The Hydrogen Fuel Quality Issue: The Vision

of a Fuel Supplier

Françoise Barbier and Martine CarréAir Liquide Research & Development

NHA Conference – 5 May 2010

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Outline

Company overview

Fuel quality issues

Hydrogen production and supply

Analytical methods capabilities

Hydrogen quality and cost

Summary

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Air Liquide overview

The world leader in gases for industry, health & the environment

Total revenue 2009 : €12 billion

Over 1 million customers in 75 countries

42300 employees

A strategy built around 5 growth drivers

Energy Environment Emergingeconomies

Health High-Tech

36% of Air Liquide’s revenue derived from gas applications designed to preserve life and protect the environment

60% of Air Liquide’s R&D budget devoted to developing technologies for sustainable development

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More than 40 years of experience with hydrogen for industrial and space applications

More than 200 H2 production units

Broad range of H2 distribution modes

pipelines, trucks, cylinders

Active since 2000 in Hydrogen Energy on the full supply chain from production to fuel cell

Research & Development

High technologies

H2 fueling stations

Fuel cells through

Deployments

Worldwide large-scale projects

Air Liquide: A global player in the Hydrogen Energy business

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Paving the way with early markets …

… to be ready for 2015

Hychain utility vehicle poweredby Axane fuel cell

Airport loader poweredby Axane fuel cell

Remote site: Bouygues Telecom antenna

Axane portable fuel cell

Hychain fuel cell cargo bike

Air Liquide H2 refueling station for a fleet of busses in the city of Whistler

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Supplying H2 at refueling stations

US Delaware, 350 bar Canada Kapuskasing, 700 bar

Canada Whistler 2010, 700 barJapan Kawasaki, 350 bar

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H2 fuel quality specifications (ISO/TS 14687-2)

International work (ISO TC 197/WG 12) is in progress to specify the quality of hydrogen for utilization in PEM fuel cell road vehicle systems

still in discussion

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Defining H2 fuel quality standard

Impurities versus fuel cell performance degradation

Trade-off between H2 purity and H2 supply costCost for production and delivery

Cost for quality assurance including impurities analysis

Analytical methods to be applied and their capabilities (quantification limits)

Factors affecting the threshold limits of impurities

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The quality of hydrogen is known to affect the operation of fuel cells

Different behavior depending on impurities Need to classify “negative” impurities: “critical” or “significant”

Effects of H2 impurities on operation of fuel cells

Effect of CO Effect of H2SPEM fuel cell performance decreases rapidly with the increase of CO or H2S

concentrations introduced into hydrogen

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Diverse H2 sourcing

Different production pathways and feedstocks

The future standard must reflect this diversity

Fossil fuels: the current route• Steam methane reforming• Partial oxydation /

autothermal reforming of hydrocarbons

• Coal gasification

Water and electricity: pathway towards renewable fuel

•Low temperature electrolysis

•High temperature electrolysis

Renewable sources: technologies being developed

•Bio-derived liquids reforming•Biogas reforming•Biomass gasification•Biological processes)•Photo(electro)catalysis•Solar thermochemical cycles

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Traditional H2 production & purification techniquesH

ydro

carb

on

sou

rce

SMR

POX

ATR

H2 + COSyngas

PSA

Membrane

Cryogenic

Purification

H2

Production

SMR = Steam Methane ReformerPOX = Partial OxidationATR = Autothermal ReformerPSA = Pressure Swing Adsorption

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Description of H2 purification with PSA

Based on adsorbent technologyAdsorb different gas impurities depending on the affinity

Multiple adsorbents: silica, alumina, molecular sieves, activated carbons

Better quality of H2 is produced compared to other purifications process

Between 99% to 99.99%RELATIVE STRENGTH OF ADSORPTION

+ ++ +++ ++++

He Ar CO C3H6

H2 O2 CH4 C4H8

N2 CO2 C5+

Alumina C2H6 H2S

Carbon Prefilter C2H4 NH3

Activated Carbon C3H8 H2O

Molecular Sieve

- Stre

ng

th +

The PSA is very effective for removing H2S, NH3, CO, CO2, CH4

but it has relatively more difficulty retaining inert gases

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General PSA relationship

PSA Unit size

H2 recovery

H2 Cost

H2 Product purity - PSA inlet

H2 Product purity – PSA outlet

Changing SMR and PSA operating conditions in existing plants to meet ISO specifications significant effect on the H2 cost

Plant design dedicated to H2 fuel quality H2 cost may be slightly affected by the ISO specifications

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Gas in tube trailer & cylinder

Liquid in cryogenic truck

Gas in pipeline

Producti

on

Purifica

tion

Compress

ion

Liquefaction

Delivery

Dispen

ser

H2 gas production

center

The hydrogen chain

Existing hydrogen infrastructure

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Impurities in the hydrogen chain

Commercial hydrocarbon feedstockH2S, MeSH, EtSH, oxygenates (CH3OH…), N2, higher hydrocarbons, alkenes, alkynes …

SMR operating conditionsCO, CO2, CH4, NH3 ...

Subsequent purification processPSA can reduce impurity concentration at very low levels

Delivery modesPipelines: chemical industry grades

Tube trailers: various grades

Cylinders: various and special grades case-by-case

Cryogenic truck: specifications > 99.999%

Purity of gaseous H2 from cryogenic methods is extremely high

Relative amount of impurities in H2 is dependent on the infrastructure diversity:

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Commercial hydrogen impurities

No grade for hydrogen as a fuel

H2 grade Minimum assay purity

Total max impurity level

ISO TS 14687-2ISO TS 14687-2 fuel specificationfuel specification

99.99 %99.99 %N40N40

100 ppm100 ppm

Compressed,Compressed,semiconductor CGA (L)semiconductor CGA (L)

99.999 %99.999 %N50N50

10 ppm10 ppm

Compressed, for Compressed, for analysis CGA (F)analysis CGA (F)

99.995 %99.995 %N45N45

50 ppm50 ppm

Compressed, for Compressed, for analysis Europe analysis Europe

99.999 %99.999 %N50N50

10 ppm10 ppm

Compressed, high Compressed, high industrial grade, Europeindustrial grade, Europe

99.995 %99.995 %N45N45

50 ppm50 ppm

Compressed, industrial Compressed, industrial grade, Europegrade, Europe

99.9 %99.9 %N30N30

1000 ppm1000 ppm

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Quality control for H2 as a fuel

Customers are requesting analysis of H2 according to the specifications defined in the ISO standard:

Which analytical protocol can be applied ?

Is it possible (or practical) for all the species in the ISO specification ?

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Which analytical protocol can be applied ?

Make difference between

Analytical methods for demonstrating compliance to specifications which can be done off-line in laboratories after sampling of H2

and

Analytical method for continuous control of species done on-line in plants

Various options

1. on-line analysis of all the species in the ISO specifications

2. on-line analysis of “canary” species

3. batch analysis of all the species in the ISO specifications

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Analytical protocol relationship

Technical capability

Guarantee for customer Cost

1. On-line analysis of all species ☹ ☺ ✰✰✰

2. On-line analysis “canary” species ☹ ☺ ✰✰

3. Off-line analysis by batch analysis ☺ ☹ ✰

Not enough available analytical methods

Which “canary” species to choose ?

High cost due to number of impurities to control and low level (ppb)

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Example: On-line analysis by FTIR method

Typical data from Fourier Transform Infra-Red (FTIR) analyzer

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Example: Off-line analysis by GC method

Typical data from Gas Chromatograph (GC)

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Traceability in H2 impurities analysis

For the development and validation of newly developed analytical methods:

Strong needs for standard and/or reference gas mixture to control the accuracy of the measurement

Strong needs for Round Robin Test for validation of selected analytical methods and getting statistically reasonable numbers of Limit of Detection and Limit of Quantification

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H2 quality assurance procedure

Continuous on-line monitoring of all impurity species with one-by-one identification

Very expensiveCannot be routinely applied

On-line analysis “canary” species (+ batch analysis of other species)

Need to identify a canary constituent: CO suggestedReasonable cost if assumption of CO detection proves that all other impurity levels will be known

Off-line analysis by batch analysis Spot analysisHave representative sampling

Various solutions more or less complex and financially viable

Work in progress with ISO TC 197 WG 12 members

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Addressing hydrogen quality and cost

Identify the impurities and the contents that have a real detrimental impact on operation of PEM fuel cells (“right” set of H2 specifications)

Define what type of analysis is needed to meet the specification (“right” analysis)

Costs need to be considered broadly

Consider impact on possibility to use existing sources• Implementation of additional measures and purification on

existing plants is costly and not always feasible

• Loss of hydrogen (= loss of efficiency and capacity)

Need for a cost-benefit analysis (“right” balance between cost and impact on fuel cell)

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Summary

H2 quality specifications must be practical, sustainable and cost effective to implement

Difficulties still exist for defining the quality specification of the ISO standard

Analytical methods are not qualified at worldwide level

All international key actors for ISO standardization are required for consensus

The target is moving: evolution of fuel cell requirements with the development of new materials

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Thank you for your attention

francoise.barbier@airliquide.com