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Hydrogen Production, Supply and Distribution
By Chris SpilsburyAir Products PLC
Hydrogen Production WorkshopUniversity of Glamorgan14 February 2001
Key Topics
l Company Overviewl Hydrogen Manufacturing Methodsl Hydrogen Manufacture Energy Requirement
and Effect of Scale on Costl Hydrogen Supply and Distributionl Summary
lCryogenic Air Sepn
– Oxygen– Nitrogen– Argon
lHydrogenlHeliuml Specialty GaseslNon-cryogenic Air Separation
Air Products Overview
INDUSTRIAL GASES$3.0 BILLION
CHEMICALS$1.6 BILLION
l Emulsion Polymersl Polyvinyl Alcoholl Polyurethane
Intermediates/AdditiveslAmines (C1-C4)l Epoxy Additives
EQUIPMENT & SERVICES$0.4 BILLION
lNatural GasLiquefaction
lHydrogen RecoverylCogenerationlAir Pollution Control
SystemslHydrocarbon
Processing
World Leader in Merchant Hydrogenl Largest merchant hydrogen producer
l Own & operate over 50 plants - Americas, Europe, Asial Installed over 1200 customer H2 installationsl Produce over 25 million m3 per day H2
l 7 H2 pipeline systems around the world– 5 Countries– 340+ miles, 21 plants
– 77 customersl 6 liquid H2 facilitiesl Sell H2 purification equipment (cryogenic, PSA, membranes)
Major Sources of Hydrogen• Steam methane reforming (SMR)• Refinery and Chemical off-gases
• Partial Oxidation Of Hydrocarbons(sometimes combined with auto-thermalreforming and gas heated reforming)
• Coal Gasification• Methanol Dissociation• Ammonia Dissociation• Water Electrolysis
Reformer
Steam EXPORTSTEAM
H2Products
Hydrocarbonfeeds
Hydro-desulphurisation
ProcessGas
Boiler
HTS/LTSSHIFT PSA
FUEL
Hydrocarbonfeeds
Hydro-desulphurisation
H2Products
HTS/LTSSHIFT PSA
FUEL
Steam
ReformerProcess
GasBoiler
EXPORTSTEAM
Steam Methane Reforming
REFORMING SHIFTCH4 + H20 3H2 + CO CO + H20 H2 + CO2
880 oC
REFORMER FUEL REFORMER FUEL
HydrocarbonFeedHydrocarbonFeed
HH22PURIFICATIONPURIFICATION
EXPORT STEAM
FD FAN
APHTFGBFGBSHOCKBOILER
HTS
PROCESSGAS BOILER
AIR COOLER
COOLER
NGF PRHT #2
BFWPREHEAT #1
LTS BFWPREHEAT #2NGF PRHT #1
FEED COMPR.
STEAMSUPER HEATER
SCR UNIT COMBUSTIONAIR PREHEAT
ID FANID FAN
PROCESSSTEAM
REFORMER
HYDRO
ZnO
PURGE GASTO FUEL
FURNACE AIR
STEAM
BFW
H2 PRODUCT
Steam Reforming - Simplified PFD
Air Products Tosco Martinez, CA
A plant of this size produces enough Hydrogen tooperate a fleet of 2000 Fuel Cell Buses
Summary of ReactionsSteam Reforming:
Shift:
POX / Gasification Reaction:
CH4 + H2O 3H2 + CO
CH4 + ½ O2 2H2 + CO
- CH2- + ½ O2 H2 + CO
CH- + ½ O2 ½ H2 + CO
CO + H2O H2 + CO2
Summary of Reactions (cont’d)Methanol Dissociation:
Ammonia Dissociation:
Electrolysis Reaction:
CH3OH + H2O 3H2 + CO2
H2O H2 + ½ O2
2NH3 3H2 + N2
300oC
300oC
70oC
Efficiency of (gaseous) Hydrogen ProductionTotal Energy Consumption
NatGas equivalent (Nm3 NG / Nm3)
Fossil Fuel Energy Consumption Excluding Electricity (Nm3 NG / Nm3 H2)
Steam Reforming 0.41 0.38
Oxygen Reforming (ATR / POX / GHR)
0.40 - 0.47 0.33 - 0.39
Gasification (coal) - current technology
0.59 0.52
(Gasification (coal) - future potential)
(0.47) (0.40)
Methanol Dissociation
0.88** 0.82
Water Electrolysis 1.30** 0
** source – ‘Hydrocarbon Processing’
Efficiency of Hydrogen Production – key points• Steam Reforming is the lowest fossil fuel energy consumer in a
non-renewable energy environment• At the present time steam reforming is the most common form of
bulk hydrogen production• Oxygen Reforming becomes increasingly attractive when plant
electric power consumption is provided via renewable means• Oxygen routes require more external ‘energy/heat’ integration to
achieve best net efficiency• Water Electrolysis results in zero fossil fuel energy consumption
in a renewable energy environment but has the highest in a non-renewable environment.
l Natural Gas (On-Purpose) 82%- Steam Methane Reforming (SMR)- Partial Oxidation (POX)- Auto-Thermal Reforming
l Purification of Chemical By-Product (Off-Gas) 18%- Chlor-Alkali Off-Gas- Ethylene, Styrene Off-Gases etc.
l Electrolysis of Water <0.1%
US Capacity
Natural Gas Reforming is DominantProduction Technology
Future Hydrogen Manufacturing Developments• Steam reforming capital costs will fall, efficiency will show little
change• Oxygen reforming routes will see new and improved technologies
commercialised e.g. Gas Heated Reformers• Increased scale may favour Oxygen based reforming routes• Coal & heavy hydrocarbons gasification efficiency will improve• There will be increased interest in pyrolysis / gasification of biomass
for H2 production• CO2 capture and sequestration from fossil fuel H2 production
processes may become reality• There will be increased interest in H2 from electrolysis (especially
50+ years from now as fossil fuels become increasingly scarce)
Size versus cost of H2 production
Typical example based on steam reforming
0
1000
2000
3000
4000
5000
6000
10 100 1000 10000 100000 1000000
Plant Size (NM3/h H2 Production)
Relat
ive H
ydro
gen
Cost
2,800 28,000 280,000 2,800,000Usage m3/Day
Hydrogen Distribution Modes
Pipeline
Large Onsite Plants
Small Onsite Plants
Liquid Hydrogen
Tube Trailer
Liquid Hydrogen
• High Purity• Extensive distribution
infrastructure• Cost-effective transport
and storage option
Hydrogen Liquefaction• Accomplished by Joule Thomson refrigeration in small
plants, mechanical expansion refrigeration in biggerplants
• Energy cost of compression and delivery as gas is 10-20% that of energy to liquefy
• Liquefaction energy is 0.2-0.3 Nm3 Nat Gas equivalentper Nm3 Hydrogen for power generation from fossilfuel.
• H2 liquefaction or compression has zero fossil fuelconsumption in renewable environment
Onsite Generation• Economical hydrogen supply• Dedicated production system• High on-stream factor with
optional back-up• Located on customer’s site• Financing, operation and
maintenanceundertaken by Air Products
• Over 50 years’ experience ofdesigning and operatinghydrogen productionsystems
Pipeline Supply
• Suited to areas of largehydrogen demand
• Multiple supply sourcesoffer added security andflexibility
• Benefits obtained fromplant scale andoperational efficiencies
CTA Fuel Station Schematic
Hydrogen Storage
Bus
Telemetry andRemote Monitoring Control
SignalTo CHC
DataTransfer
Liquid HydrogenTank
VacuumJacketed
PipeVaporizers
CryogenicHydrogen
CompressorHydrogen
Supply
H.P. StorageCHCControlPanel
Control PanelHydrogen
Transfer System
abc
H2 Production at Fuel StationNatural GasMethanolGasoline/Diesel
PSA
Water FuelProcessor
HP H2 Storage Tubes
Water
Fuel Dispenser
CompressorPurificationShiftConverter
SyngasH2, CO, CO2, N2
CO2, N2H2, CO2, N2 H2 (99.99%)
CO + H2O
CO2 + H2
SMRATRPOX
Fuel Cell Bus
FUEL STATIONFUEL STATIONFUEL STATION
FUEL STATIONFUEL STATIONFUEL STATION
FUEL STATIONFUEL STATIONFUEL STATION
FUEL STATIONFUEL STATIONFUEL STATION
FUEL STATIONFUEL STATIONFUEL STATION
Large Regional Gaseous Hydrogen Plant (1) 3 Mi PIPELINE FOR 30 TONS/DAY(10) 30 Mi PIPELINES FOR 300 TONS/DAY
GH2 PIPELINE30 Mile 400 PSI
3 Mile
3 Mile
3 Mile
3 Mile
30-300 TONS/DAYGASEOUS
HYDROGENPLANT
30-300 TONS/DAY30-300 TONS/DAYGASEOUSGASEOUS
HYDROGENHYDROGENPLANTPLANT
Key Points:• Steam Reforming is currently the dominant Hydrogen
production process• Existing ‘mature’ processes will have some further
development which will moderately lower the cost ofHydrogen production
• The cost of Hydrogen is very sensitive to scale,especially below 1000 Nm3/h H2 production
• Hydrogen delivery methods are selected based on sizeof supply and number of customers
• Economy of scale reduces cost of both manufactureand delivery
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