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EFFICIENCY and
SUSTAINABILITY
in the ENERGY
and CHEMICAL
INDUSTRIES
SECOND EDITION
Scientific Principles
and Case Studies
GREEN CHEMISTRY AND CHEMICAL ENGINEERING
Series Editor: Sunggyu Lee
Missouri University of Science and Technology, Rolla, USA
Efficiency and Sustainability in the Energy and Chemical Industries: Scientific Principles
and Case Studies, Second Edition
Krishnan Sankaranarayanan, Hedzer J. van der Kooi, and Jakob de Swaan Arons
Proton Exchange Membrane Fuel Cells: Contamination and Mitigation Strategies
Hui Li, Shanna Knights, Zheng Shi, John W. Van Zee, and Jiujun Zhang
Proton Exchange Membrane Fuel Cells: Materials Properties and Performance
David P. Wilkinson, Jiujun Zhang, Rob Hui, Jeffrey Fergus, and Xianguo Li
Solid Oxide Fuel Cells: Materials Properties and Performance
Jeffrey Fergus, Rob Hui, Xianguo Li, David P. Wilkinson, and Jiujun Zhang
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
Boca Raton London New York
EFFICIENCY and
SUSTAINABILITY
in the ENERGY
and CHEMICAL
INDUSTRIES
SECOND EDITION
Krishnan Sankaranarayanan

only for identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at

and the CRC Press Web site at

To our children and grandchildren who may witness
the emergence of a sustainable society

vii
Contents
Preface xv
About This Book xix
Acknowledgments xxi
Authors xxiii
IPart Basics
1 Introduction 3
References 6
2 Thermodynamics Revisited 7
2.1 The System and Its Environment 7
2.2 States and State Properties 7
2.3 Processes and Their Conditions 8
2.4 The First Law 8
2.5 The Second Law and Boltzmann 11
2.6 The Second Law and Clausius 12
2.7 Change in Composition 13
2.8 The Structure of a Thermodynamic Application 18
References 21
3 Energy “Consumption” and Lost Work 23
3.1 Introduction 23
3.2 The Carnot Factor 24

6.3 Example of a Simple Analysis 71
6.4 The Quality of the Joule 74
6.5 Example of the Quality Concept 77
6.6 Conclusions 80
References 81
7 Chemical Exergy 83
7.1 Introduction 83
7.2 Exergy of Mixing 83
7.3 Chemical Exergy 84
7.3.1 Reference Components from Air 85
7.3.2 Exergy Values of the Elements 86
7.3.3 Chemical Exergy Values of Compounds 88
7.3.4 The Convenience of the Chemical Exergy Concept 89
7.4 Cumulative Exergy Consumption 90
7.5 Conclusions 91
References 92
8 Simple Applications 93
References 105
Contents ix
IIPart I Case Studies
9 Energy Conversion 109
9.1 Introduction 109
9.2 Global Energy Consumption 110
9.3 Global Exergy Flows 112
9.4 Exergy or Lost Work Analysis 115
9.5 Electric Power Generation 115
9.5.1 Steam Plants 116
9.5.2 Gas Turbines 116
9.5.3 Combined Cycle 117
9.5.4 Nuclear Power 118

10.2.2 Double-Column Process 142
10.2.3 Heat Pump Process 143
10.3 Basics 144
10.3.1 Flash Distillation 144
10.3.2 Multistage Distillation and Re ux 145
10.4 The Ideal Column: Thermodynamic Analysis 149
10.5 The Real Column 152
10.6 Exergy Analysis with a Flow Sheet Program 155
10.7 Remedies 157
10.7.1 Making Use of Waste Heat 157
10.7.2 Membranes 158
10.7.3 Other Methods 159
10.8 Concluding Remarks 160
References 161
11 Chemical Conversion 163
11.1 Introduction 163
11.2 Polyethylene Processes: A Brief Overview 164
11.2.1 Polyethylene High-Pressure Tubular Process 166
11.2.2 Polyethylene Gas-Phase Process 167
11.3 Exergy Analysis: Preliminaries 168
11.4 Results of the HP LDPE Process Exergy Analysis 169
11.5 Process Improvement Options 171
11.5.1 Lost Work Reduction by the Use of a Turbine 172
11.5.2 Alternative to the Extruder 172
11.5.3 Process Improvement Options: Estimated
Savings 173
11.6 Results of the Gas-Phase Polymerization Process Exergy
Analysis 174
11.7 Process Improvement Options 175
11.7.1 Coupling Reactions and Chemical Heat Pump

13.3.4 Adjustment of the Gross National Product 206
13.3.5 Intermezzo: Thermodynamics and Economics—A
Daring Comparison and Analogy 206
13.4 Toward a Solar-Fueled Society: A Thermodynamic
Perspective 211
13.4.1 Thermodynamic Analysis of a Power Station 211
13.4.2 Some Observations 213
13.4.3 From Fossil to Solar 213
13.5 Ecological Restrictions 214
13.5.1 Ecological Footprint 214
13.5.2 Waste 218
13.6 Thermodynamic Criteria for Sustainability Analysis 221
13.6.1 Introduction 221
13.6.2 Sustainable Resource Utilization Parameter α 222
13.6.3 Notes on Determining Depletion Times
and Abundance Factors 227
13.6.4 Exergy Ef ciency η 228
13.6.5 The Environmental Compatibility ξ 229
13.6.6 Determining Overall Sustainability 232
13.6.7 Related Work 234
13.7 Conclusions 234
References 235
14 Ef ciency and Sustainability in the Chemical Process Industry 239
14.1 Introduction 239
14.2 Lost Work in the Process Industry 239
xii Contents
14.3 The Processes 242
14.4 Thermodynamic Ef ciency 243
14.5 Ef cient Use of High-Quality Resources 244
14.6 Toward Sustainability 245

16.1 Introduction 265
16.1.1 What Is Green 265
16.1.2 What Is Biomass 266
16.1.3 Biomass as a Resource 267
16.1.4 Structure of This Chapter 268
16.2 Principles of Green Chemistry 268
16.3 Raw Materials 269
16.3.1 Biomass 270
16.3.2 Recycling 272
16.4 Conversion Technologies 273
16.4.1 Combustion 274
16.4.2 Pyrolysis 275
16.4.3 Gasi cation 275
16.4.4 Upgrading Biomass 277
16.5 How Green Are Green Plastics 278
16.5.1 Optimism in the United States 278
16.5.2 Initiatives in Europe 278
16.5.3 From a Hydrocarbon to a Carbohydrate Economy 280
16.5.4 Feelings of Discomfort 280
Contents xiii
16.5.5 Short Memory: Ignorance or Not Welcome 283
16.6 Biofuels: Reality or Illusion 283
16.6.1 Multidisciplinarity 283
16.6.2 Second-Generation Biofuels 287
16.6.3 The Fossil Load Factor 288
16.6.4 Sustainability and Ef ciency 289
16.6.5 Algae 290
16.6.6 The Future 290
16.6.7 Sense or Nonsense? Discussion 291
16.7 Concluding Remarks 294

19.2 Energy Industries 338
19.3 Chemical Industries 340
xiv Contents
19.4 Changing Opinions on Investment 341
19.5 Transition 343
19.6 Concluding Remarks 344
References 345
Epilogue 347
Problems 349
Index 359
xv
Preface
For some of us, the energy crisis of the 1970s and 1980s may still be fresh
in our memory. The crisis was of political origin, not one of real shortage.
The developed countries responded by focusing on increasing energy ef -
ciency, at home and in industry, and by taking initiatives to make them less
dependent on liquid fossils from the Middle East. More than ever before,
attention shifted to coal as an alternative energy resource—its exploration,
production, transportation, and marketing. Massive research and develop-
ment programs were initiated to make available clean and ef cient coal uti-
lization and more easily handled materials as gaseous and liquid conversion
products. Obviously, large multinational oil companies played an important
role in these initiatives, as they considered energy, not oil, their ultimate
business.
At the same time, there was growing concern worldwide for the environ-
ment. With the industrial society proceeding at full speed with mass produc-
tion and consumption, the world became aware that this was accompanied
by mass emission of waste. Air pollution, water pollution, deterioration of
the soil, and so forth became topics that started worrying us immensely. The
“irreversibility” of most of our domestic and industrial activities seemed to

mous, and that nature has its own ways to be sustainable. However complex
its ways and processes, nature is the prime example of sustainability and the
source of inspiration for developing from an industrial society to what some
like to call a metabolic society: a society that makes use of an immaterial
energy source and recycles its products, including its waste. This is not only
a fascinating challenge but, more importantly, a necessity! Ef ciency will
still be an important factor, as there are serious indications that the world’s
ecological opportunity to exploit the sun as a resource is limited.
Angela Merkel, physicist and former German Minister of Environment,
de ned sustainable development as “using resources no faster than they
can regenerate themselves and releasing pollutants to no greater extent than
natural resources can assimilate them” [2].
Living systems are out of equilibrium with the dead and inorganic envi-
ronment. Thermodynamics provides us with some very useful concepts to
tell us how far out of equilibrium a system is and what it takes to main-
tain this state. The late French scientist Bernard Spinner pointed out that
these concepts allow us to integrate the environment into the analysis of any
system we are interested in, a wonderful thermodynamic principle: always
study the system in interaction with its environment. Science, in this instance
thermodynamics, can hardly offer society something better “to live in har-
mony with the Environment.” In conclusion, the main objective of this book
is to study the ef ciency and sustainability of industrial systems. In doing so,
we will be looking at these systems through the glasses of thermodynamics
and apply this impressive science wherever possible. In this second edition,
the book’s structure of “Basics,” “Thermodynamic Analysis of Processes,”
“Case Studies,” and “Sustainability” has been unaffected, but a few things
have changed. Wherever relevant, problems have been added to a chapter,
testing the students on understanding, reproduction, and application of the
discussed concepts. In Part II, special attention has been given to the pos-
sibility of integrating the environment into the thermodynamic analysis of

will ensure that however distracted we may be by short-term events and
“wisdom,” in the long term, scienti c truth will prevail.
Krishnan Sankaranarayanan
Hedzer J. van der Kooi
Jakob de Swaan Arons
References
1. Brundtland, G.H. Our common future, The world commission on environ-
mental development, Oxford University Press: Oxford, U.K., 1987.
2. Angela Merkel, Science 1998, 281, 5375, 336–337.

xix
About This Book
In the last three decades, important political events and authoritative reports
have drawn our attention to the limits of economic growth, and caused grow-
ing concern on our living environment, the latter even taking global dimen-
sions with issues as climate change and reduction of biodiversity. Most of us
now seem to be aware that our technological and economic activities should
serve also the quality of our natural environment. This is often called sus-
tainable development. The question is now what, more precisely, is meant by
this. The term becomes more relevant with talk of alternative energy sources,
hydrogen, CO
2
, and terms such as “green.” This book aims to quantify these
terms, determine the feasibility and possibility of claims, and allow for a
rational evaluation and discussion based on sound scienti c principles.
This book answers this question for industrial processes, in particular those
in the energy and chemical industry. Having a long experience in joint efforts
with industry and with teaching, the authors use the fundamental laws of
thermodynamics as a point of departure. They contrast the present industrial
society with the emerging metabolic society, in which mass production and

ject of this book, assisted by many students. He is currently active in the
Department of Architecture at Delft University of Technology.
Jakob de Swaan Arons received his MSc and PhD degrees from the
Delft University of Technology, the Netherlands. He spent some 20 years
with Shell International, before he was appointed to the chair of Applied
Thermodynamics and Phase Equilibria at Delft University of Technology.
He is an elected member of the Royal Netherlands Academy of Arts and
Sciences, and an honorary professor of the Beijing University of Chemical
Technology, China. From 2003 to 2009, he served as chair in the chemical
engineering department of Tsinghua University, Beijing, China. Much of his
inspiration was drawn from his many visits to Japan and its research cen-
ters. He received the Hoogewerff Gold Medal for his lifetime contributions
to process technology in 2006.