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

Steam Methane Reforming

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

POX Reaction: CH4 + ½ O2 2 H2 + CO (1250oC)

Partial Oxidation

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

TubeTrailers Medium Pressure

Vessels

HyPak &MaxiPak

CylinderSupply

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