 Methan CH4 Wasserstoff H 0 Slide 14

15 Slide 15 Depending on the air/fuel ratio λ, real combustion produces a number of pollutants apart from water and carbondioxide: incomplete combustion with local deficiency of air produces carbonmonoxide, hydrocarbons and carbon as basis for soot and particulate matter, high temperatures cause formation of nitronoxides... O N NO C H C CO O H CO N y x 0,1 0,79 O y x H C O N x NO Russ Russ m n H C CO O H CO y x x m n n n n n n n n n λ λ Real Combustion Internal Combustion Engine

16 Mixtures hydrogen - methane Internal Combustion Engine Vehicles with internal combustion engines for gasoline / methane (natural gas, biogas) / hydrogen / mixtures of methane and hydrogen are regarded as bridging technology: conventional functionality is combined with the option of CO -free mobility Advantages: proven, tested and cheep engines use of existing production facilities use of existing infrastructure gradual introduction of a new infrastructure reducion of carbon based pollutants CO, CO, CH synergy effects with components, infrastructure and customer acceptance Slide 16

17 Multi-Flex-Fuel Vehicle Internal Combustion Engine Prototype by Model Fuel Swept volume Power gasoline/hydrogen Tank gasoline/hydrogen Range gasoline/hydrogen IVT TU Graz, HyCentA SAE paper IJVD Mercedes E, CNG gasoline, natural gas, hydrogen 1796 cm³ 10 kw / 70 kw 65 l / kg at 350 bar 700 km / 15 km Slide 17

18 BMW Hydrogen 7 Internal Combustion Engine OEM Model Fuel Swept volume Power gasoline/hydrogen Tank gasoline/hydrogen Range gasoline/hydrogen BMW 760 h gasoline and hydrogen 597 cm³ 191 kw 75 l / 8 kg cryo 500 km / 00 km Source: BMW AG Slide 18

19 Mazda 5 RE & RX-8 Hy Internal Combustion Engine OEM Model Fuel Swept volume Power Tank Range Mazda Premacy hydrogen / electricity x 654 cm³ 110 kw,5 kg / 350 bar 00 km Source : MAZDA Motor Corporation Slide 19

20 Turbine Also in gas turbines, hydrogen allows for carbon-free combustion. To avoid nitrogen oxides: Pure oxygen instead of air (Graz Cycle) Turbine Advantages: no emissions high efficiency Disadvantages: high costs high temperatures Source : Jericha Slide 0

21 Fuel Cell Advantages: high theoretical efficiency no emissions tank to wheel no moving parts wide variety of applications Fuel Cell Disadvantages: high costs (catalyst) no H infrastructure durability?? Slide 1

22 History 1838 Friedrich Schönbein discovered the polarisation effect, the electrochemical production of electricity from water and oxygen in an electrolyte, Based on this discovery William Grove 1839 built the first fuel cell Fuel Cell First vehicles with fuel cells were built 1966 by General Motors and 1970 by Karl Kordesch Slide

23 Principle The reaction of hydrogen and oxygen yields electricity in a cold combustion H (g) ½ O (g) H O (l) R H = 86 kj/mol Fuel Cell Anode (-): H (g) OH (aq) H O (l) e oxidation (donation of electrons) Kathode (): H O (l) ½ O (g) e OH (aq) reduction (acceptance of electrons) Anode - e - e - Kathode - - OH ½ O H As the voltage of a fuel cell is low, many cells have to be combined to form a stack H OH H O e H O H O ½ O e OH E 0 = RH z F 0 m = J/mol 96485As/mol = 1,48V Slide 3

24 Efficiency The theoretical high efficiency of the fuel cell is decreased by a number of electrochemical processes, practically efficiencies of a cell range from 60 to 80 %, of a stack from 40 to 60 %. Fuel Cell Zellspannung E [V] Heizwertspannung E 0 H Standardpotenzial E 0 Nernstspannung E N Bereich der Aktivierungsüberspannungen Entropiedifferenz T S z F Bereich der Widerstandsüberspannungen Zellspannung E Z Bereich der Diffusionsüberspannungen Zellenleistung Strom I [A] Slide 4

25 Application Fuel cells are used in a wide variety of portable, mobile and stationary applications. Fuel cells can be distinguished based mainly on the operation temperature and the electrolyte used. Fuel Cell Brennstoffzelle Leistung [kw] el. Wirkungsgrad [%] Anwendung AFC Zelle 60-70, System: 60 Raumfahrt, Fahrzeuge PEMFC 0,1-500 Zelle 50-70, System Raumfahrt, Fahrzeuge DMFC 0,01-1 Zelle 0-30 Kleingeräte PAFC bis Zelle 55, System 40 Kleinkraftw. MCFC bis Zelle 55, System 50 Kraftwerke SOFC bis Zelle 60-65, System Kraftwerke und APU Slide 5

26 Honda Clarity FCX Fuel Cell OEM Model Battery Electric motor Fuel cell Hydrogen tank Range Honda Clarity FCX Lithium-Ionen Akku 100 kw 100 kw 4,1 kg / 350 bar 430 km Green Car of the Year 009 Source : HONDA Motor Slide 6

27 Daimler f-cell Fuel Cell OEM Model Battery Electric motor Fuel cell Hydrogen tank Range Daimler B Klasse Lithium-Ionen Akku 100 kw 100 kw 3,5 kg / 700 bar 400 km Source : Daimler AG Slide 7

28 Mercedes Benz Citaro OEM Model Battery (A13) Electric hub motor Daimler AG Citaro FC Hybrid Lithium-Ionen Akku 6 kwh x 80 kw Fuel Cell Fuel cell (AFCC) x 60 kw Hydrogen tank 7 x 05 l, 35 kg / 350 bar Range 50 km Source : Daimler AG Slide 8

29 Project BioEnergie Local production of electricity, heat and fuel (hydrogen) from biogas/natural gas Supply: Biogas / Natural gas Reforming Purification Electrification Electricity Heat Hydrogen Slide 9

30 Project E-LOG-BioFleet H Infrastructure Provider Vehicle-System Provider Service & Maintenance Fuel Cell-System Provider Technical assessment and project management Test customers, industrial field trial Ecological & economical assessment 30 Slide 30

31 Potentials and Perspective Hydrogen permits a CO -free sustainable closed energy cycle: produced from water by electrolysis using electricity from alternative sources (sun, wind, water) stored as compressed gas at medium energy densities at acceptable technical complexity combustion in internal combustion engines as bridging technology, especially in mixtures with (bio)methane combustion in fuel cells at high efficiencies, with high vehicle driving ranges and short filling times Expensive and sophisticated technology Political support necessary (CO -tax) Slide 31