Transportation in a Greenhouse Gas Constrained World A Transition to Hydrogen? Rodney Allam Director of Technology Air Products PLC, Hersham, UK
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The Problem: demand and cause People Prosperity Pollution The Challenge: Sustainable Development 5
US Carbon Emissions (25% of World Total) Growth of Vehicle Numbers in the UK rbon Emissions d Total) Residential Commercial Industrial Transportation Electric Utilities 6
So Why Hydrogen? Hydrogen Combustion: H 2 + ½ O 2 H 2 O H -57.8 kcal/mole H 2 is an energy carrier, is converted to water which has minimal environmental impact. H 2 is a non-polluting fuel for transportation vehicles and power production Currently road vehicles emit about the same quantity of CO 2 as power production in developed economies. H 2 can be produced from fossil fuels with CO 2 capture and storage or from renewables 7
CO 2 Capture and Storage: Hydrogen Production from Fossil Fuels H 2 production from fossil fuels will predominate H 2 for transportation fuel only makes sense if CO 2 is captured and stored 8
Production of Hydrogen Options Method Photolysis Electrolysis Power for electrolyser Thermal splitting m conc as function of temp Fossil fuel Conversion Far Future Present Fossil fuels Characteristics catalytic-water splitting water ambient high temperature ambient high pressure water high temperature freeze equilibrium Heat, water, oxygen, catalytic Non fossil fuel alternatives based on sunlight, renewables and nuclear 9
Renewable Hydrogen Production via Electrolysis Typical 2 MW Turbine gives 100 tonnes/year Hydrogen 10
Production of Hydrogen Carbon Containing Fuels Coal Natural gas Refined Hydrocarbons Heavy refinery waste Lignite Anthracite Ethane Fuel Oil Tar Pet coke 11
Production of Hydrogen Reactions Reforming With Steam - Catalytic Natural gas and light hydrocarbons CH 4 + H 2 O CO + 3H 2 CO + H 2 O H 2 + CO 2 + H - H Partial Oxidation - Non Catalytic Any hydrocarbon or carbonaceous feedstock C + ½O 2 CO - H CO + H 2 O CO 2 + H 2 - H Thermal Decomposition Only limited application as coproduct in carbon black manufacture CH 4 2H 2 + C + H 12
Production of Hydrogen Process Characteristics Open Systems External heating of a catalytic reactor Combustion products vented to atmosphere 50,000 Nm 3 /hr Steam Natural Gas Reformer 13
Production of Hydrogen Process Characteristics Closed Systems Pressurised reactors with heat supplied by direct oxidation with oxygen No venting of combustion products Natural Gas Oxygen Natural Gas Oxygen Steam POX Catalyst Partial Oxidation Autothermal Reformer 14
Production of Hydrogen Heat Integration Possibility of using high temperature H 2 /CO/CO 2 syngas to heat a convective reformer. Natural Gas Oxygen Steam Product H 2 + CO POX (Exothermic) + Steam Reforming (Endothermic) 15
Production of Hydrogen Plate-Fin Reformer Plates have chemically etched channels and are stacked then diffusion bonded Grain growth occurs between plates during the diffusion bonding process Catalyst can be a surface coating or a porous insert. Need to match the heat release rate with the steam hydrocarbon reforming rate. Very compact and potentially low cost system 16
Production of Hydrogen Ion Transport Reformer Use of an ITM membrane system diffusing oxygen into a H 2 /CO gas generation reactor ITM Syngas Chemical Potential Driven Methane Partial Oxidation CO/H 2, H 2 Air Oxygen Natural Gas Methane ITM Ceramic Membrane Syngas CH 4 + 1 / 2 O 2 CO + 2H 2 O 2-2e - ITM membrane Oxygen Passes Through Membrane Air Nitrogen Hydrogen Synthesis Gas Carbon Monoxide Depleted Air 17
18 Separation Enhanced Reactors
CO 2 Separation Technologies Capabilities Adsorption Membrane Absorption Cryogenic Feed Pressure Low to High Medium to High Low to High Medium to High CO 2 Pressure Low Low Low Low to Medium CO 2 Purity Medium to High Low to Medium Medium to High High CO 2 Recovery Medium to High Low High High 19
Adsorption Multi-bed PSA 90% H 2 recovery better than 10 ppm impurity possible 20
Absorption Remove CO 2 and H 2 S selectively Physical or chemical absorbents High purity requires further processing (methanation, drying) 21
Membrane Polymeric, low temperature low purity hydrogen, pressure reduction for H 2 Palladium diffusion, high temperature, high purity, pressure reduction for H 2 Ceramic ion conductors 22
CO 2 -Free Power and Hydrogen From Coal Fuelled System Steam 100 bar CO 2 Power H 2 380 MW 220,000 Nm 3 /hr Oxygen Coal Gasification Shift reactors and steam generation CO 2 Recovery CO 2 @ 100 bar 4,000 tonne/day Coal Water Steam Water H 2 H 2 Product Steam N 2 Power Steam Steam Turbines Air Feed Gas Turbine Heat Recovery Water Power 23
24 Timeline for Hydrogen Production Technologies
Hydrogen Supply Modes for Transportation Distribution Fuel Station Vehicle H 2 abc abc abc abc NG Ref. PSA Electrolysis Fuel Cell or ICE 25
Hydrogen Distribution Options Liquid Tank Trailer Gas Pipeline Gas Cylinders Gas Tube Trailer 26
27 Gaseous H 2 Tube Trailer Capacity 360 kg H 2
28 Liquid Hydrogen Tanker capacity 3600 kg liq H 2
Liquid Hydrogen Trailer Safety 75 Trailers With Armored Type Construction Inner Tank With Outer Thick Steel Jacket 70 Million Gallons of Liquid H 2 / Year 8 Million Miles / Year 160 Million Miles Since Inception Without Loss of Liquid Hydrogen onto the Road 1996 NASA Safety Award Winner 200 Million Pounds of Liquid H 2 Over 25 Year Period Without a Significant Incident Vehicle accidents do occur 29
30 But the difference is...
31 Rotterdam Gaseous H 2 Pipeline System
Pipeline Safety Hydrogen Industry Has 500 Miles in U.S. Air Products Hydrogen Pipelines Exceed DOT Requirements Use of Automatic Excess Flow Valves in Populated Areas Significantly Limit Amount of Release No Fires at Hydrogen Pipelines in 35 Years at Air Products 32
33 Comparative economic analysis of various hydrogen supply paths (well-to-fuel-station) from electricity and natural gas
34 Typical Fuel Cell Vehicles
Safety Considerations What people think: Hydrogen must be dangerous (but we re not sure why)? How can we use it as fuel in our vehicles? How does it compare with petrol 35
Some Properties of Transportation Fuels Hydrogen Methane Gasoline Normal Boiling Point C -253-162 35 to 210 Density at Normal Boiling Point kg/litre 0.071 0.423 ~0.7 Density relative to air 0.07 0.65 3.30 Hear of combustion (liquid) MJ/kg (LHV) 119.9 50.0 45.5 MJ/litre 8.5 21.1 31.9 Limits of flammability in air Vol % 4 to 75 5.3 to 15 1 to 7.6 Minimum ignition energy mj 0.02 0.29 0.24 Burning velocity in air at NTP cm/s 265 to 325 37 to 45 37 to 43 36
Ignition Energy of H 2, CH 4 and Gasoline with Air Flammability Limits Ignition Energy (mj mj) 100 50 20 10 Automotive Spark Plug Human Spark Brush Discharge Common Static 0.02 0 20 40 60 80 100 Fuel (% Volume) CH 4 H 2 Gasoline Flammability Limits of H 2 Are Seven Times Wider Than CH 4 37
Hydrogen as Fuel L H 2 Storage vaporizer Compressor storage Small Hydrogen Generator Larger Hydrogen Generator 500,000 SCFD Pipeline to Other Dispensing Stations Dispenser (100 cars/day) 188,000 SCFD DISPENSING STATION 38
Commercial Hydrogen Fuelling Installations BP, Singapore Air Products Hydrogen Fuelling Systems PA110008.JPG (303 KB) Supplied to major oil companies 39 Shell, Washington, DC, USA
40 Underground Liquid Hydrogen Fuelling Tank Washington, DC, USA
Hydrogen Vehicle in the Home Garage Any Leaking Hydrogen Is Buoyancy Driven Toward Ceiling Home Fueler Garage House ASHRAE Three Sigma Natural Ventilation Rate for Garage Leak Rate May Be Back Calculated Auto Manufacturers Design Hydrogen Shut-off in the Tank 41
Hydrogen Vehicles on the Highway DOE Pilot Program in the NE to Train Emergency Responders Compressed Hydrogen Tank, Typically Is Not the Threat CNG Tanks Have Not Posed a Problem at CNG Vehicle Crash Sites Many/Most Compressed Hydrogen Tanks Have Solenoid Valves Built into the Tank Closed (via an Inertia Switch) in a Crash Only Few Grams of Hydrogen Outside of the Tank vs. Several Hundred Grams of Gasoline Emergency Responder Crash Site 42
Gravimetric and volumetric storage densities of on-board hydrogen storage vessel systems 2 4 MJ/ltr and 3 7 wt% for compressed hydrogen storage systems (350 700 bar), 3 5.5 MJ/ltr and 1 5 wt% for metal hydrides storage systems (low and high temperature), 3 9 MJ/ltr and 5 6 wt% for active bulk carbon (AX21 at 77K), and 4 6 MJ/ltr and 5 12 wt% for liquid vehicle type hydrogen vessels. 43
44 Passenger Car Liquid H 2 Tank (BMW Clean Energy Car)
Summary The necessary technology for a viable H 2 infrastructure of production, distribution and storage exists. Hydrogen production from fossil fuels with CO 2 capture and storage is likely to provide the bulk of hydrogen required in the next 30-50 years More research on the optimum paths to infrastructure development R&D should concentrate on cost reduction for production, transport and storage alternatives, and demonstration projects A Hydrogen Road Map for the Eastern Mediterranean region could be developed which would build on the extensive R&D and demonstration projects worldwide 45
46 The Alternative to a Hydrogen Future
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