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 HYDROGEN: ITS TECHNOLOGY AND
IMPLICATIONS
Editors

Kenneth E. Cox K. D. Williamson, Jr.

P ro je c t M an ag er
T h erm o ch em ical H y d ro g en
L os A lam o s S cientific L a b o ra to ry
U niversity o f C a lifo rn ia
Los A lam o s, N ew M exico
A ssistan t D ivision L ead er
Los A lam o s Scientific L a b o ra to ry
U niversity o f C a lifo rn ia
Los A lam o s, N ew M exico

SERIES OUTLINE

Volume I
Hydrogen Production Technology
Volume II
Transmission and Storage of Hydrogen
Volume III
Hydrogen Properties
Volume IV
Utilization of Hydrogen
Volume V
Implications of Hydrogen Energy
 Hydrogen: Its Technology

and Implications
Volume I
Hydrogen Production
Technology

Editors:

Kenneth E. Cox K. D. Williamson, Jr.

Project Manager, Thermochemical Hydrogen Assistant Division Leader
Los Alamos Scientific Laboratory Los Alamos Scientific Laboratory
University of California University of California
Los Alamos, New Mexico Los Alamos, New Mexico

Boca Raton London New York

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First published 1997 by CRC Press
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 PREFACE TO HYDROGEN: ITS TECHNOLOGY AND IMPLICATIONS

The United States, Western Europe, Japan, and several other countries are presently
faced with an energy shortage due largely to an imbalance of energy consumption over
fossil energy production. This problem was dramatized in October 1973 during the Arab
embargo on the shipment of oil to the United States and the resultant large increases in
the price of crude oil. This shortage in energy supply was then termed the “energy crisis.”
It was a clear demonstration of the nation’s dependence on imported petroleum and its
vulnerability on both political and economic grounds. It is clear that the above problems
would worsen in the future unless more attention and effort are directed toward
increasing domestic energy production from both depletable and nondepletable sources
and reducing energy consumption.
In the short-term, until the year 2000, coal and nuclear energy are expected to play
dominant roles in meeting the energy shortage despite the environmental restrictions that
hamper the production and consumption of high-sulfur coal and similar difficulties (siting
and radioactive waste disposal) that have slowed the development of nuclear energy. In
the long-term, beyond the year 2000, it is imperative that all forms of renewable energy
be developed. These include solar energy, in such forms as wind, ocean thermal gradients,
and biomass; geothermal energy; and fusion.
A major problem with several of the renewable energy sources is that they are
intermittent and their energy density is low; thus, there is a need for an energy carrier
that can act as both a storage and transportation medium to connect the energy source to
the energy consumer. Many of the renewable energy forms, together with coal and fission
exhibit their energy in the form of heat release. It is necessary to develop an energy
carrier, other than electricity, to supply the transportation sector as well as overcome the
problems of electrical storage.
Hydrogen, the lightest element, has been suggested as the energy carrier of the future.
In itself, it is not a primary energy source but rather serves as a medium through which a
primary energy source (such as nuclear or solar energy) can be stored, transmitted, and
utilized to fulfill our energy needs. There are several distinct advantages to the use of
hydrogen as an energy medium. It can be made from water, an inexhaustible resource. On
combustion, water is the main product; thus, hydrogen can be regarded as a clean,
nonpolluting fuel. Indications from current research efforts suggest that hydrogen may be
produced from high-temperature heat sources at an efficiency greater than that of
electrical generation, thereby making hydrogen a more economical energy source than
electricity. Technology has already been developed for storing hydrogen as a pressurized
gas, a cryogenic liquid, or in the form of a metal hydride. Systems for transporting
hydrogen as a gas or a liquid have been developed with liquid hydrogen playing a major
part in NASA’s putting a man on the moon. Finally, hydrogen is of value as a chemical
intermediate, being used in fertilizer manufacture, methanol synthesis, and petroleum
treatment. This area of hydrogen utilization represents 3% of today’s energy consumption
and is expected to grow by a factor of five by the year 2000. The above concept of using
hydrogen is termed the “hydrogen energy economy” and has been receiving an increasing
amount of attention from energy scientists and engineers in the United States and abroad.
This series in five volumes represents a serious attempt at providing information on all
aspects of hydrogen at the postgraduate and professional level. It discusses recent
developments in the science and technology of hydrogen production; hydrogen
transmission and storage; hydrogen utilization; and the social, legal, political, environ­
mental, and economic implications of hydrogen’s adoption as an energy medium.
Although there are several reports of selected studies on hydrogen as a fuel, this is the
first comprehensive reference book that covers a wide range of topics of notable interest
and timely importance.
Volume I of the series discusses such topics as hydrogen production from fossil fuels,
nuclear energy, and solar energy. Hydrogen production technology from water by
traditional methods such as water electrolysis and newer attempts to split water
thermochemically are included with details of current research efforts and future
directions.
Volume II provides detailed design information on systems necessary for the storage,
transfer, and transmission of gaseous and liquid hydrogen. Cost factors, technical aspects,
and models of hydrogen pipeline systems are included together with a discussion of
materials for hydrogen service. Metallic hydride gaseous storage systems for the utility
and transportation industry are covered in detail, and the design Dewars and liquid
hydrogen transfer systems are examined.
Volume III focuses on hydrogen’s properties and provides in one location all of the
hydrogen data measured and compiled by the National Bureau of Standards, Cryogenic
Division. The properties are individually discussed, and tables of data are provided. The
properties of slush hydrogen are also included.
Volume IV covers the present and future uses of hydrogen. Hydrogen has been
suggested as a prime candidate for both air and surface transportation. In the utility
industry, hydrogen systems for peak shaving promise to play an important future role.
Both present and future domestic and industrial applications of hydrogen are surveyed.
These include present uses in ammonia and methanol synthesis and future uses in the
direct hydrogasification of coal to synthetic natural gas. Important to all of these
applications are the safety considerations in the use of hydrogen to allow for public
acceptance of hydrogen’s role as an energy medium.
Volume V is primarily concerned with the nontechnical aspects of hydrogen.
Economics of hydrogen energy systems will play a major part in determining the time
frame for hydrogen’s adoption. Cost analyses of such systems with return on investment
considerations are surveyed from the point of view of production, transmission, and
storage of hydrogen. The environmental, political, social, and legal implications of new
secondary energy forms such as hydrogen are discussed with reference to governmental
energy policy, the social costs of energy production and use, and the public’s acceptance
of a hydrogen energy medium.
The unusually broad nature of hydrogen demands the expertise that could only be
provided by a wide authorship; thus, some of the authors are the original authorities in
their respective fields. Although the subject matter treated in each chapter is, in general,
the author’s research work and his critical review of the state-of-the-art, the authors have
had complete freedom in choosing the particular important areas to be emphasized. As a
result, some chapters treat the subject matter in more detail than others with a greater
emphasis on the engineering or design aspects of a particular system. Therefore, each
chapter possesses its own special feature and appealing points. Due to the limited space in
the series, the editors have encouraged each author to supply an extensive list of
references at the end of his chapter for the benefit of interested readers. Detailed author
and subject indexes have been provided at the end of each volume.
 The editors, while striving to avoid duplication, have allowed some degree of overlap in
certain of the chapters for the sake of continuity and allowing the reader to view a
particular topic from two or more points of view. Further volumes on the topic of
hydrogen are planned, and we wish to hear from our readers as to areas that might have
been neglected or deserve a special chapter on their own.
We would like to express our sincere thanks to these authors and the staff of CRC
Press, Inc. in particular Mrs. Gayle Tavens and Miss Sandy Pearlman, for their efforts in
making these volumes possible. Lastly, we would like to thank our wives, Patricia R. Cox
and Ruth S. Williamson, for their encouragement and help during the time it took to edit
these five volumes.

K. E. Cox
Albuquerque, New Mexico
K. D. Williamson, Jr.
Los Alamos, New Mexico
March 1975
 PREFACE TO VOLUME I:
HYDROGEN PRODUCTION TECHNOLOGY

The technology of producing hydrogen has progressed considerably since the discovery
of the decomposition of water by an electric current by Nicolson and Carlisle in 1800
followed by Faraday’s discovery of the laws governing electrolysis in 1833. At present,
most of the hydrogen used is produced by schemes such as the steam reforming of
methane or the partial oxidation of petroleum. With the advent of the age of diminishing
fossil fuels, reappraisal of older technologies for producing hydrogen such as electrolysis
and development of newer methods to produce hydrogen directly from thermal energy or
light has begun.
This volume reviews and evaluates current efforts in research to produce hydrogen
from a variety of energy sources and describes some of the newer approaches undertaken
to decompose water into its elements, hydrogen and oxygen.
Chosen for fuller coverage are water electrolysis and the novel cyclic thermochemical
method that has generated considerable worldwide interest since the early 1970s. Energy
sources were selected with the future in mind. Coal, nuclear energy, and a wide variety of
renewable energy sources have been discussed in detail as potential suppliers of raw
material or energy for the conversion processes. Lesser emphasis was placed on conversion
schemes that are in the early stages of research.
A word of thanks is due all the participants in this volume, the authors who devoted
their expertise and time as well as the editorial staff of CRC Press, Terri Weintraub and
Barbara Perris, who aided in the volume’s preparation. It is our hope that this volume will
prove of use and generate interest in the fascinating field of hydrogen energy research.

Kenneth E. Cox
Albuquerque, New Mexico
March 1977
 THE EDITORS

Kenneth E. Cox, Ph.D., is a Staff Member in the High-Temperature Chemistry

Group at the Los Alamos Scientific Laboratory, Los Alamos, New Mexico. He is
currently performing research in developing practical thermochemical cycles that pro­
duce hydrogen by water-splitting. In his previous position as Professor of Chemical
Engineering at the University of New Mexico, Albuquerque, he pioneered the devel­
opment of photovoltaic-electrolytic methods to produce hydrogen from solar energy
and water.
Dr. Cox graduated in 1956 from the Imperial College of Science and Technology of
the University of London with B.Sc. and A.C.G.I. degrees in chemical engineering.
He received his M.A.Sc. from the University of British Columbia in 1959 and his
Ph.D. from Montana State University in 1962, also in chemical engineering.
Dr. Cox is a member of the American Institute of Chemical Engineers, the American
Chemical Society, and Sigma Xi, the Scientific Research Society. He is also a member
of the International Association for Hydrogen Energy and has contributed both as an
author and reviewer to the International Journal o f Hydrogen Energy.
Dr. Cox has published numerous research papers and has given over 100 presenta­
tions. His current research interest include: thermochemical generation of hydrogen
from water, use of solar energy for hydrogen generation, techno-economic energy eval­
uations as well as traditional chemical engineering, e.g., thermodynamics of separation
processes, process design, and dispersion phenomena in fluids.
K. D. Williamson Jr., Ph.D. is Assistant Division Leader of the Systems Analysis
and Assessment Division, Los Alamos Scientific Laboratory, Los Alamos, New Mex­
ico.
Dr. Williamson received his B.S., M.S., and Ph.D. degrees in chemical engineering
from Pennsylvania State University in 1957,1959, and 1961, respectively.
Dr. Williamson is a member and lecturer for the New Mexico Academy of Sciences
and has served as an invited lecturer at the Uniwersity of Tennessee and New Mexico
Highlands University.
Dr. Williamson has published more than 35 research papers. His current interests
include technology assessments and systems analyses of energy-related topics in sup­
port of research and development decision makers at Los Alamos and the State and
National government levels.
 CONTRIBUTORS
Kenneth E. Cox, P h.D .
Project Manager, Thermochemical
Hydrogen
Los Alamos Scientific Laboratory
University o f California
Los Alamos, New Mexico
A . P. Fickett, M .S.
Program Manager, Fuel Cells and
Chemical Energy Conversion
Electric Power Research Institute
Palo Alto, California
James E. Funk, P h .D .
Dean, College o f Engineering
University o f Kentucky
Lexington, Kentucky
R. J. Jiacoletti, P h.D .
Staff Member
Engineering Support Group
Los Alamos Scientific Laboratory
Los Alamos, New M exico
Fritz R. Kalhammer, P h .D .
Director, Energy Management and
Utilization Technology Department
Electric Power Research Institute
Palo A lto, California
R. I. Kermode, P h.D .
Professor o f Chemical Engineering
University o f Kentucky
Lexington, Kentucky
 TABLE OF CONTENTS

Chapter 1
Water E lec tro ly sis................................................................................................................................................... 3
A. P. Fickett and Fritz R. Kalhammer

Chapter 2
Thermochemical Water D e co m p o sitio n ............................................................................................................. 45
James E. Funk

Chapter 3
Hydrogen from Fossil F u e l s ..................................................................................................................................61
R. I. Kermode

Chapter 4
Hydrogen from Nuclear E n e r g y ........................................................................................................................ 119
R. J. Jiacoletti

Chapter 5
Hydrogen from Solar Energy ............................................................................................................................ 145
Kenneth E. Cox

Unit Conversions, Physical Constants, and S y m b o ls ........................................................................................179

In d ex .......................................................................................................................................................................185
 Chapter 1
Water Electrolysis
 Chapter 1
WATER ELECTROLYSIS

A. P. Fickett and Fritz R. Kalhammer

TABLE OF CONTENTS

1.1. Introduction ..................................................................................................................................... 4

1.1.1. Historical Background .................................................................................................... 4

1.1.2. Fundamentals of WaterE lectro ly sis.................................................................................. 5
1.1.2.1. Cell Reactions and Functional Components ................................................ 5
1.1.2.2. Cell V o lta g e ......................................................................................................... 6
1.1.2.3. Cell Current Density ......................................................................................... 9
1.1.2.4. Polarization C u r v e s ............................................................................................. 9
1.1.2.5. Effects of Temperature on Water E le c tro ly sis................................................ 9
1.1.2.6. Effects of Pressure on Water E le c tro ly sis......................................................... 9
1.1.2.7. Electrolysis Module or S t a c k .............................................................................10

1.2. Generic Types of Water Electrolysis S y s te m s ...................................................................................... 11

1.2.1. Unipolar Electrolyzer (Tank T y p e ) ..................................................................................... 11
1.2.2. Bipolar Electrolyzer (Filter Press) ..................................................................................... 11

1.3. Electrolysis System Requirements ......................................................................................................14

1.3.1. Power Conditioning and C o n t r o l ......................................................................................... 15
1.3.2. Cooling Fluid Circulation and C o n tr o l................................................................................. 16
1.3.3. Product Gas-water Removal, Purification, and Pressure
Control ..................................................................................................................................16
1.3.4. Electrolyte Monitoring and C o n tr o l..................................................................................... 17
1.3.4.1. Recirculating E lectro ly te......................................................................................... 17
1.3.4.2. Stationary Electrolyte ......................................................................................... 17
1.3.5. Instrumentation and Controls ............................................................................................. 18
1.3.6. I n s ta lla tio n ..............................................................................................................................18

1.4. Water Electrolysis Technologies ......................................................................................................... 18

1.4.1. BBC Brown, Boveri, Co., Ltd....................................................................................................19
1.4.2. Constructors John Brown (CJB) Developments, Ltd.............................................................. 19
1.4.3. The Electrolyzer Corporation, Ltd.......................................................................................... 20
1.4.4. Lurgi Apparate-Technik GmbH .......................................................................................... 20
1.4.5. Oronzio De Nora ................................................................................................................. 21
1.4.6. Teledyne Energy S y s te m s ..................................................................................................... 22
1.4.7. General Electric’s Solid Polymer Electrolyte T e c h n o lo g y .................................................. 22
1.4.8. Other Advanced Electrolyzer Concepts ............................................................................. 23
1.4.9. Summary of Technology Status ....................................................... 24

1.5. Economics of Water E le c tro ly sis.......................................................................................................... 25

1.5.1. Factors Affecting Capital and Operating Costs .................................................................26
1.5.1.1. Capital Costs ......................................................................................................... 26
1.5.1.2. Operating Costs ..................................................................................................... 26
1.5.2. Relationship of Hydrogen Cost to Capital and Operating
Costs ..................................................................................................................................... 26

3
1.6. Projection and Impact of Technological Advances .................................................................... 31
1.6.1. Advanced Alkaline Technology ..................................................................................... 32
1.6.2. SPE T e c h n o lo g y ................................................................................................................. 36

1.7. Summary and O u t l o o k ..................................................................................................................... 38

R e fe re n c e s......................................................................................................................................................... 40

1.1. INTRODUCTION for byproduct oxygen will be assumed in the

economic analyses.
Hydrogen production by the electrolytic
decomposition of water is simple, reliable, clean, 1.1.1. Historical Background
and based upon scientific principles that were In 1800, Nicholson and Carlisle first produced
demonstrated in the early 1800s. However, water hydrogen and oxygen by electrolysis of water.
electrolysis has not been used extensively for However, the first commercial water electrolyzer
hydrogen production because of the high cost of was not installed until 1902 by the Oerlikon
electric energy compared to natural gas or Engineering Company.2 Oerlikon delivered more
naphtha. Only where substantial amounts of low- than 400 filter-press electrolyzers between 1902
cost hydroelectric power are available have and 1920. The first large (>104 m3/h) North
economics favored electrolytic hydrogen; large American tank-type electrolyzer was located at
electrolysis plants have located only at such sites. Cominco Ltd., Trail, British Columbia in 1939.3
Smaller-scale applications of water electrolysis This plant was built originally to produce oxygen;
have resulted when the reliability and convenience it was later converted to supply hydrogen for
of the modular technology or the high purity of fertilizer production.
the product was more important to the user than A large filter-press electrolyzer was installed in
energy economics alone. Whether the use of Norway in 1927. This plant, which originally
electrolytic hydrogen will expand significantly in produced less than 104 m3/h, was upgraded in
the future will be determined primarily by the stages through 1965 to its present capacity of
relative cost of electric energy, fossil fuels 90,000 m3/h.
(including coal), and possibly of thermal energy if Other large electrolyzers are located in India 4
thermochemical water splitting becomes a reality. Egypt,5 and Peru.6 All are located on major rivers
Water electrolysis produces stoichiometric and operate on inexpensive hydroelectric power.
quantities of oxygen as well as hydrogen. If Table 1 summarizes features of these installations.
needed at the electrolysis site, oxygen at $17 to Until 1960, the developments in electrolyzers
$32 per to n 1 would result in a byproduct credit, concentrated on improved safety, reliability, and
reducing the hydrogen cost by $1 to $2 per 106 user convenience. A major innovation was the
Btu. However, it is not economical to transport design of an electrolyzer that could operate at
the oxygen even for short distances.1 Transpor­ pressure. This eliminated the need for an auxiliary
tation requires liquefaction or compression and compressor and enabled electrolyzer operation at
storage, offsetting any credits from the subsequent elevated temperature. The first practical high-
sale of byproduct oxygen. pressure electrolyzer was the 1948 Zdansky-Lonza
Since the electrolysis plant design is essentially design licensed by Lurgi. A plant of this design and
unaffected by the decision to use oxygen, and the capable of producing 5000 m3/h at 30 kg/cm2 was
use of oxygen on site will probably be uncommon, installed in Cuzco, Peru in 1958.6
this chapter will concentrate exclusively on hydro­ In the late 1950s and early 1960s, interest
gen as the product of water electrolysis. No credit developed in water electrolysis as a source of

4 H y d r o g e n : I t s T e c h n o lo g y a n d I m p lic a tio n s
 TABLE 1

Major Electrolysis Installations

Location Type Supplier Year installed Hydrogen output (m3 /h)

Trail, B.C., Canada Tank Cominco 1939 17,000

Nangal, India Filter press De Nora 1958 26,000
Aswan Dam, Egypt Fliter press Demag/BBC 1 9 60-19773 4 1 ,000-21,600
Rjukan, Norway Filter press Norsk Hydro 19 2 7 -1 9 6 5 b 90,000
Cuzco, Peru Filter press Lurgi 1958 5,000

aThe original Demag plant is being replaced by BBC electrolyzers. The 1977 BBC electrolyzer’s capacity will be 21,600
m3 /h.
bBegun in 1927, upgraded through 1965.

TABLE 2 plants. Table 3 lists six of the more notable

suppliers.
Chronology of Significant Events in the Development of
Water Electrolysis
1.1.2. Fundamentals of Water Electrolysis
Date Event 1.1.2.1. Cell Reactions and Functional Com­
ponents
1800 Nicholson and Carlisle demonstrated Electrolysis of water occurs when a direct
concept of water electrolysis electric current is passed between two electrodes
1902 First commercial installation by Oerlikon
immersed in an aqueous electrolyte. For water to
ca. 1930 First large filter-press installation
(Norsk Hydro) decompose, the voltage across the two electrodes
1939 First large tank-type installation must be greater than that corresponding to the
(Trail, B.C., Canada) free energy of formation (decomposition) of water
1948 Zdansky and Lonza pressurized electrolyzer plus the voltage needed to overcome electrode and
1958 First large pressurized Lurgi installation ohmic polarizations.
(Cuzco, Peru)
1970 Development of efficient, compact Figure 1 depicts water electrolysis cells with an
electrolyzers for life-support applications alkaline or acid electrolyte. The hydroxyl
(alkaline) ions or hydronium (acid) ions are re­
quired for the water to be conductive. In alkaline
electrolytes (Figure 1a), the key reactions associ­
o x y g e n fo r life su p p o rt in su b m arin es and space-
ated with water electrolysis are
craft. In these applications, light weight and low
volume rather than cost became the primary Cathode (hydrogen electrode):
criteria. During the same period, the transfer of 4 e + 2 H 20 -> 2 H 2 + 40H ~ 0)
elements of new fuel-cell technologies to electroly­
sis helped achieve improvements in electrolyzer Anode (oxygen electrode):
performance and efficiency. Several advanced
electrolyzer concepts were developed for life 4 0 H " - 0 2 + 2H20 + 4e (2)
support applications. The more notable of these
Net reaction:
are the General Electric SPE technology, based on
a solid polymer electrolyte, and the Teledyne 2H20 -* 2H2 + 0 2 (3)
technology, based on a potassium hydroxide
electrolyte. The General Electric unit is not (Figure lb) acid electrolyte cathode (hydrogen
anticipated to be commercially available on a large electrode):
scale before 1980.1 Teledyne is delivering eight 4e + 4H* -* 2H2 (4)
units for application in argon purification that
have a combined output of ~100 m3/h.7 Anode (oxygen electrode):

2H20 -> 0 2 + 4H+ + 4e (5)

A chronology of several important events in the
development of water electrolysis is given in Table Net reaction:
2. About a dozen companies are now developing
and manufacturing industrial electrolytic hydrogen 2H20 -> 2H2 + 0 2 (3)

5
 TABLE 3
Suppliers of Industrial Electrolyzers
Company
BBC, Brown, Boveri & Company, Ltd.
Constructors John Brown
Developments, Ltd.
The Electrolyzer Corporation, Ltd.
Lurgi Apparate-Technik GmbH
Oronzio de Nora
Teledyne Energy Systems
As shown in Figure 1, the critical components
of the electrolysis cell are the cathode, anode,
electrolyte, and diaphragm; these must meet a
number of specific criteria. The cathode must be
corrosion resistant in the electrolyte at very low
(reducing) potentials, be a good electronic
conductor, catalyze the evolution of hydrogen,
and, in most systems, have structural integrity.
Similarly, the anode must be corrosion resistant in
the electrolyte at oxidizing potentials, be a good
electronic conductor, catalyze the evolution of
oxygen, and, in most systems, have structural
integrity.
The electrolyte must be stable at the reducing
and oxidizing potentials of the cathode and anode,
respectively, and must provide a sufficient concen­
tration of hydroxyl or hydronium ions for good
electrolytic (ionic) conductivity. The diaphgragm
must be stable in the electrolyte, either have ionic
conductivity or adsorb electrolyte to provide
adequate ionic conduction, have physical integrity,
and separate the hydrogen and oxygen (both as
gases and dissolved in the electrolyte).
The significant electrochemical parameters of a
water electrolysis cell are the cell voltage (a direct
measure of the energy required for electrolysis and
thus closely related to the efficiency of the cell)
and the cell current density, which is a measure of
the quantity of hydrogen produced by a unit area
of cell and is thus related to capital costs.
L l.2.2. Cell Voltage
The theoretical minimum, or reversible,
electrolysis cell voltage (E) is determined by the
minimum electric energy that must be supplied to
the cell for electrolysis to occur. This energy in
turn, is given by the decrease in free energy, AG,
required to decompose water into its elements.
Written for molar quantities of the cell reaction:6
(6 )
6 Hydrogen: Its Technology and Implications
Location
Baden
Portsmouth, England
Toronto
Frankfurt
Milano
Timonium, Md.
where E = the theoretical or minimum voltage at
which electrolysis can occur, F = the Faraday
constant, n = the number of electrons transferred
in the reaction, and AG = the change of the Gibbs’
free energy for the reaction.
As with any chemical reaction, a change AH of
heat content (enthalpy) is associated with the
water electrolysis reaction. For a constant-
pressure, isothermal process such as water
electrolysis, AH is related to AG by:
(7a)
where
AQr = TAS (7b)
and AH = the enthalpy (heat content) change for
the reaction; the enthalpy change at standard
conditions is equal to the higher heating value of
hydrogen; AQr = the heat that must be exchanged
with the environment if the reversibly conducted
cell reaction is to remain at constant temperature;
T = cell temperature; and AS = the entropy change
for the electrolysis reaction.
For electrolysis to occur at practical rates, the
voltage (V) applied to the cell must exceed the
reversible cell voltage (E0). The difference V -EQ is
needed to overcome the resistances (electric and
polarization) associated with the electrolysis
process; the corresponding energy is eventually
dissipated within the cell as irreversible heat (AQj)
according to:
( 8)
Rewriting Equation (8) using Equations (6) and
(7a) yields:
(9)
 FIGURE 1. Electrolysis of water in alkaline and acid electrolyte.
Equation 9 states that the reversible endo­
thermic heat requirement (AQr) of the electrolysis
reaction is exactly balanced by the irreversible
heat (AQj) liberated due to cell inefficiency when
the applied cell voltage equals sometimes
referred to as the ΔΗ voltage. Since under these
conditions no heat is exchanged with the cell
environment, the ΔΗ voltage is also termed the
“ th e rm o n e u tra l voltage.” Electrolysis cells
operated at voltages between E and the ΔΗ voltage
must be supplied heat from an external source to
maintain the constant-temperature operation of
practical interest; cells operated above the ΔΗ
voltage must be cooled.
Figure 2 depicts both AG and ΔΗ as a function
of temperature. It is apparent that the minimum
7
 FIGURE 2. Theoretical electrolysis voltage vs. temperature.
electrolysis voltage decreases substantially with
increasing temperature; on the other hand, the
thermoneutral voltage increases somewhat with
temperature. This means that, with increasing
temperature, a larger driving force (V - E) is
available for cell operation at the thermoneutral
voltage - that is, this desirable operating condition
becomes more feasible at higher temperatures.
The thermal efficiency of an electrolysis cell
customarily is defined as the ratio of the heat
content (= higher heating value) of the product
hydrogen to the input electrolysis energy:
GO)
Since water can be electrolyzed at voltages
8 Hydrogen: Its Technology and Implications
above E but below the ΔΗ voltage, efficiencies
above 100% are possible; under these conditions,
energy is conserved through absorption of heat
from the cell environment. However, at present all
practical electrolyzers operate at voltages in excess
of the ΔΗ voltage (and, hence, at efficiencies
below 100%), which require cooling.
The voltage of an operating cell can be
represented as follows:
( 11)
where V = the cell operating voltage (volts), E =
the theoretical cell voltage (volts), 7?c = the
cathode overvoltage (volts), rja = the anode over­
voltage (volts), I = the cell current (amperes), and
R0 = the cell resistance (ohms).
 Overvoltages, t?c and r?a are a measure of the
kinetic limitations of the reactions at the
respective electrodes. IR0 is a function of the
e le c tro ly te conductivity, distance between
electrodes, diaphragm conductivity, electrode
conductivity, and contact resistance between cell
components. A major objective of electrolysis
design and development programs is to minimize
the ?7C, 77a, and IR0 terms, with a view to achieving
high efficiency.
1.1.2.3. Cell Current Density
The rate of hydrogen generation is proportional
to the current that passes through an electrolysis
cell according to:
( 12)
where Rq = the rate of hydrogen generation, m3/h
(assumes no recombination within the cell), and I
= the current (amperes).
Dividing both sides of Equation 12 by cell area
results in a corresponding relationship between the
rate of hydrogen production per unit cell area and
the current density:
(13)
where A = the cell area (square meters), and J =
the current density (amperes per square meter).
The capital cost of an electrolysis module, Cem,
is inversely proportional to R q /A and directly
proportional to the capital cost per unit area of
cell, Cf. Thus, the current density becomes a very
significant economic parameter as:
(14)
where Cem = the electrolysis module capital cost
(dollars) per kilowatt of hydrogen produced
(higher heating value), K = proportionality
constant, CF = the capital cost per unit area of cell
(dollars per square meter), and J = the current
density (amperes per square meter).
1.1.2.4. Polarization Curves
Since cell voltage and current density are very
important when optimizing an electrolysis cell or
system, the relationship of these parameters is
especially significant. This relationship, called a
“polarization curve,” is depicted schematically in
Figure 3. The operating voltage of a practical
electrolysis cell approaches the theoretical
minimum voltage E only at very small current
densities. As J increases, the i?c ,T7a, and IR0
(JR 'q) polarization terms become major contri­
butors to the operating voltage.
Different cell technologies can have markedly
different polarization curves. As will be discussed
later, some developers choose to use low-cost
materials and operate at low current densities
(Figure 3, Curve A). Others operate at high current
densities that tend to require more expensive
materials (Figure 3, Curve B).
1.1.2.5. Effects o f Temperature on Water
Electrolysis
As depicted in Figure 2, increasing temperature
decreases the theoretical voltage required for water
electrolysis. On the other hand, the voltage corre­
sponding to ΔΗ increases slightly with increasing
temperature. Thus, while slightly more total
energy is needed at higher temperatures, the
theoretical minimum requirement of electric
energy is lower.
Even more important in practice, the voltage-
loss terms r?a, r?c, and IR0 are reduced consider­
ably by increased temperature. As a result, the
polarization curves of all practical electrolysis cells
improve with increased temperature. Several
developers8’9 report that (at constant current
density) cell voltage decreases almost linearly with
temperature.
Most commercial electrolyzers operate between
70 and 90°C. As temperature is raised above this
level, material compatibility problems (corrosion)
begin to limit life. In addition, it becomes neces­
sary to pressurize the system to reduce water loss
through evaporation. These complications limit
the temperature capability of present technology.
However, as will be discussed later, increasing cell
temperature is an important route to improved
performance and decreased cost.
1.1.2.6. Effects o f Pressure on Water Electrolysis
One advantage of electrolysis is that the hydro­
gen and oxygen gases can be delivered at pressure
with little energy penalty. Assuming reversible
thermodynamics, the theoretical minimum energy
required for pressurization of the product gases
from the reaction 2H2 O H2 + 2 0 2 is:
(15)
9
 FIGURE 3.
where ΔΕ = the change in cell voltage due to
pressure (volts), R = the gas constant, T =
temperature, °K, F = the Faraday constant, and y -
= the ratio of pressures for which ΔΕ applies.
For example, at 25°C, ΔΕ = 0.044 log10 P.
Thus, 44 mV would be required to deliver the
gases at 10 atm, 88 mV at 100 atm, and so on.
However, in practice, the voltage penalty for pres­
surization is even less than the theoretical for two
reasons. First, reversible thermodynamics only ap­
ply for reversible electrode processes. If the elec­
trode process is irreversible (i.e., r?c or r?a is large),
most of the energy of activation can be recovered
as pressure-volume work. For example, in acid
systems where r?c is large, one does not observe a
voltage penalty for pressurizing the oxygen.
Instead of Equation 15, the following equation
applies:
(16)
Equation 13 essentially accounts for the
pressurization of the hydrogen only. Second, the
volume of the evolving gas bubbles is reduced as
pressure is increased. Since evolving bubbles can
10 Hydrogen: Its Technology and Implications
Typical polarization curves.
cause increased resistance of aqueous electrolytes,
reducing bubble volume can significantly decrease
the IR0 term. In agreement with this concept,
some developers observe10 that electrolysis cell
performance improves with increased pressure.
Higher pressures, however, do cause difficulties
in separating and containing the pressurized gases,
as well as greater materials problems such as
hydrogen embrittlement. Also, at higher pressures,
hydrogen and oxygen will more rapidly diffuse
across the diaphragm and recombine before they
leave the system. This causes the apparent rate of
hydrogen generation to be less than that calculated
from Equation 12. At high pressures and tempera­
ture, this current inefficiency can cause significant
losses (1 to 10%) of the hydrogen generated.
1.1.2.7. Electrolysis Module or Stack
Individual electrolysis cells are grouped
together in modules or stacks to form con­
veniently sized packages with common electrical,
thermal, and fluid interfaces — tank-type or
filter-press configurations. These configurations
are discussed in detail in Section 1.2.
 1.2. GENERIC TYPES OF
WATER ELECTROLYSIS SYSTEMS
The two basic types of water electrolyzer
designs are the unipolar (tank type) and bipolar
(filter press). The main difference between the two
types is that in the unipolar design, individual cells
are grouped in parallel and share a common
electrolyte, while in the bipolar design, cells are
connected in series and each cell has its own
electrolyte. Commercial versions of both electro­
lyzer types use 25 to 35 wt% potassium hydroxide
as electrolyte and operate at 70 to 85°C.
1.2.1. Unipolar Electrolyzer (Tank Type)
A schematic diagram of a unipolar electrolyzer
is given in Figure 4a. Figure 5 is a photograph of
the Stuart Cell, a tank electrolyzer manufactured
by the Electrolyzer Corporation, Ltd. The con­
struction of the tank electrolyzer is simple. Single
cells are placed in a common electrolyte tank.
Each tank is called a “module.” All anodes and
cathodes are connected in parallel. Thus, the
overall module voltage is the same as the voltage of
a single cell. Alternate electrodes are surrounded
by diaphragms that prevent hydrogen and oxygen
from mixing. Modules are connected in series to
achieve the hydrogen production capacity desired.
The advantages of the tank design over the
filter-press design are
• Simpler construction
• Common electrolyte with no shunt
currents
• Ease of maintaining the electrolyte
concentration
• No electrical contact surfaces within the
cell
• Lower material cost per unit cell area
• High reliability
• Easy removal of individual cells for
maintenance and repair
The major disadvantage of the tank design is
that each module requires very large currents at
low voltage due to the large number of cells
connected in parallel. Thus, large copper busbars
are required. The cost of the copper plus the high
cost of a high-current dc power conditioner tend
to offset the low cell cost; thus, the total plant
costs of unipolar electrolyzers are comparable to
the costs of bipolar plants.
1.2.2. Bipolar Electrolyzer (Filter Press)
In the filter-press electrolyzer, shown in Figure
4b, one electrode serves both as the cathode for
one cell and the anode for the adjacent cell. Since
the cells are in series, the voltage increases in
proportion with the number of cells in the stack.
For example, a module of 100 cells would have a
total voltage of ~200 Vdc. Figure 6 is a photo­
graph of the Lurgi “electrolytor.” This filter-press
electrolyzer contains over 500 cells and produces
740 m3/hr of hydrogen. With the bipolar configu­
ration, each cell must contain its own electrolyte.
(If the electrodes of a bipolar module were all
placed in the same electrolyte tank, the high
voltage would cause short circuits through the
electrolyte with large currents.) The purity and
concentration of the electrolyte are controlled by
continuous circulation, which also removes waste
heat. However, even the electrolyte path provided
by the plumbing required for circulation can cause
shunt currents.
The major advantages of the filter-press over
the tank-type design are
• No external busbars are required to
connect individual cells;
• The modules occupy a smaller volume for
a given hydrogen output;
• Lower currents and higher voltages are
required, simplifying the power conditioning and
controls.
The major disadvantage of the filter-press
design is that greater sophistication is required in
design and fabrication; construction is, therefore,
more expensive.
The acid solid polymer electrolyte (SPE)
electrolyzer, shown in Figure 4c, is a special
filter-press configuration. The unique feature of
this concept is that an ion-exchange membrane is
used as the electrolyte as well as the diaphragm.
Ionic conductivity is provided by the mobility of
the hydrated hydrogen ions within the SPE
membrane. Water is consumed in the electrolysis
process and must be replenished. The water is
circulated to remove waste heat. Thus, water is
both the reactant and the cooling medium.
Advantages of the SPE configuration are
• Elimination of corrosive liquids
• Compact design — ten cells can be
packaged in one linear inch
11
 FIGURE 4. Types of electrolysis modules.

12 Hydrogen: Its Technology and Implications

FIGURE 5. Stuart cell - a tank electrolyzer capable of providing 818 m3/h hydrogen. (Cour­
tesy of The Electrolyzer Corporation, Ltd.)

13
 FIGURE 6. Lurgi “Electrolytor” - a filter press electrolyzer capable of producing 740 m3/h hydro­
gen. (Courtesy of Lurgi-Apparate-Technik GmbH.)
• Relatively simple pressurized operation
due to the physical characteristics of the SPE
• Efficient operation at high current
densities.
The major disadvantage of the SPE technology
is that its key components — electrodes, the
membrane, and structural materials — are more
expensive than those used in alkaline electrolyzers;
the SPE alone costs $100 to $200 per square
meter. Thus, the SPE electrolyzer is more
expensive on a cost per unit area basis. However,
the more important cost per unit of hydrogen
production capacity can be comparable to higher
current densities that can be achieved with SPE
electrolyzers at a given voltage.
1.3. ELECTROLYSIS
SYSTEM REQUIREMENTS
Many auxiliary components and services are
required to support the operation of an electroly­
sis module. In its simplest form, the electrolysis
module must be supplied with conditioned and
controlled dc power, pure reactant water, and a
14 Hydrogen: Its Technology and Implications
coolant fluid. The module produces hydrogen
saturated with water, oxygen saturated with water,
and waste heat (in the coolant fluid). Accordingly,
the overall electrolysis system must provide the
following functions:
• Power conditioning
• Reactant water purification and flow
• Coolant fluid circulation, heat removal,
and temperature
• P ro d u c t gas w a te r removal and
purification (and pressurization, if required)
• Electrolyte monitoring and concentration
(related to reactant water flow control)
• Instrumentation, master control console,
and sufficient automation of control functions to
provide cost-effective, safe, and reliable operation
Some installations may also require means for
compressing and storing the product gas.
Plant size and services — including availability
of power and water - must be carefully con­
sidered before selecting the installation site.
Electrolysis plants occupy floor areas ranging from
16 to 160 m2 per 1000 m3/h of hydrogen
 FIGURE 7. Typical electrolysis installation.
produced. The newer aerospace concepts require
smaller areas; older commercial concepts require
larger areas. Plant heights typically range from 5 to
8 m.
Support subsystems, components, and instal­
lation costs usually represent between 30 and 50%
of the total cost of an electrolysis plant. The
actual cost depends on the purity and pressure of
hydrogen required, the electrolysis concept
selected, the nature of the installation site, and the
level of automation required.
A schematic diagram of a typical electrolysis
plant is given in Figure 7; the major auxiliary
subsystems are discussed below.
1.3.1. Power Conditioning and Control
A transformer-rectifier unit is required to
supply the electrolysis module with dc power;
silicon diodes or thyristors are used as rectifier
elements. The major complication is the control
circuit. The polarization curves (Figure 3) of
commercial electrolyzers are relatively flat. Small
changes in voltage can cause large changes in
hydrogen output. Thus, a precise and infinitely
variable control of the dc supply voltage is
required to provide a variable but controlled
hydrogen output. DC voltage control is obtained
by one of three methods:
1. Thyristor regulation: The dc voltage is
varied by proper phase positioning of the con­
duction period of the thyristors during the ac
half-wave;
2. Induction regulation: The induction
regulator is connected in series with an additional
rectifier-transformer. With induction regulators,
only silicon diodes are required for rectification;
3. Tap changer-transducer regulation: the
coarse voltage control is obtained by positioning a
tap changer on the transformer-rectifier; the fine
voltage control is obtained automatically by means
of a transducer.
Most large commercial electrolyzers use the
tap-change method. Induction regulation is limited
both in current and voltage and is not useful in
15
large plants. Historically, thyristor controls have
been more expensive than other types. However,
with recent improvements in thyristor per­
formance and cost, thyristor control is now
competitive, especially for large installations.
Power conditioners are about 97% efficient and
are usually designed to provide a variable output
of from 25 to 100% of the rated hydrogen
generation rate. Output voltages range from 200 to
1000 Vdc. The trend is to change to higher
voltages as improved electronic components
become available. Higher dc voltages reduce the
current that must be handled and produce higher
conversion efficiencies. Eventually, the need for
power conditioning might be eliminated by the use
of cyclic or homopolar generators, which could
pro v id e dc power directly from rotating
machinery.
1.3.2. Cooling Fluid Circulation and Control
All commercial electrolyzers operate at voltages
well above the thermoneutral voltage of 1.48 Vdc
and therefore require cooling. The amount of
cooling required is approximately:
(17)
where C = the cooling requirement (kilowatts), V
= the cell voltage (volts), and Pa = the kilovolt­
ampere of ac power supplied to the power
conditioner.
Most of the heat is removed from the electro­
lyte (or from the recirculating water, in the
case of General Electric’s SPE electrolyzer) in one
of two ways. (1) If the electrolyte is recirculated,
it can be passed through a heat exchanger external
to the cell. In the heat exchanger, the heat can be
removed from the system by transferring it to a
coolant (water or air). (2) If the electrolyte is not
recirculated, coolant must be circulated through
the electrolyzer to remove heat. This method
requires separate cooling coils within the
electrolyzer.
The cooling system often has an intermediary
or secondary coolant to interface with the
electrolyte heat exchanger. For example, the Lurgi
“electrolytor” uses an “intermediate water loop”
to transfer heat from the electrolyte heat ex­
changer to the plant cooling water heat exchanger.
The intermediate loop is easily kept clean,
reducing maintenance of the “electrolytor.”
Air can be used to reject waste heat to ambient
16 Hydrogen: Its Technology and Implications
atmosphere. However, the quantity of heat to be
rejected plus the cost of air/liquid cooling towers
makes this method much less attractive than water
cooling.
Temperature is controlled by thermo regulating
schemes that control the coolant flow. For
startup, heaters are often used to bring the coolant
and the electrolyzer to the desired temperature
quickly.
At least two other significant cooling inter­
faces are needed for an electrolysis system. The
gases must be cooled to lower their dew
points, and the power conditioner must also be
cooled. In commercial practice, the coolant is
passed in series through the gas coolers, the
electrolyte heat exchanger, and the power
conditioner. The gas coolers are usually an integral
part of the gas separation-purification subsystems.
The objective is to lower the dew point of the
gases, increasing the purity of the gases as much as
possible. Gas coolers are located upstream froni
the main electrolyte cooler where the cooling
water is coldest. Since the power conditioner can
operate at a warmer temperature than the
electrolyzer, it is located downstream from the
electrolyte heat exchanger.
For commercial electrolyzers, the cooling
water requirement is about 30 times that of the
electrolyzer feed (reactant) water, or about 301 of
cooling water per m3/h hydrogen produced.
About 90% of the heat is removed from the
electrolyte, 5% from the gases, and 5% from the
power conditioner.
1.3.3. Product Gas-water Removal, Purification,
and Pressure Control
The product gases exit from the electrolyzer
and enter a gas separator, which allows the liquid
to be separated from the gas by gravity. The
separator is sometimes designed to bubble the gas
through a head of electrolyte. The electrolyte level
is maintained by a distilled-water feed. This
removes particulates from the gas and provides an
interface for adding feed water to the electrolyzer.
The gases next enter gas coolers where the dew
point is reduced to near ambient temperature.
If required, the gases are further purified by
in-line filtering and catalytic devices. Even without
further catalytic purification, most electrolyzers
provide > 99% pure gases; with catalytic devices,
purities of > 99.9% are readily attained.
The gases are pressurized by a pressure regu­
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