Tyndall˚Centre

for Climate Change Research

Hydrogen Energy Technology

Geoff Dutton

April 2002

Tyndall Centre for Climate Change Research

Working Paper 17

Hydrogen Energy Technology

Dr Geoff Dutton Energy Research Unit (ERU) CLRC Rutherford Appleton Laboratory Chilton, Didcot, Oxon. OX11 0QX Tel: 01235 445823 Fax: 01235 446863 Email: a.g.dutton@rl.ac.uk Tyndall Working Paper No. 17 April 2002

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Contents
Introduction Hydrogen Hydrogen production Steam methane reforming (SMR) Partial oxidation Integrated gasification combined cycle (IGCC) Pyrolysis Water electrolysis Reversible fuel cell Hydrogen bromide electrolysis Hydrogen production during manufacture of chlorine Photoelectrolysis Biological hydrogen production Hydrogen storage and distribution Compressed gas Liquefaction Solid state hydrogen storage Metal hydride storage systems Hydride hydrolysis Glass microspheres Relative merits of hydrogen storage systems and comparison of costs Hydrogen distribution and transport Hydrogen end use systems Hydrogen-fuelled internal combustion engines Hydrogen-fuelled turbines Fuel cells Hydrogen systems Overall economics of hydrogen systems Conclusions Appendix 1: Energy units Appendix 2: Hydrogen characteristics and safety Appendix 3: Basic format for technology summaries References

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Introduction
The term hydrogen economy was first used during the energy crises of the 1970s to describe a national (or international) energy infrastructure based on hydrogen produced from non-fossil primary energy sources. Within this concept, hydrogen is regarded as a suitable storage and transmission vector for energy from renewable or nuclear power systems, allowing the generator or utility increased flexibility in responding to fluctuations in wind or solar input or consumer demand, on a short term (minutes/hours) or seasonal basis. Hydrogen can be stored and transported in pressure vessels or transmitted by pipeline to the point of enduse. It is a versatile fuel, which can easily be substituted for traditional fuels, whether for stationary or transport applications, resulting in improved efficiency and negligible pollution at the point of use. Considering the current need to develop responses to human-induced climate change, a fully developed hydrogen economy has the potential to drastically reduce emissions of carbon dioxide within the electrical power, transport, and low grade heat supply sectors. However, the energy path from solar, wind, and other renewable generators, through hydrogen production via electrolysis and widespread storage and distribution, to end-use in cars, aeroplanes, and domestic and business premises is complex and currently very expensive. Intermediate paths, employing hydrogen derived from fossil fuel sources, are already used to produce merchant hydrogen and are likely to be more economic (subject to fluctuations in fossil fuel price) in the short to medium term. Most, but not all, of these fossil fuel based paths will require potentially expensive carbon dioxide sequestration, if they are to contribute to the reduction of greenhouse gases. This report on hydrogen energy conversion technologies aims to identify the current state of the art in terms of typical plant sizes, readiness for large scale application, estimated capital and running costs, and the need and potential for significant innovation against time scales of 10, 20, and 50 years. The report has been prepared as the first of a series of three documents being prepared with funding from the Tyndall Centre for Climate Change, as Phase I of the project: The Hydrogen Energy Economy: its long term role in greenhouse gas reduction. The other two reports are concerned with lessons to be learned for hydrogen energy development from previous transitions in large technical systems and energy futures scenarios, and the potential use of hydrogen within transport systems. It has been prepared by consulting many sources, including presentations made by leading industrial and academic experts to the UK Hydrogen Energy Network (H2NET), but has drawn most heavily on the following studies: (i) Lakeman and Browning (2001): Global Status of Hydrogen Research1 carried out by DERA for the DTI and which includes a state of the art overview of hydrogen energy technologies, (ii) Padro and Putsche (2001): Survey of the economics of hydrogen technologies2 carried out by NREL for the US Department of Energy and which includes an attempt to produced levelised cost comparisons for the major production and distribution technologies, (iii) Ogden (1999): Prospects for building a hydrogen energy infrastructure3 which considers a wide range of possible architectures for hydrogen energy systems. US $/GJ has been adopted as the standard measure for comparing cost estimates, since this is the approach adopted in (ii) above (at current exchange rates, this is approximately a factor of 4 greater than the equivalent cost in p/kWh). Comparisons of common energy equivalents are presented in Appendix 1.

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Hydrogen
Hydrogen is an energy vector, not a primary fuel. It does not exist in pure molecular form naturally on Earth (although hydrogen atoms are estimated to comprise 0.14% by weight of the earth's crust), but must be produced from other sources. Hydrogen has more energy per unit mass than any other fuel and it avoids or substantially reduces CO2 and other emissions at the point of use (which makes it attractive for transport applications). Hydrogen can be produced, stored, and used in many diverse ways, but the ultimate energy paths can be complex and the most commonly suggested fuel cycles (usually involving electrolysis) are expensive, by comparison with existing fossil fuel prices. It is interesting that some of the less talked about production routes (from fossil fuels) are relatively inexpensive and the perceived environmental problems (continued need for extensive carbon dioxide sequestration) may be soluble. The basic properties of hydrogen are tabulated in Appendix 2 and compared with the equivalent data for petrol and natural gas. Hydrogen is safer than commonly held perceptions might suggest. Leaks are difficult to detect because the gas is colourless and odourless, but it mixes much faster with air than either methane or petrol vapour (see high diffusion coefficient) which makes accidents in the open air less critical. In confined spaces, there are potential problems, which should be addressed by the provision of suitable vents. Hydrogen has a much wider explosive range in air (13%-59%) than methane (6.3%-14%), but the latter is explosive at lower concentrations. There is a factor 10 difference in minimum ignition energy between hydrogen and either methane or petrol, but this is of little significance when it is considered that even the spark from a static electric discharge has sufficient energy to ignite natural gas. In all other respects, hydrogen is broadly similar to the fuels it might replace. Hydrogen's main drawback is that of low density and consequent low volumetric heat content (approximately 25% that of natural gas). The principal drivers behind the current interest in the hydrogen economy are: oil and gas resource depletion, global warming, urban air quality, security of energy supply, lack of suitable large scale electricity storage media.

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Hydrogen production
Currently hydrogen is used almost exclusively as an industrial chemical, within which capacity it is applied to a wide variety of uses, including ammonia production (for fertiliser manufacture), refinery use for desulphurisation and other processes, and methanol production. The annual world production is around 500 billion Nm3. The largest producer is Air Products, who operate more than 50 individual plants, producing over 25 million Nm3 per day, and 7 pipeline systems totalling more than 340 miles1. The bulk of hydrogen (almost 50%) is produced by steam methane reforming (SMR), which is the most economical (large scale) route. Partial oxidation of hydrocarbon fuels can be competitive where a cheap source of oxygen is available. The US DOE hydrogen production cost target2 from fossil fuel based sources is 5.70-7.60 $/GJ. Steam methane reforming (SMR) Four stage process: (i) feedstock preheating and purification (needed because catalyst is highly sensitive to impurities, e.g. sulphur, mercury, and other metals), (ii) steam reformer (iii) CO shift (iv) PSA purification (absorb compounds other than H2; hydrogen recovery 80%-90%) Reformer reaction (for methane):

CH 4 + 2 H 2 O ↔ CO2 + 4 H 2 ( ∆H 0 = +164kJ / mol ; typical operating temperature 850 oC) 0 CH 4 + H 2 O ↔ CO + 3H 2 ( ∆H = +205kJ / mol )
operates at < 40 bar (Jacobs plant typically 20-30 bar) highly endothermic reaction conversion favoured by higher temperature and steam; conversion reduced by higher pressure need highly active nickel catalysts possibility to enhance reaction by adsorption of CO2, enabling reaction temperature to be reduced to 550 oC

CO shift reaction (favoured by lower temperature):

CO + H 2 O ↔ CO2 + H 2
uses CO shift catalysts: iron oxide based (conventional HT 340-460 oC), (MT) iron + copper oxide (modified HT 310-370 oC), copper, zinc, aluminium (low T 180-280 oC) small and medium-sized plants have single MT shift reactor large plants have 2 x MT reactors or HT plus MT reactors

Typical plant sizes: Small Medium
1

500 - 3000 Nm3/hr up to 25,000 Nm3/hr
Hydrogen Production, Supply, and Distribution, C. Spilsbury, Air Products plc, H2NET Hydrogen Production meeting, University of Glamorgan, 14 February 2001 A multi year plan for the Hydrogen R&D Programme rationale, Structure and Technology Roadmaps, Office of Power Delivery, Office of Power Technologies Energy, Energy Efficiency, and Renewable Energy, US DOE, August 1999 - cited in Lakeman and Browning (2001)1

2

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Large Very large World max. Potential max.

over 25,000 Nm3/hr over 150,000 Nm3/hr 300,000 Nm3/hr (tar sands project) 950,000 Nm3/hr

Partial oxidation Hydrogen may be formed by the non-catalytic partial oxidation of hydrocarbons. Any hydrocarbon feedstock that can be compressed or pumped may be used. Overall process efficiency is only 50% (c.f. SMR at 65%-75%)3. Pure oxygen is required as a feed. Partial oxidation - Reformer reaction: Natural gas : Coal :

1 CH 4 + O2 → CO + 2 H 2 2 1 C + O2 → CO 2 CO + H 2 O ↔ CO2 + H 2

(1350 oC) (1350 oC)

- Syngas (Synthesis Gas) process

Partial oxidation - CO shift conversion:

-

uses any fossil fuel and can operate at high pressure (> 100 bar) BP Amoco Bulwer Island Refinery (Australia) POX unit produces 35,000 Nm3/hr, which is very low for a POX unit (not normally economic)

A fuel processor is a mechanical device that uses heat and a catalyst to initiate changes in the chemical composition of a hydrocarbon to release hydrogen molecules. HydrogenSource4 lists three technologies: (i) catalytic steam reforming (CSR) involves reacting a hydrocarbon fuel and steam in the presence of a catalyst - an external heat source is required, the process is high efficiency, (ii) auto thermal reforming (ATR) involves reacting a hydrocarbon fuel and steam in the presence of a catalyst and oxygen - some of the fuel is used to generate the required heat for the reaction, the process can be used on many different types of fuel, (iii) catalytic partial oxidation reforming (CPOX) is similar to auto thermal reforming but allows use of a simpler and smaller operating system. ICI have developed a gas-heated reforming5 (GHR) process to reduce the size of the large steam system required when methane steam reforming. Note that the oil majors have a vested interest in making sure that the reformer is placed on the vehicle (they can then deliver a liquid fuel with relatively little change to their existing infrastructure), which makes CO2 sequestration much harder to achieve. General Motors recently announced they had developed such an on-board gasoline reformer. However, there is considerable difficulty in ensuring that when the driver wants to accelerate the reformer-fuel cell system can deliver the required response. Methanol is easier to reform (and the process can be carried out at lower temperatures) than either kerosene or diesel. Technology developments are concentrating on:
3 4

5

Vezirogulu and Babir (1998), Kirk-Othmer (1991) and Leiby (1994) quoted in Padro and Putsche (1999)2 HydrogenSource is an independent company formed between International Fuel Cells and Shell Oil Company (see http://www.hydrogensource.com/whoweare.html) See Synetix Web site : http://www.synetix.com/methanol/technology-ghr.htm

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(i) (ii) (iii) (iv)

reactor design (e.g. use of micro-channels to enhance heat and mass transfer capabilities currently being developed for small scale reformers, e.g. Pacific Northwest National Laboratory 1 kW steam reformer), plasma reformation (MIT) can be applied to POX, SR, and pyrolysis, compact design to incorporate reforming and water gas shift operations in single stage, outlet gas clean-up (required for PEMFC operation).

Integrated gasification combined cycle (IGCC) In an IGCC system, a coal gasifier converts pulverised coal into a synthesis gas (mixture of H2 and CO) by adding steam and oxygen. This Syngas is then cleaned of impurities and used to produce energy in a gas turbine. (Alternatively the product gas could be used to produce hydrogen, chemicals, or other fuels.) Waste heat from the gas turbine is used in a steam turbine to generate more electricity. Integrating gasifier technology with a combined cycle in this way offers high system efficiencies and ultra-low pollution levels. Systems are designed to handle a variety of feedstocks, including low and high sulphur coal, anthracite, and biomass. Typical systems range in size from 200-800 MWe; although modular designs of 50-150 MWe are expected to be the basis for future plants6. Typical plants offer an improvement of 10% in thermal efficiency over conventional coal-fired stations. The operating efficiency is between 29-41%, depending on the fuel characteristics (ie sulphur content, ash content and calorific value), type of IGCC system (ie entrained, moving-bed or fluidised-bed) and peak gas turbine temperature. Due to high costs and low efficiencies, IGCC remains a demonstration technology, but it is hoped that second-generation technologies will realise efficiencies from 45-50% and reduced costs. Capture of CO2 is considered difficult without incurring significant efficiency and cost penalties7. Possible future technological developments include Entrained Flow Gasifiers and Water-wall Cooled Gasifiers. Pyrolysis Hydrocarbons can be converted to hydrogen without producing carbon dioxide, if they are decomposed at a sufficiently high temperature in the absence of oxygen (pyrolysis). For example methane can be "cracked" in the presence of a catalyst such as carbon felt (or novel carbon families, such as C60 soots, graphite, or activated carbons). Carbon black can either be sequestered or used further by a number of industries (e.g. car tire production, metallurgic industries). This process has been developed commercially by Kvaerner under the process name "Kvaerner Carbon Black and Hydrogen Process" (KCB&H). A pilot plant has been operating since 1992 and a commercial plant (first stage produces 50 million Nm3/year of hydrogen and 20,000 tonnes/year of carbon black) started operation in Canada during mid-1999. The process is projected4 to be slightly more expensive than steam methane reforming before carbon black revenues are taken into account; with these revenues it may even be cheaper. Cost projections have been presented for plants producing 100 million Nm3/year and 500 million Nm3/year of hydrogen. In principle, pyrolysis could also be applied to more complex hydrocarbons, biomass, and municipal solid waste.

6 7

See IEA GREENTIE : http://www.greentie.org/class/ixa10.htm John Griffiths, Jacobs Consultancy, IChemE Sourcing the Hydrogen Economy meeting, October 2001

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Table 1 : Type of plant SMR - small SMR - very large POX

Typical plant sizes for hydrogen production Typical plant size 500-3000 Nm3 /hr < 150,000 Nm3 /hr Future developments Currently 200-800 MWe Modular designs of 50-150 MWe are expected in near future 10% more efficient than conventional coal stations Modular design 5,000 Nm3/hr (demonstration) 100-40,000 Nm3/hr (costestimated) Modular units reactor design plasma reformation compactness outlet gas clean-up

Integrated Gasification Combined Cycle (IGCC)

Pyrolysis

Water electrolysis

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Table 2 :

Reference costs for hydrogen production from more conventional technologies (derived from Padro and Putsche, 19992) Hydrogen price ($/GJ) 11.22 7.46 6.90 6.26 5.44 5.97 11.57 9.87 10.73 7.39 6.94 9.83

Facility size References Specific TCI (106 Nm3/day) ($/GJ) Steam methane reforming − 48% of world hydrogen production (1998) 0.27 (small) Leiby 1994 in Padro and Putsche (1999)2 27.46 1.34 (large) Leiby 1994 in Padro and Putsche (1999)2 14.74 2.14 Leiby 1994 in Padro and Putsche (1999)2 12.61 2.80 Kirk-Othmer 1991 in Padro and Putsche (1999)2 9.01 6.75 Foster-Wheeler 1996 in Padro and Putsche (1999)2 10.00 25.4 Blok et al 1997 in Padro and Putsche (1999)2 10.82 Coal gasification - economic where oil and/or natural gas is expensive 2.80 Kirk-Othmer 1991 in Padro and Putsche (1999)2 34.2 6.78 Foster-Wheeler 1996 in Padro and Putsche (1999)2 33.1 Partial oxidation of hydrocarbons 0.27 (small) Feedstock - coker off-gas (Leiby 1994 in Padro and Putsche (1999)2) 1.34 (large) Feedstock - coker off-gas (Leiby 1994 in Padro and Putsche (1999)2) 2.14 Feedstock - coker off-gas (Leiby 1994 in Padro and Putsche (1999)2) 2.80 Feedstock - residual oil (Kirk-Othmer 1991 in Padro and Putsche (1999)2) Biomass gasification - costs vary depending on gasifier technology 0.720 Mann 1995 in Padro and Putsche (1999)2 2.16 Larson 1992 in Padro and Putsche (1999)2 2.26 Larson 1992 in Padro and Putsche (1999)2 Biomass pyrolysis 0.024 Mann 1995a in Padro and Putsche (1999)2 0.243 Mann 1995a in Padro and Putsche (1999)2 0.811 Mann 1995a in Padro and Putsche (1999)2 Methane pyrolysis - Gaudernack and Lynum (1998)4 SMR without CO2 sequestration SMR with CO2 sequestration CB&H process without carbon black revenue CB&H process with carbon black revenue 21.96 11.24 9.63 22.28

38.19 20.60 26.91 30.66 19.31 16.74

13.099 8.69 10.03 12.73 10.11 8.86 6.0 7.5 10.6 5.8

8 9

More expensive than coker off-gas due to increased equipment for feed handling and impurity removal Delivered hydrogen price depends on biomass feedstock costs which can vary widely from expected price for dedicated biomass production ($46.30/dry tonne) to the price for waste product ($16.50/dry tonne)

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Water electrolysis Hydrogen can be produced from water by electrolysis. If the electricity is produced from a renewable technology (such as solar, hydro, wind, or tidal) then the process is carbon-free. The electrochemical splitting of water is well known:

1 H 2 O → H 2 + O2 2
Commercial electrolysis plants typically achieve efficiencies of 70-75%. There are two basic types of electrolyser: (i) liquid alkaline (easy to scale up, easier thermal management by circulation of electrolyte, likely to remain popular choice for large plants in foreseeable future), (ii) proton exchange membrane (PEM) (driven by small to medium-sized applications, such as homebased systems, single vehicle refuelling). Typical operating pressures are up to 50 bar (750 psig) which is insufficient for charging high pressure cylinders. Electricity consumption of the electrolysis process can be reduced in principle by operating at high temperatures (900 - 1000 oC). A high temperature steam electrolyser (HTSE) is currently under development at the Lawrence Livermore National Laboratory. In order to achieve high energy storage densities it is necessary to store hydrogen (and oxygen for closed regenerative systems) at high pressure. This can be achieved through the use of compressors or high pressure electrolysers (which requires reactor containment in a pressure vessel, see current US research). Reversible fuel cell Attractive in principle, but limited so far in realisation due to the fact that electrode design (particularly with regard to catalysts) is different for the electrolysis and fuel cell energy flows. Hydrogen bromide electrolysis The electrolysis of hydrogen bromide to hydrogen and bromine:

2 HBr → H 2 + Br2
requires half the voltage of the water electrolysis reaction and is therefore potentially more efficient. The reaction is reversible and can therefore be incorporated in a closed loop energy storage/generation system. This concept can be thought of as an adaptation of the RegenesysTM regenerative fuel cell being developed by Innogy Technology Ventures Ltd in the UK, which uses a bromide/bromine cathode (i.e. one half of the proposed system), by the addition of a hydrogen anode. This technology is being investigated by ITVL in collaboration with SRT in the US under US DOE funding. A further potentially useful development of this technology is that hydrogen bromide can be produced by the reaction of methane with bromine:

CH 4 + 2 Br2 → C + 4 HBr
with the production of carbon black. The bromine can be recycled after the hydrogen bromide electrolysis reaction.

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Hydrogen production during manufacture of chlorine Hydrogen is produced as a by-product in the manufacture of chlorine by electrolysis of brine in a mercury based membrane cell. Chlorine and hydrogen are explosive and so must be kept apart when evolved.

2 NaCl → 2 Na + Cl 2 2 Na + 2 H 2 O → 2 NaOH + H 2
Brine is introduced to the anode side of the electrolysis cell and the chlorine ions are oxidised to produce chlorine gas; the sodium ions pass through the central membrane and combine with hydroxide ions to produce sodium hydroxide (caustic soda); while the hydrogen ions are reduced to give off hydrogen gas. The process takes place at 75-90 oC. Global production of chlorine is 40.0 Mt/year (producing approximately 1.0 Mt/year of H2) and is growing 2%-3% per annum. In the UK, production is about 1.06 Mt/year (with 0.03 Mt/year of H2). 35% of the H2 is used as a chemical feedstock, 50% as fuel, and the remaining 15% is currently unused (vented) The H2 gas is saturated and contains NaOH and mercury impurities. Photoelectrolysis Photoelectric systems split water directly into hydrogen and oxygen using sunlight as the only energy input. Such a system does away with the need for external wiring, convertors, etc. The system must generate sufficient internal voltage to decompose the water molecules. Multi-junction cell technology, developed by the photovoltaics industry, involves the series connection of photovoltaic layers with different semiconductor band gaps to produce a single cascade device. This configuration uses a higher proportion of the solar spectrum than a simple photovoltaic cell and therefore has a higher theoretical conversion efficiency. The cascade structure minimises surface area requirements. Amorphous silicon (a-Si) is being considered for this technology, but stability in an aqueous environment is a key research area. See work at NREL, Golden, Co., and Hawaii Natural Energy Institute. DOE hydrogen production cost target10 9.50-14.20 $/GJ (US $10-15 per million BTUs). DOE photo-conversion efficiency target 15%. Biological hydrogen production Hydrogen can be produced biologically in two distinct ways: (i) photosynthesis process, (ii) fermentation process. Green algae capture energy from sunlight. Under anaerobic conditions, the green algae produce a hydrogenase enzyme which produces hydrogen from water by a process known as bio-photolysis. The conditions must be carefully regulated, since the hydrogenase enzyme works in the dark phase and is sensitive to the presence of oxygen produced from photosynthesis. A two stage process is used to maximise hydrogen yield. The major research challenges are: (i) increase hydrogen production by a factor of 10, or better, (ii) increase solar energy conversion efficiency from 5% to at least 10%, (iii) producing a non-living membrane cell with oxygen- and hydrogen- producing enzymes. (Hydrogen can also be produced photosynthetically by harnessing nitrogenase reactions on blue-green algae and photosynthetic bacteria, but the reaction is inhibited by nitrogen, ammonia, and oxygen, and the
10

A multi year plan for the Hydrogen R&D Programme rationale, Structure and Technology Roadmaps, Office of Power Delivery, Office of Power Technologies Energy, Energy Efficiency, and Renewable Energy, US DOE, August 1999 - cited in Lakeman and Browning (2001)1

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production rate is 1000 times slower than the hydrogenase process.) Research work is progressing under IEA Task 15 (Japan, Norway, Sweden, US, Canada). The second main biological pathway to hydrogen uses fermentation without need for light. This is a dark, anaerobic process carried out by many species of bacteria, one of which, Clostridia, has been singled out for particular attention. The reaction involves a hydrogenase enzyme acting on carbohydrates to produce hydrogen (and carbon dioxide):

C6 H 12O6 + 2 H 2 O → 2CH 3COOH + 2CO2 + 4 H 2
Laboratory studies have concentrated on pure microbial cultures, sterile feedstocks, and batch operation. Commercialisation requires use of stable, mixed micro-flora, non-sterile feedstocks, and continuous process operation. Potential feedstocks include sugar cane or the organic fraction of muncipal waste. The theoretical yield is 0.5 m3 H2/kg carbohydrate, although this is yet to be achieved, largely because the reaction is hindered by increasing hydrogen concentration. University of Glamorgan researchers have achieved 36% of theoretical maximum in a continuously operating reactor using mixed micro flora and non-sterile feedstocks by sparging the reactor with inert gas. Fermentative bacteria can multiply rapidly and produce high quantities of hydrogen, but the design and operational parameters are not yet well established.

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Table 3 :

Reference costs for hydrogen production from electrolysis and less conventional technologies (derived from Padro and Putsche, 19992) Specific TCI ($/GJ) 31.88 2.95 (?) 30.97 158.6 (165.7) 92.5 (91.1) 485.8 242.0 Hydrogen price ($/GJ) 28.7 20.6 24.5 20.2 (22.6) 11.0 (12.6) 41.8 24.8

Facility size References (106 Nm3/day) Electrolysis- non-specific technologies 0.096 Andreassen 1998 in 2 2.8 Kirk-Othmer 1991 in 2 6.75 Foster-Wheeler in 2 Electrolysis - wind based 0.247 (0.02311) Mann et al 1998 in 2 − technology 200012 0.279 (0.028) Mann et al 1998 in 2 − technology 2010 Electrolysis - solar photovoltaics based 0.195 (?) Mann et al 1998 in 2 − technology 2000 0.209 (?) Mann et al 1998 in 2 − technology 2010

Mann et al. (1998)5 observe that economics of renewable powered electrolysis can be improved by: use of off-peak electricity when wind/solar energy not available, sale of electricity from wind/solar energy during peak tarif times (i.e. suspend hydrogen production). For the US cases studied, a combination of these can potentially improve economics by a factor of 2 (dependent on wind/solar regime, electricity tarifs, feed-in contracts, etc.). It is desirable to evaluate case studies for equivalent situations within the UK electricity network and this will be carried out as part of the Phase II study.

11

12

Author's spreadsheet calculation based on data given in original paper - the original capacity throughput is incompatible with the size of the wind farm cited (10 MW) Mann et al note the potential to increase revenue from these plants by utilising a grid connection to purchase power at offpeak periods when the renewable generators were not operating and/or to sell electrical power at peak time (at the cost of reduced hydrogen production)

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Hydrogen storage and distribution
To achieve a fully functioning hydrogen economy, hydrogen will need to be stored on a wide range of scales. Large, centralised storage would be required if hydrogen is produced in large plants for wider distribution; longer term or seasonal storage would be required in systems relying on large penetrations of renewable energy; comparatively small scale storage is required on board vehicles, possibly in homes, and for portable devices. Technology Automotive applications Portable power systems (military) Stationary systems Surface storage in large compressed gas tanks Storage in depleted gas wells, salt caverns, etc Novel composite cylinders Liquefied hydrogen Conventional metal hydrides Specific developments Targets 6.5 wt% (US DOE) 62 kg H2 m-3 11.0 wt% likely to be cost driven

Already used for natural gas storage Ambient temperature hydrides FeTi, LaNi5, typically < 2.0 wt% Little improvement in capacity likely - improve cycle life - improve impurity tolerance - improve kinetics - improve T of operation UBirm using palladium, platinum, ruthenium to improve kinetics and impurity tolerance

Novel metal hydrides

Carbon nano-adsorbents (nanofibres, nano-tubes, etc)

Higher temperature hydrides usually contain Mg (e.g. Mg2Ni), can store up to 7.0 wt% Sodium aluminium hydrides with titanium or zirconium catalyst (e.g. NaAlH4, Na3AlH6) - titanium doping makes reaction reversible - currently slow kinetics Lithium beryllium hydride, reversible hydrogen capacity of almost 9.0 wt%, but requires T > 250 oC to achieve useful pressures Claims of 0.0 to > 50.0 wt% have been made - a growing consensus appears to be that early results were due to water absorption and only a few wt% will be achieved, in practice

5.0 wt% (IEA Task 12)

Work continuing under IEA Annex 12

Hydride hydrolysis Glass microspheres

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Compressed gas Conventional steel cylinders are heavy and bulky. In a typical system, hydrogen is compressed to about 20.7 MPa (i.e. 200 bar / 50 litre), requiring around 2.3 kWh/kg13. Larger, spherical pressure vessels are used where larger volumes of hydrogen are required (say > 14,000 Nm3). Composite cylinder technology - inner aluminium or thermoplastic liner providing gas barrier, strengthened by overwrapping layers of glass or carbon fibre reinforcement, lighter weight. Initial cylinders manufactured by EDO and Luxfur realised around 3.0 wt% H2 at pressures 200-300 bar. Lawrence Livermore National Laboratory (with IMPCO Technologies, Thiokol Propulsion, and Aero Tec laboratories) have produced a prototype composite cylinder which can store 11.3 wt.% H2 at a working pressure of 5000 psi [345 bar] (equating to 3.8 kWh/kg specific energy storage). Burst pressure safety margin was found to be 2.15 (2.25 design). Development plans include a 10,000 psi unit (but note higher compression cost and complexity) and examining way to deal with heating problems during fast filling of the cylinders. There is a trade-off between improved gravimetric performance from using higher grade carbon fibre and the overall cost per tank. Preliminary cost estimates suggest that at high volume production (>500,000 units per year) tanks holding 3.6 kg H2 at 345 bar will cost $640 (£444), the largest cost component being high grade carbon fibre. The requirement for additional compression consumes energy, adds to expense, and has a significant footprint. Compressor development is required in the areas of new materials, improved efficiency, and more compact designs. Problems also arise with heating of tanks on fast filling, which may limit the rate at which tanks can be refilled. Pre-cooling of the hydrogen or the use of heat exchangers may be required to overcome this barrier. Thiokol Propulsion is also considering designs for conformable tanks to fit existing vehicle envelopes, since it is often difficult to accommodate cylindrical tanks. This may not be such a problem if the vehicle is designed around the tank. Liquefaction The energy required for liquefaction14 ranges between 8.5 kWh/kg and 13.0 kWh/kg, depending on plant size. Energy requirements as low as 5.0 kWh/kg may be achievable in future magnetocaloric cooling15. Very efficient tank insulation (cryogenic dewar vessels) is required to keep temperatures below the boiling point of hydrogen (only 20 K at 1 bar). Spherical shape reduces surface area to volume ratio and hence heat losses, but are difficult to accommodate in a car envelope. Insulation increases volumetric size of tanks. Sizes range from several litres to 3,800 m3 (the largest in the world at NASA). Transport and stationary infrastructures can potentially be linked. The value of intermittent renewable power sources can be enhanced by use of hydrogen as an energy vector. Boil-off rates quoted by BMW are around 3% per day, but this is only a problem if the hydrogen is stored for longer periods of time, since in normal applications the gaseous phase will be used first.

13 14

15

Wurster, R., Zittel, W., http://www.hydrogen.org/Knowledge/Ecn-h2a.html, section 9.7 This includes the energy required to convert all the -ortho form of H2 to the -para form (at ambient temperature, the gas is 75% -ortho and 25% -para) Amos, W.A., 1998, p. 23, and Wurster, R., Zittel, W., http://www.hydrogen.org/Knowledge/Ecn-h2a.html, section 9.8

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An alternative to cryogenic storage at ambient pressure is to use insulated pressure vessels with the capacity to operate at LH2 temperatures and high pressure (24.8 MPa; 3600 psig). These vessels can accept either LH2 or CH2 as fuel. Capacity, and hence range, are reduced to one-third of the LH2 capacity when using CH2. The cost of liquefaction need only be paid where journey ranges in excess of 200 km are required. Solid state hydrogen storage • metal hydride • intermetallic compounds (LaNi5, ZrMn2, TiFe) - can achieve around 2.0 wt/% H2; to achieve higher need to use other materials • solid solution alloys (V-Ti-Fe, V-Ti-Mn) • magnesium (nanocrystalline) - high T (~300 oC), but quite slow kinetics (even after surface treatment), nanotechnology with low T and p ~7.0 wt.% seems possible (check) carbon-based • cryo-adsorption (77 K, 60 bar) • nanotubes, nanofibres (C60 required high T, so researchers looked at other structures, 10.0 wt.% to 50.0 wt.% originally claimed, but not independently verified and appear to have been due to water absorption) - mechanism has yet to be proved, but thought to be due to hydrogen condensing in the spaces between the graphite layers of the fibre novel hydride • hydride complexes (Mg2NiH4, NaAlH4) • non-reversible (sodium borohydride with product recycling) - used by Millennium Cell and Powerball

NaBH 4 + 4 H 2 O → NaOH + H 3 BO3 + 4 H 2
Metal hydride storage systems Two classes : (i) those which operate at ambient temperature, (ii) those which require higher temperatures (> 200 oC) Target : 7 wt.% of H2 Low desorption temperature (< 100 oC) Low operating pressure Ability to recycle many times Fast recharge kinetics Hydride hydrolysis Hydrogen can be liberated by the action of water on certain hydride materials:

MH + H 2 O → MOH + H 2
Historically water has been added to solid powder hydrides, giving rise to an exothermic reaction which is difficult to control. Current research is concentrating on fluid forms of the hydride, which improves heat and reaction control. There are two approaches: (i) stabilisation of the hydride in an aqueous hydroxide solution (Millennium Cell LLC using sodium borohydride and Pt or Ru catalyst; the reaction product sodium metaborate is a safe compound found in laundry detergents and can be recycled at centralised processing plants; theoretical storage of 10.8 wt%, values of 7.0 wt% claimed),

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(ii)

stabilisation of the hydride in an organic oil slurry (Thermo Technologies, USA using light metal hydride such as lithium hydride in an organic dispersant such as light mineral oil; likely efficiency of between 6.4 wt% and 15.3 wt%).

Glass microspheres Hydrogen can be contained at very high pressures in small glass microspheres, which perform as tiny pressure vessels. Research funded by the US DOE has recently been suspended following a detailed cost and performance analysis. Relative merits of hydrogen storage systems and comparison of costs The two main factors affecting the cost of a hydrogen storage system are production rate and storage time. The required production rate determines the size of compressors and liquefaction plants and their operating costs (electricity, heating/cooling requirements); the production rate multiplied by the number of storage-days gives the overall capacity, which in turn determines the unit size and capital cost. Amos (1998) 6 compares the relative merits and costs of competing hydrogen storage technologies. When considering final hydrogen delivered cost it is necessary to take account of delivery distance, as well as production cost, production rate, and storage time, making the optimum economic storage solution casedependent. Nonetheless, it is possible to draw some general conclusions: • Underground storage is the cheapest method at all production rates and storage times (due to low capital cost of the cavern): biggest cost item is electricity cost for compression; relatively insensitive to changes in production rate and storage time; additional transport cost to consumer may be high, but underground storage may have applications for seasonal storage or security of supply. Metal hydride storage is perceived to have no economy of scale (high capital cost of storage alloy), so does not compete with other options at high production rates or long storage times, but may be ideal at low flow rates and short storage times. Since it is also considered the safest storage option, this makes it a leading candidate for on-vehicle storage, subject to achieving satisfactory energy densities. Liquid hydrogen storage is not economic at low production rates (high capital cost of liquefier) and struggles to compete with compressed gas at higher production rates unless longer storage times are required, when the lower capital cost of liquid hydrogen dewars compared to compressed gas pressure vessels becomes the chief factor. The comparatively low dewar capital cost makes liquid hydrogen storage costs relatively insensitive to storage time. At very high production rates, economy of scale reduce storage costs until they are limited by the electricity costs associated with liquefaction. Compressed gas hydrogen storage is competitive with liquid hydrogen and metal hydride storage for small quantities and low production rates. At low production rates, the capital cost of the pressure vessel dominates, at higher volumes the critical factor is electricity cost for compression. As storage time increases, the capital cost of the pressure vessel begins to dominate the cost. A further option is to increase the operating pressure of the system (smaller, lower cost tank; higher compressor capital and compression running costs): for short times, there is a balance between these costs, at longer times the capital cost reduction is the dominant factor resulting in an optimum at maximum operating pressure.

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Table 4 :

Reference costs for hydrogen storage systems (derived from Padro and Putsche, 19992) Specific TCI ($/GJ) 9,008 2,992 2,285 1,726 3,235 1,028 580 35,649 7,200 1,827 3,235 1,687 1,055 363 169 4,191 18,372 18,372 18,372 Hydrogen price ($/GJ) 4.21 1.99 1.84 1.53 36.93 12.34 7.35 17.12 6.68 5.13 5.26 22.81 25.34 8.09 5.93 2.89 7.46 205.31 205.31 1.0-5.0

Facility size References (GJ) Compressed gas storage − short term (1-3 days) 131 13,100 20,300 130,600 Compressed gas storage − long term (30 days) 3,900 391,900 3.9 million Liquefied hydrogen − short term (1-3 days) 131 13,100 20,300 130,600 Liquefied hydrogen − long term (30 days) 3,900 108,000 391,900 3.9 million Metal hydride − short term (1-3 days) 131 130,600 Metal hydride − long term (30 days) 3,900 3.9 million Underground hydrogen storage − short term (1 day)

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Hydrogen distribution and transport
Hydrogen is conventionally distributed in gaseous form in cylinders or large tanks, or in liquid form by tanker or occasionally pipeline. Future applications may include storage and transport as a solid metal hydride. The optimum method depends on quantity delivered and distance transported. A large scale hydrogen pipeline distribution infrastructure is conceivable, but would be expensive. There are significant technical problems (arising from embrittlement of metals and the use of certain kinds of plastic pipe) related to the use of the existing natural gas pipeline network (although it is considered feasible to dilute the natural gas supply by up to 10% by volume with hydrogen). However, a complete changeover to pure hydrogen distribution is probably logistically impractical since some consumers would still require natural gas during any changeover period. Some researchers have suggested that local production of hydrogen − by steam methane reforming or electrolysis of water − may be economically feasible.

Table 5 : Transmission/ Transport distance (km)

Hydrogen transmission and transportation costs (derived from Padro and Putsche, 19992) References Specific TCI ($/GJ) Hydrogen price ($/GJ)

Hydrogen transmission costs (pipeline) − transmission rate 0.15 GW (2 studies) 161 14.14/21.22 805 67.53/106.24 1609 134.18/210.32

2.03/2.83 8.87/13.84 17.41/27.23

Hydrogen transmission costs (pipeline) − transmission rate 1.5 GW (47.3 million GJ/year) (2 studies) 161 2.13/2.83 0.49/0.83 805 7.47/11.59 1.17/2.09 1609 14.13/22.3 2.03/3.53 Hydrogen transport as liquefied hydrogen by truck − 45,418 - 45.6 million GJ/year 16 0.44-11.0 161 0.77-11.0 805 2.70-11.0 1609 5.10-11.0 Hydrogen transport as compressed gas by truck − truck tube unit capacity 21.72 GJ 16 4.10 161 8.20 805 30.20 1609 57.60 Hydrogen transport via truck using metal hydrides − metal hydride at $18,375/GJ 16 7.54 161 15.08 805 55.28 1609 105.54 0.24-1.60 0.52-1.84 2.00-3.10 3.90-4.70 4.70 10.60 41.10 79.40 2.63 5.75 21.92 42.11

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Hydrogen end use systems
Car (fuel cell)7 Bus (fuel cell)7 : : 0.037 GJ/day (3.4 Nm3/day) 2.4 GJ/day (222 Nm3/day)

Hydrogen-fuelled internal combustion engines Hydrogen is a good fuel for IC engines and can improve efficiency by around 20% compared to the use of gasoline. Although still limited by the Carnot efficiency, this is comparable with the efficiencies achieved in practice with PEM fuel cells. The ideal thermal efficiency of an IC engine is given by:
k −1

1 η =1 −   r

where r = compression ratio and k = ratio of specific heats (Cp/ Cv). In hydrogen engines both ratios are higher due to hydrogen's lower self-ignition temperature and ability to burn in lean mixtures. The downside in a standard engine is a loss of power due to the lower energy content of the fuel/air mixture in the combustion chamber. Although NOx emissions are produced, they can be limited to an order of magnitude less than from a petrol engine. Work is needed to develop more advanced fuel injection techniques and to re-design combustion chamber and cooling system topography to hydrogen characteristics, rather than simply modifying conventional gasoline engines. Hydrogen fuelled turbines Hydrogen use in turbines and jet engines is similar to use of conventional jet fuel. There are some avoided problems from sediment and corrosion and considerably lower pollutant levels. Overall efficiency improvements are likely due to the capacity to increase gas inlet temperatures beyond the current limit of 800 oC. Fuel cells A fuel cell utilises a chemical process to convert hydrogen (or a hydrogen-rich fuel) into electrical energy and heat8. It can do so at high efficiency (not subject to limitations of the Carnot cycle), producing a nonfluctuating, DC power output. Most fuel cells (notably PEMs) have high power densities (i.e. high power output per unit weight, volume, or area). Different types of fuel cell are distinguished by their different electrolytes and the different temperatures reached during operation. There are limitations to fuel cell operation which mean that the theoretical cell voltage cannot be fully utilised: these include the oxygen deactivation barrier at the cathode, and mass transport problems caused by diffusion of gaseous species and water through the electrodes, electrolyte, and any catalyst layers in the fuel cell. Only about half the energy released by the reaction: can be converted into useful electrical energy. A typical fuel cell will have an area of 50 cm2 and generate a potential difference of 0.7 V. A stack of such cells is required to produce a useful overall voltage. Fuel cells display high efficiency across most of their output power range. This means that, whereas the internal combustion engine has a point of maximum operating efficiency (usually at high revolutions with large fall-off at low revolutions), the fuel cell has a very flat characteristic and is generally more efficient at

H 2 + O2 → 2 H 2 O

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fractions of its rated power. As a consequence, the fuel cell will show even larger advantages over an IC engine during a drive cycle compared to continuous output tests. The main disadvantage of fuel cells is the large number of ancillary units required, the so-called balance of plant. This equipment, for fuel supply, water removal, metering, fuel reformation (if required), pumps, compressors, and heat exchangers, makes a 200 kW phosphoric acid fuel cell generating system several times the volume of a similarly rated diesel or natural gas CHP unit.

Table 6 : Type of fuel cell

Fuel cell characteristics16 Electrolyte Mobile ion Potassium hydroxide (85 wt% high T) (35-50 wt% low T) OHOperating temperature Typical efficiency 50 - 90…(200) oC Applications Drawbacks/ research topics CO2 intolerant (problem if not acid electrolyte) Electrolyte retained in matrix (usually asbestos) Electrocatalysts (Ni, Ag, metal oxides, noble metals) Novel AFC designs using hydroxylconducting polymer electrolyte mebrane Requires CO levels < 10 ppm Develop to increase operating T towards 200 oC, increase efficiency, decrease CO sensitivity Catalyst typically Pt (being reduced) or Pt-Ru where CO impurities exist High T proton conducting electrolytes are

Alkaline

Space applications

Proton exchange membrane (PEM)

Polymeric H+

50 - 125 oC 40% +

Vehicles and mobile applications Low power CHP - higher power density than SOFC Start up time 1-3 s

16

Table data assembled from Rodney Allam presentation at IChemEng meeting and Larminie and Dicks (2000)8 and Lakeman and Browning (2001)1

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Phosphoric acid (PAFC)

Orthophosphoric acid H+

~ 220 oC 37%-42% (HHV)

Large numbers of 200 kW CHP systems in use Still low T so hydrocarbons reformed externally Suitable for medium to large scale CHP, up to MW capacity Potential to use CO and CH4 as fuels with catalyst

being developed SiC matrix Electro-catalyst in anode and cathode is platinum black

Molten carbonate (MCFC)

Lithium/potassium or sodium/potassium carbonate mixture CO32-

~ 650 oC

Electrolyte retained in a ceramic matrix of LiAlO2 Noble metal catalysts usually not required at this temperature Noble metal catalysts usually not required at this temperature

Solid oxide (SOFC)

Stabilised zirconia O2-

500 - 1000 oC

Suitable for all sizes of CHP systems, 2kW to multi-MW - more tolerant of impurities than PEMFC Potential to use CO and CH4 as fuels

Direct methanol

Sulphuric acid or polymer

50 - 120 oC

High temperature fuel cells were originally developed to make fuel cells more compatible with direct use of fossil fuels, but still need an external reformer (few kW - 11 MW = biggest ever built, but still a very low throughput!). With high temperature can do internal reforming (at the anode). US DOE cost goals for PEM fuel cells are capital cost < $500 (£350) / kW and electricity production cost $12.5/GJ ($0.045/kWhr); unpressurised cells should be able to produce 600 mA/cm2 at 0.6 V.

Table 7 : Fuel cell type/size Alkaline FC PEMFC 10 kW (today) 10 kW (future)

Economics of fuel cells (derived from Padro and Putsche, 19992) References Specific TCI ($/kW) Electricity price ($/kWh)

Barbir and Gomez 1997 in Padro and Putsche (1999)2 Barbir and Gomez 1997 in Padro and Putsche (1999)2

3,000 1,150

0.25-0.30 0.09-0.095

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7 kW (today) 7 kW (future) PAFC 25 kW (future) 200 kW (today) 250 kW (future) MCFC 25 kW (future) 250 kW (future) 3.25 MW (future) 100 MW (future) SOFC Direct methanol

Plug Power 1999 in Padro and Putsche (1999)2 Plug Power 1999 in Padro and Putsche (1999)2 Mugerwa et al 1993 in Padro and Putsche (1999)2 Garche 1998 in Padro and Putsche (1999)2 Mugerwa et al 1993 in Padro and Putsche (1999)2 Mugerwa et al 1993 in Padro and Putsche (1999)2 Mugerwa et al 1993 in Padro and Putsche (1999)2 Mugerwa et al 1993 in Padro and Putsche (1999)2 Mugerwa et al 1993 in Padro and Putsche (1999)2

8,500 4,000 2,250 3,000 2,440 1,355 1,740 1,330 600

(not provided) 0.07-0.10 0.13 (not provided) 0.13 0.12 0.11 0.10 0.06

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Hydrogen systems
Ogden and co-workers3 have worked extensively on possible architectures for hydrogen production and delivery systems for transport applications. Figure 1 shows potential near-term options and Figure 2 shows long-term options. In the short term, Ogden considers the main options to comprise: (a) hydrogen produced from natural gas in large, centralised reforming plant and delivered to the user as a liquid via refuelling stations, (b) hydrogen produced from natural gas in large, centralised reforming plant and delivered to the user via small scale pipeline networks to refuelling stations, (c) hydrogen derived from chemical industry waste sources and delivered to the user via small scale pipeline networks to refuelling stations, (d) hydrogen produced at the refuelling station via small-scale steam reforming of natural gas, (e) hydrogen produced at the refuelling station via small-scale water electrolysis. In the long term, Ogden expects that the options might increase to include: (a) a broadening of the fuel base for centralised hydrogen production to include gasification of biomass, coal, or muncipal solid waste, (b) large scale centralised electrolysis plants powered by wind, solar, or nuclear power, (c) centralised hydrogen production from gasification of biomass, coal, or muncipal solid waste, but including CO2 sequestration. There is a broad consensus that steam methane reforming (SMR) is the cheapest conventional option for large scale hydrogen production. However, there is a tendency to dismiss this route, due to the continued emission of CO2. Kvaerner have argued in favour of SMR coupled to CO2 sequestration in large scale plants, or the use of pyrolysis (which appears to have been neglected in many studies) with zero CO2 process emissions. Even without CO2 sequestration, it is possible that process efficiencies may result in overall CO2 emissions reductions from fuel cycles including the SMR process. Given the high costs of hydrogen storage and distribution, the optimisation between large scale centralised hydrogen production compared with small scale distributed production has yet to be resolved. Development work is continuing to reduce the costs of small to medium scale electrolysis plants and the development of advanced steam reformer technology as part of combined heat and power systems is seriously considered, lending an impetus to proposals for distributed systems. However, CO2 sequestration within SMR plants is only likely to be economically feasible in large plants, which will mitigate in favour of these plants and associated transmission grids if governments impose harsh penalties to encourage CO2 emissions reduction. Overall economics of hydrogen systems Taking the cost estimates above and considering only the best and worst cases, without reference to likely technological development, a snapshot is obtained of the current economic feasibility of hydrogen energy systems. These costs are compared with the current cost of petrol (at the pump and pre-tax) and natural gas supplies. The comparison must be considered in the light of overall system costs and energy efficiency ("well-to-wheels") and possible future tax regimes to mitigate against the emission of greenhouse gases. Comparing the costs of natural gas at the wellhead (1.80-5.98 $/GJ) or petrol on the open market at $20/barrel (3.5 $/GJ) with levelised costs for hydrogen production from SMR (5.44-11.22 $/GJ) or renewable-electrolysis systems (20-42 $/GJ), it is clear that hydrogen is expensive. However, the assessment is based on current fossil fuel prices and must be considered against a background of falling costs for renewable electricity generation. The work by Mann et al (1998)5 shows that costs for hydrogen from renewable-electrolysis systems could fall considerably (11-25 $/GJ) by 2010, due to cost improvements for large wind systems (currently being realised) and electrolyser systems (which can be expected to benefit from technology improvements in fuel cell design and manufacture).

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The pre-tax UK pump price for petrol (i.e. including all delivery and transportation costs) is around 8 $/GJ, rising to 31 $/GJ when tax is included. Given short term compressed hydrogen gas storage and only local transportation, hydrogen from renewable-electrolysis could be competitive if it was zero-rated for tax, even today. Table 8 : Reference costs for overall hydrogen production Fuel price ($/GJ) 11.22 5.44 20.2 (22.6) 11.0 (12.6) 41.8 24.8 31 7.9 3.5 1.80 5.98

Facility size References Specific TCI (106 Nm3/day) ($/GJ) Steam methane reforming − 48% of world hydrogen production (1998) 0.27 (small) Leiby 1994 in Padro and Putsche (1999)2 27.46 6.75 Foster-Wheeler 1996 in Padro and Putsche (1999)2 10.00 Electrolysis - wind based 0.247 (0.02317) Mann et al 1998 in Padro and Putsche (1999)2 − 158.6 (165.7) technology 200018 0.279 (0.028) Mann et al 1998 in Padro and Putsche (1999)2 − 92.5 (91.1) technology 2010 Electrolysis - solar photovoltaics based 0.195 (?) Mann et al 1998 in Padro and Putsche (1999)2 − 485.8 technology 2000 0.209 (?) Mann et al 1998 in Padro and Putsche (1999)2 − 242.0 technology 2010 Petrol 70p/litre Pump price (December 2001) 17.8p/litre Estimated pre-tax (Dec 2001) $20/barrel Natural gas $1.90/MBtu Average annual wellhead price (Henry Hub 199099) $6.31/MBtu Average wellhead spot price (Henry Hub Dec 2000)

17 18

GD spreadsheet calculation based on data given in original paper Mann et al note the potential to increase revenue from these plants by utilising a grid connection to purchase power at offpeak periods when the renewable generators were not operating and/or to sell electrical power at peak time (at the cost of reduced hydrogen production)

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Conclusions
While most attention is focussed on producing hydrogen from renewable power sources such as wind and solar, current cost projections clearly favour the production of hydrogen from fossil fuel sources, most notably from methane by the SMR process. Some improvements in overall efficiency (arising largely from the good performance of fuel cells used on an urban driving cycle) may result in reduced carbon dioxide emissions from this latter route, but a large reduction in emissions would require sequestration at significant extra cost. The costs of storage and transportation of hydrogen lead many analysts to favour the development of small scale distributed production systems (with reduced storage requirements) close to the point of end-use of hydrogen. However, if SMR is the chosen technology and CO2 sequestration is regarded as mandatory or, at the very least, highly advisable, then this can be achieved more cheaply in larger, centralised plants. With regard to carbon sequestration, a still more promising route would appear to be pyrolysis (e.g. the Kvaerner CB&H process) by which means hydrocarbons are decomposed in the absence of oxygen. According to Kvaerner's cost projections, the cost of hydrogen from pyrolysis is only slightly greater than from the SMR process, even before income from carbon black sales are accounted for. Of course, sequestration of carbon black would be a more straightforward process than for CO2. Hydrogen production by electrolysis depends on the price of electricity and the capital cost of the electrolysis plant. It is possible that early niche markets may arise where excess off-peak electricity is available or the costs can be used to offset the need for grid reinforcement for large renewable energy developments. Technological developments are required in the field of hydrogen storage and distribution. The large current activity in fuel cell technology is expected to result in significant cost reductions for fuel cells. Much of the technical knowledge should be relevant to reducing costs for electrolysers as well and a more detailed study of cost projections for renewable-electrolysis is required. Overall, it is evident that increased use of hydrogen as an energy carrier could result in substantial improvements in greenhouse gas emissions through: (i) sequestration of carbon or CO2 in large, centralised plants processing fossil fuels, (ii) efficiency improvements from using fuel cells (and possibly even IC engines) with hydrogen, (iii) generation of hydrogen using renewable energy resources and its subsequent use as a transport fuel.

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Figure 1 : Near term options for supplying hydrogen transportation fuel (reproduced from Ogden, 19993)

Figure 2 : Long term options for supplying hydrogen transportation fuel (reproduced from Ogden, 19993)

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Appendix 1 : Energy units
OECD uses tonnes of oil equivalent (toe) as the basic unit to compare disparate energy balances. 1 toe is defined as 107 kilocalories (41.868 GJ), equal, within a few per cent, to the net heat content of 1 tonne of crude oil19. 1 Mtoe 1 Mtoe 1 Mtoe 1 Mtoe 1 TWh(e) 1 TWh(e) 1 Mtce 1 Mtce = = = = = = = = 4.1868 x 104 TJ 3.968 x 107 MBtu 11630 GWh 7.3 million barrels21

=

average power of 1.33 GW over 1 year20

0.086 Mtoe (primary energy equivalent for hydro, non-thermal electric) (0.086 / 0.33) Mtoe (primary energy equivalent for nuclear) 1 million tonnes of coal equivalent (= 0.697 Mtoe)22 8141 GWh

Coal: 1 MW (thermal power) [MWth] = approx 1,000 kg steam/hour 1 MW (electrical power) [MWe] = approx MWth / 3 A 600 MWe coal-fired power station operating at 38% efficiency and 75% overall availability will consume approximately: - Bituminous coal (CV 6,000 kcal/kg NAR): 1.5 Mt/annum - Brown coal (CV 2,250 kcal/kg NAR): 4.0 Mt/annum Hydrogen: Lower heating value = Upper heating value = Density (gaseous) = Density (liquid) = 1 Nm3 H2 = 106 Nm3 H2 = 106 Nm3 H2 = 1 Mtoe = 1 kWh 1 million BTU 1 $/GJ = = = 10800 kJ/Nm3 = 120.0 MJ/kg = 12770 kJ/Nm3 = 141.9 MJ/kg 0.09 kg/m3 70.9 kg/m3 (-252 oC) 10,800 kJ (LHV) 10,800 GJ (LHV) 0.258 x 10-3 Mtoe 3.877 x 103 million Nm3 H2 3.6 x 10-3 GJ 1.055 GJ 0.25 p/kWh (@ $1.44 = £1.00) 3.0 kWh/Nm3

19 20 21 22

International Energy Agency web site: http://www.iea.org/stats/files/mtoe.htm Royal Commission on Environmental Pollution preferred comparison Oil Industry Conversions: http://www.nepo.go.th/ref/UNIT-OIL.html World Coal Institute web site : http://www.wci-coal.com/facts_conversion.htm

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Appendix 2 : Hydrogen characteristics and safety
Hydrogen characteristics23: Units Lower Heating Value (MJ/kg) Auto-ignition Temperature24 (°C) Flame Temperature (°C) Limits of Flammability in Air (Vol. %) Minimum Ignition Energy25 (µJ) Limits of Detonation in Air26 (Vol. %) Theoretical Explosive Energy (kg TNT/m3 gas) Diffusion Coefficient in Air27 (cm2/s) Standard atmosphere : 14.696 lbf in-2 105 Pa = = Hydrogen Natural gas Gasoline 120 50 44.5 585 540 228-501 2045 1875 2200 4-75 5.3-15 1.0-7.6 20 290 240 13-65 6.3-13.5 1.1-3.3 2.02 7.03 44.22 0.61 0.16 0.05

1.01325 x 105 Pa 1 bar

23 24 25

26 27

IEA Greenhouse Gas R&D Programme : http://www.ieagreen.org.uk/h2rep.htm Potential for spontaneous combustion (i.e. hydrogen is marginally safer) Hydrogen appears more likely to ignite, but even the spark from a static electric discharge has sufficient energy to ignite natural gas, so the factor 10 difference has little practical significance Explosive range of hydrogen is greater, but methane is explosive at much lower concentrations Hydrogen mixes much faster in air than natural gas or gasoline vapour; this is an advantage in the open, but a disadvantage in enclosed spaces (hydrogen being very much lighter than air rises quickly, as does methane to a lesser extent; petrol fumes remain close to the ground)

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Appendix 3 : Basic format for technology summaries
Item Technology type Specific model Typical plant size(s) Efficiency Lifetime Capacity factor H2 throughput (Nm3/day; GJ/year) Capital cost / unit H2 throughput Running costs / unit H2 throughput Selling cost of H2 Likely innovations (next 10 years) Possible innovations (> 10 years) Likely selling cost of H2 (after 10 years) Likely selling cost of H2 (after 20 years) Likely selling cost of H2 (after 50 years) Typical data

The economics are clearly affected by the required rate of return on investment and the total lifetime of the plant.

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References
1 2 3 4 5

6 7 8

Lakeman, J.B., Browning, D.J., DERA, Global Status of Hydrogen Research, ETSU F/03/00239/REP, 2001 Padro, C.E.G., Putsche, V., Survey of the economics of hydrogen technologies, NREL Technical Report NREL/TP-570-27079, 1999 Ogden, J.M., Prospects for building a hydrogen energy infrastructure, Ann. Rev. Energy Environ. 1999, Vol. 24, p. 227-279, 1999 Gaudernack, B., Lynum, S., Hydrogen from natural gas without release of CO2 to the atmosphere, Int. J. of Hydrogen Energy, Vol. 23, No. 12, p. 1087-1093, 1998 Mann, M.K., Spath, P.L., Amos, W.A., Technoeconomic analysis of different options for the production of hydrogen from sunlight, wind, and biomass, Proc. of the 1998 US DOE Hydrogen Program Review, NREL/CP-570-25315 Amos, W.A., Costs of storing and transporting hydrogen, NREL/TP-570-25106, November 1998 Ogden, J.M., Hydrogen energy systems studies, Proc. of the 1999 US DOE Hydrogen Program Review, NREL/CP-570-26938, 1999 Larminie, J., Dicks, A., Fuel cell systems explained, Wiley, 2000

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The inter-disciplinary Tyndall Centre for Climate Change Research undertakes integrated research into the long-term consequences of climate change for society and into the development of sustainable responses that governments, business-leaders and decisionmakers can evaluate and implement. Achieving these objectives brings together UK climate scientists, social scientists, engineers and economists in a unique collaborative research effort. Research at the Tyndall Centre is organised into four research themes that collectively contribute to all aspects of the climate change issue: Integrating Frameworks; Decarbonising Modern Societies; Adapting to Climate Change; and Sustaining the Coastal Zone. All thematic fields address a clear problem posed to society by climate change, and will generate results to guide the strategic development of climate change mitigation and adaptation policies at local, national and global scales. The Tyndall Centre is named after the 19th century UK scientist John Tyndall, who was the first to prove the Earth’s natural greenhouse effect and suggested that slight changes in atmospheric composition could bring about climate variations. In addition, he was committed to improving the quality of science education and knowledge. The Tyndall Centre is a partnership of the following institutions: University of East Anglia UMIST Southampton Oceanography Centre University of Southampton University of Cambridge Centre for Ecology and Hydrology SPRU – Science and Technology Policy Research (University of Sussex) Institute for Transport Studies (University of Leeds) Complex Systems Management Centre (Cranfield University) Energy Research Unit (CLRC Rutherford Appleton Laboratory) The Centre is core funded by the following organisations: Natural Environmental Research Council (NERC) Economic and Social Research Council (ESRC) Engineering and Physical Sciences Research Council (EPSRC) UK Government Department of Trade and Industry (DTI) For more information, visit the Tyndall Centre Web site (www.tyndall.ac.uk) or contact: External Communications Manager Tyndall Centre for Climate Change Research University of East Anglia, Norwich NR4 7TJ, UK Phone: +44 (0) 1603 59 3906; Fax: +44 (0) 1603 59 3901 Email: tyndall@uea.ac.uk

Other titles in the Tyndall Working Paper series include: 1. A country-by-country analysis of past and future warming rates, November 2000 2. Integrated Assessment Models, March 2001 3. Socio-economic futures in climate change impact assessment: using scenarios as ‘learning machines’, July 2001 4. How high are the costs of Kyoto for the US economy?, July 2001 5. The issue of ‘Adverse Effects and the Impacts of Response Measures’ in the UNFCCC, July 2001 6. The identification and evaluation of suitable scenario development methods for the estimation of future probabilities of extreme weather events, July 2001 7. Security and Climate Change, October 2001 8. Social Capital and Climate Change, October 2001 9. Climate Dangers and Atoll Countries, October 2001 10. Burying Carbon under the Sea: An initial Exploration of Public Opinions, December 2001 11. Representing the Integrated Assessment of Climate Change, Adaptation and Mitigation, December 2001 12. The climate regime from The Hague to Marrakech: Saving or sinking the Kyoto Protocol?, December 2001 13. Technological Change, Industry Structure and the Environment, January 2002 14. The Use of Integrated Assessment: An Institutional Analysis Perspective, April 2002 15. Long run technical change in an energy-environment-economy (E3) model for an IA system: A model of Kondratiev waves, April 2002 16. Adaptation to climate change: Setting the Agenda for Development Policy and Research, April 2002 17. Hydrogen energy technology, April 2002 18. The development of large technical systems: implications for hydrogen, March 2002 19. The role of hydrogen in powering road transport, April 2002 20. Reviewing organisational use of scenarios: case study - evaluating UK energy policy options, August 2002 The Tyndall Working Papers are available online at: http://www.tyndall.ac.uk/publications/working_papers/working_papers.shtml