Materials for the Hydrogen Economy 2007 pot

Materials for the Hydrogen Economy... Materials for the Hydrogen EconomyEdited by Russell H.. Reasonable efforts have been made to publish reliable data and information, but the author

Materials for the Hydrogen Economy

Materials for the Hydrogen Economy

Edited by

Russell H Jones George J Thomas

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International Standard Book Number‑13: 978‑0‑8493‑5024‑5 (Hardcover)

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Library of Congress Cataloging‑in‑Publication Data

Materials for the hydrogen economy / editors, Russell H Jones, George J

Thomas.

p cm.

Includes bibliographical references and index.

ISBN‑13: 978‑0‑8493‑5024‑5 (alk paper)

1 Hydrogen‑‑Industrial applications 2 Materials‑‑Research 3 Hydrogen as fuel‑‑Research 4 Hydrogen industry I Jones, Russell H II Thomas, George J

to assemble this book, the contributors who helped make it a

reality, and the publisher for their patience with this project.

— Russell H Jones

Preface ix

Introduction xi

Contributors xix

Abstract xxi

Editor xxiii

Chapter 1 Issues.in.Hydrogen.Production.Using.Gasification 1

James P Bennett Chapter 2 Materials.for.Water.Electrolysis.Cells 37

Paul A Lessing Chapter 3 High-Temperature.Electrolysis 61

S Elangovan and J Hartvigsen Chapter 4 Materials.Development.for.Sulfur–Iodine.Thermochemical. Hydrogen.Production 81

Bunsen Wong and Paul Trester Chapter 5 Materials.Requirements.for.Photobiological.Hydrogen. Production 123

Daniel M Blake, Wade A Amos, Maria L Ghirardi, and Michael Seibert Chapter 6 Dense.Membranes.for.Hydrogen.Separation.and.Purification 147

U (Balu) Balachandran, T H Lee, and S E Dorris Chapter 7 Effects.of.Hydrogen.Gas.on.Steel.Vessels.and.Pipelines 157

Brian P Somerday and Chris San Marchi Chapter 8 Hydrogen.Permeation.Barrier.Coatings 181

C H Henager, Jr.

used.in.their.manufacture In.other.words,.materials are a key enabling technology

to a viable hydrogen economy

be overcome Each of the stages in the hydrogen fuel chain—production,

distri-bution, storage, utilization (e.g., fuel cell, internal combustion engines)—employs

gas.emissions.from.fossil.fuels.while.also.reducing.our.dependence.on.foreign.fos-sil fuels Photoelectrochemical and photobiological processes are two examples.

that are solar energy driven Photobiological hydrogen production is a process

anode catalyst materials Some non-Pt cathode catalysts that are being evaluated

include.TaO0.92,.N1.05 ZrOx,.pyrolyzed.metal.porphyrins.such.as.Fe-.or.Co-Nx/C.and

A primary limitation of YSZ is its low ionic conductivity To overcome this,.

thinner electrolyte layers have been developed and yttria has been replaced with

5 Roberts,.Paul The End of Oil: On the Edge of a Perilous New

T H Lee

Energy.Technology.DivisionArgonne.National.LaboratoryArgonne,.Illinois

Paul A Lessing

Materials.DepartmentIdaho.National.LaboratoryINL.Research.CenterIdaho.Falls,.Idaho

Paul Trester

General.AtomicsSan.Diego,.California

Bunsen Wong

General.AtomicsSan.Diego,.California

Zhenguo Yang

Pacific.Northwest.National

LaboratoryRichland,.Washington

Xiao-Dong Zhou

Pacific.Northwest.National

LaboratoryRichland,.Washington

Production Using Gasification

O2/C ratios, and the level of carbon beneficiation In the reducing environment of.

gasification, between 20 and 30% of the O2 required for complete combustion of

the.C.and.H2.in.the.carbon.feedstock3.is.supplied Because.of.the.controlled.oxygen

shortage, gasification produces a primary product of CO and H2, called synthesis

bon.material.generated.as.a.by-product.or.as.a.bottom.material.from.petroleum.refin-ing (environmentally sensitive materials that are difficult to find applications for).

is easily and economically processed by gasification into CO and H2 used in the

manufacture of high-value chemicals and energy.9 Varying amounts of V and Ni

Partial oxidation

.is.the.basic.gasification.reaction,.breaking.down.a.hydroge-nated.carbon.feedstock.(typically.coal.or.petroleum.coke).using.heat.in.a.reducing

environment,.producing.CO.and.H2

.(equation.1.2) A.number.of.techniques.are.uti-lized.to.separate.H2.from.the.CO.in.syngas.or.to.enrich.the.H2.content.of.the.syngas

These.include.H2.membranes,.liquid.adsorption.of.CO2.or.other.gas.impurities,.and

the.water.shift.gas.reaction.(equation.1.4)

CxHy.+.x/2.O2.→.xCO.+.y/2.H2

Autothermal reforming is a term used to describe the combination of steam.

. TyPes of CommerCIal gasIfIers

Different types of high-temperature gasifiers are commercially used to produce

fIgure .

Several.designs.of.commercially.used.gasifiers:.(a).General.Electric,.(b).Con-ocoPhillips,.(c).Shell—gas.and.liquid.feedstock,.(d).Shell—solid.feedstock,.and.(e).Sasol–

Lurgi.fixed-bed.dry-bottom.gasifier.

Two.Shell gasifiers.(figure.1.3c.and.d).are.used.commercially,.one.for.gas.and.

liquid carbon feedstock (figure.1.3c) and one for solid carbon feedstock such as

pulverized coal or petcoke (figure.1.3d) The first Shell gasifier (figure.1.3c) was

at the gasification temperature Other important coal feedstock variables for a.

Sasol–Lurgi gasifier include burn rate, particle sizing, thermal fragmentation of

Tropsch conversion processes used to produce acetone, acetic acid, and ketones,

and low-temperature Fischer–Tropsch conversion processes used to produce

feedstocks using a slagging gasifier

Carbon feedstock in different Types of gasifiers used or Planned

throughout the World

gasifier Type Carbon feedstock Type (number of gasifiers utilizing)

. gasIfICaTIon for h  ProduCTIon

Worldwide, it is estimated that approximately 50 million tons of H2 is produced

syngas applications output for gasifiers That are operating or are Planned

gasifier Type gasification end Product use (number of gasifiers dedicated to That Purpose)

Chemicals Power

gaseous fuels fT liquids multiple

not specified

Industrial applications for syngas from Those gasifiers

Primary syngas application number of gasifiers Percent of Total

a pressure swing adsorption (PSA) unit where remaining impurities are

approximately 3,100 t/d of carbon feedstock, producing H2 for

An.integrated.gas.treatment.unit.removes.H2S.and.CO2.from.the.syngas,

with.about.3,000.t/d.of.CO2.released.to.air Future.use.of.the.CO2.by.nearby

greenhouses to enhance plant growth is being considered The CO level

As.noted.previously,.syngas.must.be.cleaned.or.processed.to.reduce.or.remove.impu-rities such as H2S, COS, HCN, CO2, N2, and carbon/soot, and may be processed.

to.concentrate.or.increase.the.quantity.of.gases.like.H2,.CO,.or.CO2 The.level.of

S.and.produce.sodium.sulfide,.remov-ing.from.85.to.95%.of.the.H2S.from.the.sour.gas CO2.in.the.syngas.is.also.removed

by the sodium.hydroxide, forming.sodium.bicarbonate.24.Multiple.stages.of.these

4 Claus unit—Produces.S.from.syngas.H2S.concentrate

5 PSA unit—Used.to.purify.a.H2

(gas/liquid feed or solid materials like coal or petcoke), whether the gasification.

chamber is designed to liquefy feedstock ash or keep it as discrete particles, the

linings has not shown promise because of constant attack of the lining, with no.

it.to.be.reduced.to.SiO.vapor.and.removed.or.transferred.elsewhere.in.the.refrac-tory lining.30 This reaction becomes very likely at temperatures over 1,200°C.28.

Research30.has.indicated.that.the.removal.of.SiO2.from.a.refractory.is.impacted.by

point liquids in an Al2O3 lining, leading to rapid and excessive refractory wear

In practice, the valance of vanadium depends on the oxygen partial pressure of

Chemical Composition of Three Classes of high Chrome oxide refractories

used in air-Cooled slagging gasifiers (wt%)

fIgure . Spalling.examples.in.gasifier.refractory:.(a).pinch.spall.along.refractory.joint,.

(b).thermal.spall,.and.(c).structural.spall.(circled.material).

fIgure . Stages.of.refractory.wear.

Creep Chemical Corrosion

feedstock,.differences.in.manufacturers’.equipment,.and.differing.pro-ibility.to.meet.varying.market.demands This.may.include.co-produc-tion.capability.so.two.or.more.products,.such.as.H2,.syngas,.or.power,.

during.gasifier.operation

2 Syngas.processing:

gas,.with.an.emphasis.on.gas.throughput,.composition,.and.purification

Advanced.cleaning.and.processing.technology.is.necessary.for.raw.syn-Advanced.syngas.cleaning.and.conditioning.processes.are.needed.that

clean.syngas

The.development.of.novel.membranes.for.advanced,.low-cost.separa-H2,.CO2,.CO,.and.gaseous.impurities.(such.as.H2arate.other.gases.from.air,.such.as.O2.or.N2,.are.also.needed Improve-ments.could.include.a.reduction.in.the.number.of.steps.or.stages.in.a

S) Membranes.to.sep-process.or.in.processing.speed

bine.processing.stages.such.as.H2.separation.and.the.water.shift.reaction

gas.reaction.[CO.+.H2O.(gas).→.H2.+.CO2] Currently.about.10%.of.all.H2.produced

Applications and News,.9,.26–31,.2004.

9 Phillips, G., Gasification Offers Integration Opportunities and Refinery

14 The Fuel Cell Handbook,.6th.ed.,.produced.by.E.G and.G Services.under.contract.

for the U.S Department of Energy, Morgantown, W VA., Publication

DOE/NETL-2002/2270, available from National Technical Information Services, chapter 8.1.1,.

2002.

15 Donaldson,.A.M and.Mukherjee,.K.K.,.Gas.Turbine.“Refueling”.via.IGCC,.Power,.

March.2006,.pp 34,.36–38.

16 U.S.Environmental.Protection.Agency,.Texaco Gasification Process Innovative

Tech-nology Evaluation Report,.EPA/540/R-94/514,.July.1995.

17 U.S Department of Energy, National Energy Technology Laboratory, Gasification:.

paper presented at the World Hydrogen Energy Conference, Yokohama, Japan, July.

speech_whec.pdf.

23

Zuideveld,.P and.J de.Graaf,.P.,.Overview.of.Shell.Global.Solutions,.Worldwide.Gas-

ification.Developments,.paper.presented.at.the.Proceedings.of.Gasification.Technolo-gies.2003,.San.Francisco,.October.12–15,.2003.

Technical Conference on Refractories, UNITECR ’05,.Orlando,.FL,.November.2005,.

4.pp.

28 Taber, W.A., Refractories for Gasification, Refractories Applications and News, 8,.

18–22,.2003.

29 U.S Department.of.Energy,.Gasification Markets and Technologies — Present and

Future: An Industry Perspective,.Report.0447,.July.2002,.pp 1–53.

30 Johnson, R.C and Crowley, M.S., State of the art refractory linings for hydrogen.

reformer.vessels,.in.Proceedings of the Unified International Technical Conference on

Refractories, UNITECR ’05,.Orlando,.FL,.November.2005,.4.pp.

2.6.1 High-Temperature.Oxygen.Ion.Conductors 52Acknowledgments 53References 54

most.widely.used.and.economical.process.is.steam.reforming.of.natural.gas,.a.pro-cess.that.results.in.CO2.emissions

. loW-TemPeraTure eleCTrolysIs of WaTer soluTIons

The.reversible.electrical.potential.(∆G/nF.=.Erev).to.split.the.O–H.bond.in.water.is

1.229.V In.addition,.heat.is.needed.for.the.operation.of.an.electrolysis.cell If.the

heat.energy.is.supplied.in.the.form.of.electrical.energy,.then.the.thermal.potential

is.0.252.V.(at.standard.conditions),.and.this.voltage.must.be.added.to.Erev.(i.e.,.add

entropic term T∆S to ∆G) The (theoretical) decomposition potential for water at

standard conditions (for ∆H.≅.∆H°).is.then 1.480 V This.is.shown in.figure.2.1

Anode.and.cathode.reactions.for.electrolysis.(see.figure.2.1).are:

Anode:.2.OH–.→.1/2.O2.+.H2O.+.2.e– (2.1)

Cathode:.2.H2O.+.2.e–.→.H2.+.2.OH– (2.2)

energy consumption), many different catalytic materials have been examined for

use as anodes or cathodes (or coatings on underlying electrodes) Research was

conducted.in.Germany.in.the.1980s.and.1990s.on.advanced.materials.and.designs

substrates).were.prepared.using.anodic.deposition.from.MnSO4-Na2MoO4.solutions

to replace the conventional asbestos diaphragm (that dissolves in caustic KOH at

temperatures above 90°C) with polymer-bonded (PTFE-type) composites These

fIgure . (a).Schematic.of.water.(alkaline).electrolysis (b).Two.large.(200.Nm3

/h).atmo-spheric,.alkaline,.multicell.electrolysis.stacks.generating.hydrogen.at.the.Norsk.Hydro.Company.

Research is currently being conducted into PEM-type membranes that have

to decompose two water molecules to simultaneously generate one molecule of.

hydrogen and one of hydrogen peroxide (used in paper/pulp and chemical

.pulsed-laser.plasma.evap-oration,46 or chemical vapor deposition (CVD).47 Very thin electrolytes generally

Over the last decade there has been significant R&D to reduce the operating.

or occasionally Ba on the A site.50 Other studies have been conducted to measure

doped.LaGaO3’s.electronic.conductivity51–53.and.develop.suitable.electrodes.54–57

et.al.67.has.also.reported.that.doped.PrGaO3.is.a.fast.oxygen.ion.conductor,.but.it.does

crystallographic.and.chemical.stability.problems.that.have.prevented.implementa-tion.in.practical.long-lived.cells As.reviewed.by.Azad.et.al.,74.α-Bi2O3.(monoclinic)

is.stable.below.730°C,.while.the.very.high.conductivity.δ-Bi2O3.(cubic,.CaF2.type).is

than.700°C,75.some.research.was.conducted.on.rhombohedral.phase.Bi2O3.stabilized

by alkaline–earth oxide dopants (e.g., CaO-Bi2O3, SrO-Bi2O3, or BaO-Bi2O3)76 or

partial substitution of various metal ions for vanadium These compounds were

termed BIMEVOX Investigations of fabrication with possible application as an

electrolyte,.with.particular.interest.in.copper.substituted.material.(BICUVOX,.e.g.,

Be2V0.9Cu0.1O5.35),79.followed There.is.some.electrical.conductivity.data.measured

on.BICUVOX.“cells,”80,81.but.no.actual.fuel.cell.data.seem.to.be.available This.may

be.an.indication.of.increased.electronic.conductivity82.(electronic.shorting.of.cells)