Fundamentals of Renewable Energy Processes

Table of Contents

Cover image

Title page

Copyright

Foreword to the Third Edition

Foreword to the Second Edition

Foreword to the First Edition

Acknowledgements

Chapetr 1. Generalites

1.1 Units and Constants

1.2 Energy and Utility

1.3 Conservation of Energy

1.4 Planetary Energy Balance

1.5 The Energy Utilization Rate

1.6 The Population Explosion

1.7 The Market Penetration Function

1.8 Planetary Energy Resources

1.9 Energy Utilization

1.10 The Efficiency Question

1.11 The Ecology Question

1.12 Financing

1.13 The Cost of Electricity

PROBLEMS

References

Part I: Heat Engines

Chapter 2. A Minimum of Thermodynamics and of the Kinetic Theory of Gases

2.1 The Motion of Molecules

2.2 Manipulating Confined Gases (Closed Systems)

2.3 Manipulating Flowing Gases (Open Systems)

2.4 Entropy and Lossy Systems

2.5 Distribution Functions

2.6 Boltzmann’s Law

2.7 Phases of a Pure Substance

2.8 Symbology

PROBLEMS

References

Chapter 3. Mechanical Heat Engines

3.1 Heats of Combustion

3.2 Carnot Efficiency

3.3 Engine Types

3.4 The Otto Engine

3.5 Gasoline

3.6 Knocking

3.7 Rankine Cycle

3.8 The Brayton Cycle

3.9 Combined Cycles

3.10 Hybrid Engines for Automobiles

3.11 The Stirling Engine

PROBLEMS

References

Chapter 4. Ocean Thermal Energy Converters

4.1 Introduction

4.2 OTEC Configurations

4.3 OTEC Efficiency

4.4 OTEC Design

4.5 Heat Exchangers

4.6 Siting

PROBLEMS

References

Chapter 5. Thermoelectricity

5.1 Experimental Observations

5.2 Thermoelectric Thermometers

5.3 The Thermoelectric Generator

5.4 Figure of Merit of a Material

5.5 The Wiedemann-Franz-Lorenz Law

5.6 Thermal Conductivity in Solids

5.7 Seebeck Coefficient of Semiconductors

5.8 Performance of Thermoelectric Materials

5.9 Some Applications of Thermoelectric Generators

5.10 Design of a Thermoelectric Generator

5.11 Thermoelectric Refrigerators and Heat Pumps

5.12 Temperature Dependence

5.13 Battery Architecture

5.14 The Physics of Thermoelectricity

5.15 Directions and Signs

5.16 Appendix

PROBLEMS

References

Chapter 6. Thermionics

6.1 Introduction

6.2 Thermionic Emission

6.3 Electron Transport

6.4 Lossless Diodes with Space Charge Neutralization

6.5 Losses in Vacuum Diodes with No Space Charge

6.6 Real Vacuum-Diodes

6.7 Vapor Diodes

6.8 High-Pressure Diodes

PROBLEMS

References

Chapter 7. AMTEC

7.1 Operating Principle

7.2 Vapor Pressure

7.3 Pressure Drop in the Sodium Vapor Column

7.4 Mean Free Path of Sodium Ions

7.5 V - I Characteristics of an AMTEC

7.6 Efficiency

7.7 Thermodynamics of an AMTEC

References

Chapter 8. Radio-Noise Generators

8.1 Sole Section

References

Part II: The World of Hydrogen

Chapter 9. Fuel Cells

9.1 Introduction

9.2 Voltaic Cells

9.3 Fuel Cell Classification

9.4 Fuel Cell Reactions

9.5 Typical Fuel Cell Configurations

9.6 Fuel Cell Applications

9.7 The Thermodynamics of Fuel Cells

9.8 Performance of Real Fuel Cells

References

Chapter 10. Hydrogen Production

10.1 Generalities

10.2 Chemical Production of Hydrogen

10.3 Electrolytic Hydrogen

10.4 Thermolytic Hydrogen

10.5 Photolytic Hydrogen

10.6 Photobiologic Hydrogen Production

PROBLEMS

References

Chapter 11. Hydrogen Storage

11.1 Introduction

11.2 Compressed Gas

11.3 Cryogenic Hydrogen

11.4 Storage of Hydrogen by Adsorption

11.5 Storage of Hydrogen in Chemical Compounds

11.6 Hydride Hydrogen Compressors

11.7 Hydride Heat Pumps

PROBLEMS

References

Part III: Energy from the Sun

Chapter 12. Solar Radiation

12.1 The Nature of the Solar Radiation

12.2 Insolation

12.3 Solar Collectors

12.4 Some Solar Plant Configurations

12.5 The Measurement of Time

12.6 Orbital Mechanics

PROBLEMS

References

Chapter 13. Biomass

13.1 Introduction

13.2 The Composition of Biomass

13.3 Biomass as Fuel

13.4 Photosynthesis

PROBLEMS

References

Chapter 14. Photovoltaic Converters

14.1 Introduction

14.2 Theoretical Efficiency

14.3 Carrier Multiplication

14.4 Spectrally Selective Beam Splitting

14.5 Thermo-photovoltaic Cells

14.6 The Ideal and the Practical

14.7 Solid-State Junction Photodiode

14.8 The Reverse Saturation Current

14.9 Practical Efficiency

14.10 Dye-Sensitized Solar Cells (DSSC)

14.11 Organic Photovoltaic Cells (OPC)

14.12 Solar-Power Satellite

14.13 Solar Energy to DC Conversion

14.14 Microwave Generation

14.15 Radiation System

14.16 Receiving Array

14.17 Attitude and Orbital Control

14.18 Space Transportation and Space Construction

14.19 Future of Space Solar Power Projects

Appendix A: Values of two definite integrals used in the calculation of photodiode performance

PROBLEMS

References

Part IV: Wind and Water

Chapter 15. Wind Energy

15.1 History

15.2 Wind Machine Configurations

15.3 Measuring the Wind

15.4 Availability of Wind Energy

15.5 Wind Turbine Characteristics

15.6 Principles of Aerodynamics

15.7 Airfoils

15.8 Reynolds Number

15.9 Aspect Ratio

15.10 Wind Turbine Analysis

15.11 Magnus Effect

PROBLEMS

References

Chapter 16. Ocean Engines

16.1 Introduction

16.2 Wave Energy

16.3 Tidal Energy

16.4 Energy from Currents

16.5 Salination Energy

16.6 Osmosis

16.7 Further Reading

PROBLEMS

References

Chapter 17. Nuclear Energy

17.1 Introduction

17.2 Fission Reactors

17.3 Fusion Reactors

17.4 Cold Fusion

PROBLEMS

References

Chapter 18. Storage of Energy

18.1 Generalities

18.2 Electrochemical Storage (Batteries)

18.3 Capacitive Storage

PROBLEMS

References

Index

Copyright

Academic Press is an imprint of Elsevier

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225 Wyman Street, Waltham, MA 02451, USA

First edition 2005

Second edition 2009

Third edition 2013

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This book and the individual contributions contained in it are protected under copyright by the Publisher (other than as may be noted herein).

Notices

Knowledge and best practice in this field are constantly changing. As new research and experience broaden our understanding, changes in research methods, professional practices, or medical treatment may become necessary.

Practitioners and researchers must always rely on their own experience and knowledge in evaluating and using any information, methods, compounds, or experiments described herein. In using such information or methods they should be mindful of their own safety and the safety of others, including parties for whom they have a professional responsibility. To the fullest extent of the law, neither the Publisher nor the authors, contributors, or editors, assume any liability for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions, or ideas contained in the material herein.

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Foreword to the Third Edition

Think of the field of energy endeavors as having two dimensions: it has a breadth (or width) that encompasses all the scientific aspects of the various technologies used or proposed for the generation, storage, delivery, and utilization of energy. This breadth is open ended—it is always possible to suggest a new way to handle energy. A book that proposed to fully cover all topics would be an encyclopedia of unlimited size. Thus, there is a need to select what a book should cover, a selection that is necessarily arbitrary, frequently left at the whim of the author.

The energy activity field has also a depth (or height) that measures the path of the implementation of any energy system, the path of translating a sound scientific solution into a practical result. This path involves aspect of economy, finance, environmental impact, politics, etc. It is, of course, impossible to put these ideas on a quantitive base, but the author, freelythat most of the difficulty lies in moving an idea up the implementation path given that a scientific solution exists.

The lowest slice of the energy activity space requires rigorous handling and, for this reason, attracts fewer people than the rest of the implementation path that is much more qualitative. This is one reason for there being many more books on the latter area than on the scientific area.

In the illustration, we depicted the energy endeavor space, and indicated by a shaded area, the area of scientific activity, which occupies only a small fraction of the total area but is, nevertheless is an sine qua non activity.

By design, this book limits itself to the scientific area, actually, to only a small fraction of this area, indicated by heavily shaded portions. The much larger unshaded area is covered by many good books.

Professors who have adopted this book, either as a text or a reference, have made numerous suggestions regarding topics to be added. Almost invariable such suggestions have been excellent but, if all were to be adopted, then this book would become unmanageably long.

On the other hand, there have been suggestions to drop some of the irrelevant topics such as the short chapters on radio noise generators. It is almost certain that this technology will never become practical, and, probably no one will include such topics in there formal lectures.

Nevertheless, we have opted to leave them in the book as an intellectual exercise for the curious student. This will give him a chance expand his horizon and to learn how to think out of the box. Clearly, this was what drove the editors of Physical Review to publish, and Professors Panofsky and Feynman to approve the publication of such an outlandish idea.have, however, decided to eliminate Appendix B of Chapter 14, A Semiconductor Primer that is, indeed, written at too low a level for a book meant for graduate students.

Taking all the above into account, it was decided to add a Part V, Land and Beyond to the book. It contains three chapters: Chapter 17, Geothermal Energy, Chapter 18, Nuclear Energy (containing material that was, in the Second Edition, part of Chapter 1), and Chapter 19, Energy Storage, (containing material that was the Appendix Batteries to Chapter 9).

This book discusses a collection of energy topics, whose sequence does not lend itself to a formal course. In such a course, many chapters must be omitted (although the students might be encourage to read up on them). In fact, it is expected that whoever teaches these courses will pick a few pertinent chapters and rearrange their order in an appropriate way.

Foreword to the Second Edition

The widespread desire of the public to become informed about energy has been, in part, satisfied by excellent media coverage and by a plethora of good books on the subject. Most of these are, quite naturally, journalistically slanted and treat technology superficially. Granted that of the various components of the problem—technology, economics, politics—technology represents only a small fraction of the total, but it is the one fraction that must be tackled first.

Those who need to understand the limitations of technical solutions require a good scientific grasp of what is being proposed. This book tries to explain how each energy process discussed actually works. A reasonable degree of mathematics is used to unify and clarify the explanations. By discussing fundamentals more than the state of art, it is hoped to delay the obsolescence of this writing, especially in this moment of very fast evolution of ideas. Those wanting want to labor in this field may find this book useful in preparing themselves to comprehend more specialized articles on whatever energy process they may be especially interested in.

In spite of its fundamentalist approach, this book will eventually become dated, not because fundamentals change but because different fundamentals will be invoked. This second edition discusses several scientific areas that only recently have been recruited to resolve energy problems.

After more than two century of intense development, even very mature technologies such as heat engines (Chapter 2), can still find new and improved forms. This is the case of the free-piston Stirling engine whose high efficiency and very long maintenance-free life has made it now a favorite for generation of electricity in remote, unmanned locations, such as in spacecraft and in planetary exploration. This second edition expands the seven pages of the first edition dedicated to Stirling engines so induced these ultramodern free-piston devices.

Thermoelectrics (Chapter 5) has also progressed in recent years with a better understanding of artificially created nano materials and superlattices that, in a way, get around the limitations of the Wiedemann-Frank-Lorentz law, allowing the synthesis of materials that have large electric conductivity but small heat conductivity.

Fuel cells have matured substantially. Those described in the first edition were adequately light and efficient, but were short-lived and expensive. Catalysis problems were responsible for these shortcomings. The second edition has a much expanded discussion of chemical kinetics and describes very recent work (late 2008) that completely avoids precious metals as catalysts, while substantially outperforming these metals.

Hydrogen production, a fairly old technique, is now beginning to lean on photolytic processes that were of only marginally of interest when the first edition was prepared.

It is perhaps in biomass that the most dramatic evolution has occurred. Public enthusiasm for ethanol and biodiesel has propelled biomass from a minor energy source into one that can contribute markedly to the fueling ofvehicles. Biomass will be firmly entrenched in such a role if the economical hydrolysis of cellulose can be achieved. The second edition delves deeper into the mysteries of the required biochemistry.

Utility-size photovoltaics plants expanded in the fast few years at a sustained rhythm of over 40% per year. They face now a moment of decision: to continue with efficient but expensive silicon devices or to adopt cheap though much less efficient plastic cells. It may all hinge on finding a way to improve the lifespan of the latter. The second edition, discusses theand technology of these polymer cells.

Finally, wind energy has established itself as a major player in energy production. Wind farms are expanding at the same 40% per year rate as photovoltaics, but having started from a much higher base, are now beginning to make significant contributions to the energy mix. When the first edition was prepared, wind energy played a minor role and it was not entirely clear which type of turbine (horizontal or vertical axis) would win out. It is now clear, that the horizontal axis (propeller-type) is the dominant solution. The second edition treats the fundamentals of these machines (Betz limit, Rankine-Froude law, wake rotation, etc), subject that were omitted in the first edition.

This book is based on class notes created in the teaching of Fundamentals of Energy Processes at Stanford since 1976. As both the cost of energy and our dependence on foreign suppliers have rose, so has the interest in these lectures, reflecting the mood of the American people.

Aldo Vieira da Rosa

Palo Alto, CA

August 2008

Foreword to the First Edition

This book examines the fundamentals of some non-traditional energy processes. Little effort is made to describe the state of the art of the technologies involved because, owing to the rapidity with which these technologies change, such description would soon become obsolete. Nevertheless, the underlying principles are immutable and are essential for theof future developments. An attempt is made to present clear physical explanations of the pertinent principles.

The text will not prepare the student for detailed design of any specific device or system. However, it is hoped that it will provide the basic information to permit the understanding of more specialized writings.

The topics were not selected by their practicability or by their future promise. Some topics are discussed solely because they represent good exercises in the application of physical principles, notwithstanding the obvious difficulties in their implementation.

Whenever necessary, rigor is sacrificed in favor of clarity. Although it is assumed that the reader has an adequate background in physics, chemistry, and mathematics (typical of a senior science or engineering student), derivations tend to start from first principles to permit the identification of basic mechanisms.

Energy problems are only partially technical problems—to a large extent economics and politics dominate the picture. In a limited presented here.

The organization of the book is arbitrary and certainly not allencompassing. Processes that can be considered traditional are generally ignored. On the other hand, the list of nontraditional processes considered is necessarily limited.

Acknowledgements

There is no way I could have written this book, or, for that matter, have achieved anything at all, were it not for the steady, unwavering, support and encouragement from Aili, who has stood by me these last 67 years. Thank you, so much, Aili!

My thanks go to Dr. Edward Beardsworth, a renowned expert in new energy technologies, for keeping me continuously alerted to the latest ideas and developments advanced by the numerous workers in the energy field.

My gratitude goes also to the over one thousand students who, since 1976, have read my notes and corrected many typos, and principally, kept me focused on the areas in which their collective interest lay.

Chapetr 1

Generalites

1.1 Units and Constants

Although many different units are employed in energy work, we shall adopt, when possible, the Système International, SI. This means joules and wattsjoules, respectively. See Table 1.1.

Table 1.1 SI Prefixes and Symbols

One might wish for greater consistency in the choice of names and symbols of the different prefixes adopted by the SI. The symbols for submultiplier prefixes are all in lowercase letters, and it would make sense if the multipliers —others to the multiplier itself—kilo (meaning one thousand) indicates the multiplier directly.

We cannot entirely resist tradition. Most of the time we will express pressures in pascals, but we will occasionally use atmospheres because most of the existing data are based on the latter. Sometimes electron-volts are more convenient than joules. Also, energy in barrels of oil or kWh may convey better the idea of cost. On the whole we shall avoid quads, BTUs, calories, and other non-SI units. The reason for this choice is threefold: SI units are easier to use, they have been adopted by most countries, and are frequently better defined. Consider, for instance, the calorie, a unit preferred by chemists. Does one mean the international steam table calorie (4.18674 J)? Or the mean calorie (4.19002 J)? Or the thermochemical calorie (4.18400 J)? Or the calorie measured at 15 C (4.18580 J)? Or at 20 C (4.18190 J)?

Americans like to use the BTU, but, again, there are numerous BTUs: steam table, mean, thermochemical, at 39 F, at 60 F. The ratio of the BTU to the calorie of the same species is about 251.956 with some variations in the sixth significant figure. Remember that 1 BTU is roughly equal to 1 kJ, while 1 quad equals roughly 1 EJ. The conversion factors between the different energy and power units are listed in Table 1.3.

Some of the fundamental constants used in this book are listed in Table 1.2.

Table 1.2 Fundamental Constants

Table 1.3 Conversion Coefficients

1.2 Energy and Utility

of wood or about 2200 kg. The heat of combustion of wood varies between 14 and 19 MJ/kg. If one assumes a mean of 16 MJ per kilogram of wood burned, one cord delivers 35 GJ. Therefore, the cost of energy from wood was $8.5/GJ in northern California.

Still in 2011, the price of gasoline was nearly $4 per gallon, ($1.5 per kg). Since the heat of combustion of gasoline is 49 MJ/kg, gasoline energy used to cost $30.8/GJ, over 3.6 times the cost from burning wood.

In California, the domestic consumer paid $0.15 per kWh or $41/GJ.

From the above, it is clear that when we buy energy, we are willing to pay a premium for energy that is in a more convenient form—that is, for energy that has a higher utility. Utility is, of course, relative. To stoke a fireplace in a living room, wood has higher utility than gasoline and, to drive a car, gasoline has higher utility than electricity, at least for the time being. For small vehicles, liquid fuels have higher utility than gaseous ones. For fixed installations, the opposite is true.

The relative cost of energy is not determined by utility alone. One barrel contains 159 liters or 127 kg of oil. With a heat of combustion of 47 MJ/kg, this corresponds to 6 GJ of energy. In mid-1990, at a price of $12/barrel or $2/GJ, oil cost less than wood (then at $3.2/GJ) notwithstanding oil being, in general, more useful. However, oil prices are highly unstable depending on the political circumstances of the world. The 2012 price of oil (more than $100/barrel or $17/GJ) is now, as one might expect, substantially higher than that of wood, and is one of the driving forces towards the greening of energy sources. Perhaps more importantly, there is the dangerous dependence of developed nations on oil importation from some countries whose interest clashes with that of the West.

Government regulations tend to depress prices below their free market value. During the Carter era, natural gas was sold in interstate commerce at the regulated price of $1.75 per 1000 cubic feet. This amount of gas yields 1 GJ when burned. Thus, natural gas was cheaper than oil or wood.

1.3 Conservation of Energy

Energy can be utilized but not consumed.¹ It is a law of nature that energy is conserved. We degrade or randomize energy, just as we randomize mineral resources when we process ores into metal and then discard the product as we do, for example, with used aluminum cans. All energy we use goes into heat and is eventually radiated out into space.

The consumable is not energy; it is the fact that energy has not yet been randomized. The degree of randomization of energy is measured by the entropy of the energy. This is discussed in some detail in Chapter 2.

1.4 Planetary Energy Balance

.

Besides solar energy, there is a contribution from tides (3 TW) and from heat sources inside the planet, mostly radioactivity (32 TW).

Some 52,000 TW (30% of the incoming radiation) is reflected back to the interplanetary space: it is the albedo of Earth. All the remaining energy is degraded to heat and re-emitted as long-wave infrared radiation. Figure 1.1 shows the different processes that take place in the planetary energy balance mechanism.

Figure 1.1 Planetary energy balance.

concentration is the result of the combustion of vast amounts of fossil² fuels and the destruction of forests in which carbon had been locked.

1.5 The Energy Utilization Rate

The energy utilization rate throughout the ages can only be estimated in a rough manner. In early times, man was totally non-technological, not even using fire. He used energy only as food, probably at a rate somewhat below the modern average of 2000 kilocalories per day, equivalent to 100 W. Later, with the discovery of fire and an improved diet involving cooked foods, the energy utilization rate may have risen to some 300 W/capita.

In the primitive agricultural Mesopotamia, around 4000 B.C., energy derived from animals was used for several purposes, especially for transportation and for pumping water in irrigation projects. Solar energy was employed for drying cereals and building materials such as bricks. Per capita energy utilization may have been as high as 800 W.

Harnessing wind, water and fire dates from early times. Sailboats have been used since at least 3000 B.C. and windmills were described by Hero of Alexandria around 100 A.D. By 300 A. D., windmills were used in Persia and later spread to China and Europe. Hero’s toy steam engines were apparently built and operated. Vitruvius, the Roman architect whose book, first published in Hero’s time, is still on sale today (Vitruvius, 1960), discusses waterwheels used to pump water and grind cereals. In spite of available technology, ancients limited themselves to human or animal power. Casson (1981), a professor of ancient history at New York University, argues that this was due to cultural rather than economic constraints. Only at the beginning of the Middle Ages did the use of other energy sources become fashionable. The second millennium exploded with windmills and waterwheels.

The widespread adoption of advanced agriculture, the use of fireplaces to heat homes, the burning of ceramics and bricks, and the use of wind and water led to an estimated energy utilization rate in Europe of 2000 watts per capita in 1200 A.D. Since the popular acceptance of such activities, energy utilization has increased rapidly. Figure 1.2(left) illustrates (a wild estimate) the number of kilowatts utilized per capita as a function of the date. If we believe these data we can conclude that the annual rate of increase of the per capita energy utilization rate behaved as indicated in Figure 1.2(right). Although the precision of these results is doubtful, it is probable that the general trend is correct: for most of our history, the growth of the energy utilization rate was steady and quite modest. With the start of the industrial revolution at the beginning of the 19th century, this growth accelerated dramatically and has now reached a worrisome level.

Figure 1.2 (left) Rough plot of historical increase in the per capita energy utilization rate. (right) Annual rate of increase of energy/capita was small up to the 19th century.

The increase of the worldwide per capita energy utilization rate was driven by the low cost oil before 1973 when it was substantially lower than now.³ Perez Alfonso, the Venezuelan Minister of Oil in 1946, was among those who recognized that this would lead to future difficulties. He was instrumental in creating OPEC in 1954, not as a cartel to squeeze out higher profits but to reduce the predatory oil consumption to guarantee humanity enough time to develop an economy based on renewable energy sources. Alfonso also foresaw the ecological benefits stemming from a more rational use of oil.

OPEC drove the oil prices high enough to profoundly alter the world economy causing the overall energy utilization rate to slow its increase. Owing to the time delay between the price increase and the subsequent response from the system, several years elapsed before a new equilibrium was established. We witnessed a major overshooting of the oil producing capacity and a softening of prices up to the 1991 Iraqi crisis.

The recent effort of less developed countries (LDCs) to catch up with developed ones has been an important factor in the increase in energy demand. Figure 1.3 shows the uneven distribution of energy utilization rate throughout the world. 72% percent of the world population uses less than 2 kW/capita whereas 6% of the population uses more than 7 kW/ capita.

Figure 1.3 Most countries use little energy per capita while a few developed ones use a lot.

There is a reasonable correlation between the total energy utilization rate and the annual gross national product. About 2.2 W are used per dollar of yearly GNP. To generate each dollar, 69 MJ are needed. These figures, based on 1980 dollars, vary with time, owing to the devaluation of the currency, and to changing economic circumstances. In fact, it has been demonstrated that during an energy crisis, the number of megajoules per dollar decreases, while the opposite trend occurs during financial crises.

Further industrialization of developed countries may not necessarily translate into an increase of the per capita energy utilization rate—the trend toward higher efficiency in energy use may have a compensating effect. However, in the USA, the present decline in energy utilization⁴ is due mainly to a change in the nature of industrial production. Energy intensive primary industries (such as steel production) are phasing out owing to foreign competition, while sophisticated secondary industries (such as electronics and genetic engineering) are growing.

Technological innovation has lead to more efficient energy use. Examples include better insulation in houses and better mileage in cars. Alternate energy sources have somewhat alleviated the demand for fossil fuels. Bio-ethanol is replacing some gasoline. It is possible that the development of fusion reactors will, one day, bring back the times of abundant energy.

Introduction of a more efficient device does not immediately result in energy economy because it takes a considerable time for a new device to be widely accepted. The reaction time of the economy tends to be long. Consider the privately owned fleet of cars. A sudden rise in gasoline price has little effect on travel, but it increases the demand for fuel efficiency. However, car owners don’t rush to buy new vehicles while their old ones are still usable. Thus, the overall fuel consumption will only drop many years later, after a significant fraction of the fleet has been updated.

Large investments in obsolete technologies substantially delay the introduction of more efficient systems. A feeling for the time constants involved can be obtained from the study of the market penetration function, discussed in Section 1.7.

1.6 The Population Explosion

In the previous section we discussed the per capita energy utilization rate. Clearly the total rate of energy utilization is proportional to the planetary population which has been growing at an accelerated rate.⁵

The most serious problem that confronts mankind is the rapid growth in population. The planet has a little more than 7 billion inhabitants, and the growth rate these last few decades has been a steady 1.4% per year. Even if, right now, everyone were to agree on a limit of two children per family, then, under present-day actuarial conditions, the population would stabilize at around 11 billion only by 2050. Population growth alone could account for 1.4% a year increase in energy demand. In fact the recent growth rate of energy use exceeded the population growth rate. The worldwide rate of energy use was 9 TW in 1980 and 15.2 TW in 2008, a yearly growth of 1.9%. EIA, the Energy Information Administration (Energy Information Administration, 2007), has used this constant 1.9% per year growth rate to estimate an energy usage rate of slightly over 22 TW in 2030. Clearly, supplying this much energy will not be an easy task.

The constant population increase has its Malthusian side. About 10% of the world’s land area is used to raise crops—it is arable land, hectares are dedicated to agriculture. Up to the beginning of the 20th century, on average, each hectare was able to support 5 people (Smil, 1997), thus limiting the population to 7.4 billion people. More arable land can be found, but probably not enough to sustain 11 billion people. What limits agricultural productivity is nitrogen, one kilogram of which is (roughly) needed to produce one kilogram of protein. Although it is the major constituent of air, it is, in its elemental form, unavailable to plants and must either be fixed by appropriate micro-organisms or must be added as fertilizer.

Nitrogen fertilizers are produced almost exclusively from ammonia. When used in adequate amounts they can increase productivity by nearly an order of magnitude. The present day and the future excess population of the planet can only exist if sufficient ammonia is produced. Although there is no dearth of raw materials (it is made from air and water), its intensive use has a serious adverse environmental effect as discussed by Smil (1997).

1.7 The Market Penetration Function

The enormous body of literature accumulated throughout the centuries makes it impossible for even the most assiduous readers to have studied the writings of all scientist and philosophers of the past. Hence, modern writers have built up a large roster of often cited, rarely read authors whose ideas are frequently mentioned even when only nebulously understood. This is, for instance, the case of Thomas Robert Malthus. We all have an idea that he had something to say about population growth. In 1846, Pierre François Verhulst put this population growth idea in the plausible mathematical form known now as the Verhulst equation. This equation is an excellent starting point to understand the problem of technological substitution, that is, the question of how a more advanced technology will replace a more cumbersome older one.

Adapting the Verhulst equation to this problem we have

(1.1)

where f ), t is time, and a is a constant. In words, the Verhulst equation states that the fractional rate of change in f (represented by ) must be proportional to that fraction of the market, , not yet taken over by the new technology. This makes intuitive sense.

Verhulst equation is a non-linear differential equation whose solution is

(1.2)

b being an integration constant.

f can be expressed explicitly

(1.3)

which allows the plot f as a function of t, as it was done in .

Figure 1.4 The Verhulst function.

Equation 1.3, is an example of the logistics function. One defines a takeover time interval:

(1.4)

Equivalently, we can define a market penetration time,

(1.5)

is called the market abandonment time.

In 1970, two General Electric scientists, as a function of t) not in the form of Equation 1.3because the former yields a straight line plot and is, thus, much easier to handle analytically and to extrapolate.

Figure 1.5 shows the rates of penetration of the oxygen steel process into the market previously dominated by the open-hearth and Bessemer technologies. It can be seen that the penetration rate was fastest in Japan (a takeover time interval of 8.3 years). In Germany and in the U.S., the takeover time was 11.8 years, while in the Soviet Union it was 14.0 years. The results show surprisingly small dispersion—the observed points fall all very nearly on the straight line regression. As an example, in the case of Germany and USA, the regression is

(1.6)

where t is the time in years, expressed as 19xx.

Figure 1.5 Penetration of the oxygen-steel technology in the steel production market.

The graph shows that the takeover times were different in different countries and, as Fisher and Pry point out, the technique appears to work even in a centralized command economy. In addition, it turns out, as expected, that even in a same country, substitutions of different types of products have different penetration rates. Some substitutions occur rapidly, others take a long time. Fisher and Pry list a number of substitutions with takeover times ranging from just over 8 years for the case of detergents replacing natural soaps in Japan to 58 years for the case of synthetic rubber replacing natural rubber in the U.S.A.

The plots of Figure 1.5 depend on two parameters, a and b. The former is related to the takeover time and determines the slope of the graph. If instead of using the actual time, t, then all plots will have the same slope and can be integrated into a single graph. See Figure 1.6 showing how 17 different substitutions fit with surprising accuracy a single straight line.

Figure 1.6 Fisher-Pry plot for 17 different substitutions.

, is introduced as follows.

and

(1.7)

and

(1.8)

, hence, subtracting Equation 1.8 from Equation 1.7.

(1.9)

Thus, the market penetration formula can be written as:

(1.10)

A remarkable and useful property of the market penetration function is its insensitivity to many factors that profoundly affect the overall market. Thus, although variations in political or geopolitical circumstances can substantially affect market volume, they frequently have a minimal effect on the fractional market share, probably because they influence simultaneously all competing technologies.

. Since the behavior of the technology being replaced is, in this case, simply a mirror image of the advancing technology, graphs are shown only for the latter. This is not true for the case of multivariate competition when several different technologies compete to fill the market needs.

Fisher and Pry’s results are entirely empirical. Marchetti (1977), working at the International Institute for Applied System Analysis in Austria (IIASA), still using an empirical approach, extended the Fisher-Pry idea in two meaningful ways. One was to make it possible to consider cases in which the market for a given product was supplied by more than two technologies. To this effect, Marchetti introduced the rule of first in, first out. The other was the application of the Fisher-Pry procedure to the case of various energy sources. This allows the prognostication of the market share of individual energy supplying technologies. In his 1976 paper, Marchetti presents the available data on the market share of different fuels used in the U.S.A. during the 1850 to 1975 period. From these data, he obtained the different coefficients of Equation 1.2 for each fuel. Wood was already abandoning the market with a characteristic abandonment time of 60 years being replaced by coal (takeover time of 66 years). This substitution was driven by the much greater usefulness of coal in driving the locomotives of the expanding railroad system. Increasing use of oil and natural gas, beginning at the turn of the 20th century, caused the turn around of the coal share (but not of the total coal use). Coal started abandoning the market with a characteristic time of 99 years. Initially, oil’s takeover time was 52 years, but then rose to 135 years and showed signs of turning around in the early 1970s. All this is illustrated in Figure 1.7.

Figure 1.7 Market share of different fuels in the U.S.A. reported by Marchetti, 1976. Plots of ln (f/1-f) vs. time exhibit surprising regularity.

As an exercise in prognostication, Marchetti, using the trend lines of Figure 1.7derived only from data before 1935, calculated the behavior of the oil market share, employing the formula,

(1.11)

The results are displayed in Figure 1.8. They are very accurate, a fact that led Marchetti to comment: …we were able to predict the fractional market share of oil in the U.S.A. up to 1970 with a precision of better than one percent. Alas, It’s tough to make predictions, especially about the future.⁶ If we extend Marchetti’s graph to 2008, we find that the nice regularity of the behavior of the coal and gas shares, on which the prognostication is based, breaks down badly, in modern times. See Figure 1.9. To understand why, we must refer to the work of Peterka (1977), which, dropping the empiricism of previous authors, put the analysis of market penetration on a firmer theoretical basis. Peterka carefully defines the conditions under which the empirical models hold.

Figure 1.8 Prognostication of the behavior of the oil market share up to 1990 using only observed data from before 1935. The results are surprisingly accurate and predict the peak that actually occurred in the 1960s. This is unrelated to the OPEC crisis in the early 1970s.

Figure 1.9 The regular and predictable behavior of the market penetration function for coal and gas used by Marchetti breaks down if modern data are added to his graph of Figure 1.8 .

Peterka argues that scientific forecasting must be based on a priori assumptions. In the case being discussed here, a fundamental assumption is that there be no external infusion of capital once the technology has established itself. This is self evident—if during the penetration period, a substantial increase in capital becomes available this will alter the rate of penetration even though it may not increase the profitability of the enterprise. It would be of great value if it were possible to estimate how much it would cost to accelerate the penetration by a given amount. Unfortunately, this is not yet possible. The assumption above, implies that when a technology starts to penetrate the market it must already be well developed and its degree of maturity determines the eventual penetration rate, thus, the magnitude of the original external investment actually determines the initial conditions for the model… (Peterka, op. cit.).

The market penetration rules discussed in this section provide a powerful tool for planning, but must be used with caution and with close attention to possible violations of implicit assumptions.

1.8 Planetary Energy Resources

In Section 1.5, we pointed out that the rate of per capita energy utilization rose rapidly in the last century. This, combined with the fast increase in population mentioned in Section 1.6, leads one to the inescapable conclusion that we are facing a serious challenge if we hope to maintain these trends in the foreseeable future. To investigate what can be done to resolve this difficulty we must first inquire what energy resources are available (Section 1.8) and, next, (Section 1.9) how we are using the resources at present. Figure 1.10 shows the planetary energy resources. These can be renewable or nonrenewable.

Figure 1.10 The energy resources of Earth.

Geothermal energy has been used for a very long time in Iceland and more recently in Italy, New Zealand, and the United States. In many places it is possible to take advantage of the stability of the ground temperature a few meters below the surface. The ground can, thus, be used as a source of heat in the winter and of cold in the summer.

Gravitational energy—that is, energy from tides (see Chapter 16) has been used in France. Tides can only be harnessed in certain specific localities of which there is a limited number in the world. Gravitational energy is also important in all hydroelectric plants.

Of the renewable resources, solar energy is by far the most abundant. A small part of it has been absorbed by plants and, over the eons, has been stored as coal, oil, and gas.

1.8.1 Mineral Assets

A mineral that exist in a given territory but has no great probability of economical exploitation, constitutes an occurrences of the mineral. If it exists in greater abundance and appears to have economic value, then this mineral is a resource. Finally, if the mineral is valuable, legally exploitable economically, it is a reserve. Proved reserves are minerals that have been discovered but not yet produced. Reserve growth is the increase in the reserves owing to further development or to the introduction of better extraction technology. Undiscovered reserves represent the best possible guess of the magnitude of plausible new discoveries. The magnitude of the reserves of a given mineral depends on the price one is willing to pay. As the prize rises, resources that previously were uneconomical will become attractive and are included in the estimated reserves.

Estimates of reserves, fossil or nuclear, are extremely uncertain and are sure to be greatly underestimated because of incomplete prospecting. Table 1.4 gives us only a very rough idea of our fossil fuel reserves and Table 1.5 shows an even more uncertain estimate of reserves of fissile materials. The estimates of nuclear fuels do not include the reserves of the old Soviet Union and China. Values given in the tables are far from precise. They probably represent a lower limit, because people who estimate these numbers tend to be conservative, as testified by the secular increase in proved reserves: reserves of dry natural gas, 2,200 EJ in 1976, rose to 6,200 EJ in January 2007 not withstanding the substantial consumption of gas in the intervening years. A similar situation exists with respect of proved oil reserves: 7,280 EJ in 2002 and 7,900 EJ in 2007. For oil and gas, the table lists the sum of proved reserves, reserve growth and undiscovered reserves. Proved reserves are fuels that have been discovered but not yet produced. Those for oil and gas are reported periodically in the Oil and Gas Journal.

Table 1.4 Known Fossil Fuel Reserves

Table 1.5 Known Reserves of Fissile Materials †

† Does not include the former USSR and China.

Reserve growths and undiscovered reserves are estimated by the US Geological Survey. For example, in 2002 the Oil and Gas Journal reported proved reserves of oil of 7,280 EJ and the USGS estimated a growth of 4,380 EJ and undiscovered oil reserves amounting to 5,630 EJ adding up to the total of 18,900 EJ listed in the table. For coal, the table shows only proved reserves. The total reserves for this fuel are, thus, substantially larger than listed.

A particularly uncertain number is that for hydrated methane. William P. Dillon, a geologist of the USGS, testified in the U.S. House of Representatives in 1998, that the amount of methane contained in the world’s gas hydrate accumulations is enormous, but estimates of the amounts are speculative and range over three orders-of-magnitude from about 100,000 to 270,000,000 EJ of gas. We, being ultraconservative, listed the lower figure.

Methane Clathrate.

Clathra is the Latin word for bar or cage. Atoms in a number of molecules group themselves in such a fashion that a cavity (or cage) is left in the center. The most famous of these arrangement is the buckyball, a molecule consisting of 60 carbon atoms arranged as a hollow sphere capable of engulfing a number of substances. Buckyballs, discovered in the early 1980s, are not alone among hollow molecules. Under appropriate circumstances, water will freeze forming a cage consisting, sometimes, of 20 water molecules, but more commonly, of 46 water molecules. The configuration is unstable (it decays into a common ice crystal) unless certain gases become trapped in the central cage of the large molecule. Gases commonly trapped are methane, ethane, propane, iso-butane, n-butane, nitrogen, carbon dioxide, and hydrogen sulfide. Ice crystals consisting of 46 water molecules trap up to 8 guest gas molecules (a water-to-gas ratio of 5.75:1). In natural deposits, methane is by far the most abundant guest and the one of greatest economic interest. Usually, up to 96% of the cages are fully occupied. These solid hydrates are called clathrates. This means that the methane is highly compressed. See Problem 1.28. Notwithstanding its low density, water ice clathrate does not float up from the bottom of the ocean because it is trapped beneath the ocean sediment. Clathrates form at high pressure and low temperature under sea and are stable at sufficient depth. The methane is the result of anaerobic digestion of organic matter that continuously rains down on the ocean floor. See Chapter 13. There is no mature technology for the recovery of methane from clathrates. Proposed processes all involve destabilizing the clathrate and include:

1. Raising the temperature of the deposits.

2. Depressurization the deposits.

3. Injecting methanol or other clathrate inhibitors.

The latter process may be environmentally undesirable. There are dangers associated with methane clathrate extraction. The most obvious ones are the triggering of seafloor landslides and the accidental release of large volumes of methane into the Earth’s atmosphere where it has a powerful greenhouse effect. Some scientists attribute the extinction that marked the end of the Permian era (300 to 250 megayears ago), to an enormous bubbling up of methane. The Permian–Triassic extinction (P-Tr extinction) was the worst catastrophe to hit the biosphere of Earth—96% of all ocean species disappeared, together with 70% of land species.

1.9 Energy Utilization

Most of the energy currently used in the world comes from non-renewable sources as shown in Figure 1.11 which displays energy sources in 2011 for the whole world and for the United States, respectively.

Figure 1.11 Energy sources: (left) World, (right) United States.

Regrettably, most of the renewable resources (geothermal, biomass, solar and wind) still make only a small contribution to the overall energy picture. Figure 1.12 shows that as late as 2008 only 8.3% of the energy used to generate electricity in the USA came from renewable sources. Of these, 83% came from hydroelectrics. Thus, only 2% of the total came from the remaining renewables.

Figure 1.12 Sources of electric energy in the United States.

Disappointingly, so far, the contribution of solar and wind energy has been small. But this is beginning to change significantly in these last few years (since about 2004).⁷

For all sources of energy, the cost of the plant is proportional to the installed capacity, while the revenue is proportional to the energy generated. The plant utilization factor is the ratio of the energy produced to that which would be produced if the plant operated uninterruptedly at full capacity (as a result of the great variability of wind velocity. Although specific data for solar plants are not available, they also suffer from a low utilization factor owing the day/night cycle and the vagaries of meteorological conditions.

Table 1.6 Electric Energy Use, USA 2005

These data are from EIA (Energy Information Administration.).

It is of interest to know which are the main users of energy in the United States. (See Figure 1.13) American residences account for a bit more than 20% of all energy used. Most of it is employed for ambient heating, an area in which considerable economy can be realized, especially through better home design, and, in some areas, by use of geothermal energy.

Figure 1.13 The different users of energy in the USA.

Waste heat from electric power plants can be used for residential and commercial water and space heating and constitutes a form of District heating. The other form uses dedicated centrally located boilers, not a co-genertion scheme. Some decades ago, when steam plants had an average efficiency of 30%, a whopping 70% of the fuel energy was either thrown away or was piped as hot water to consumers. The latter option increased the overall system efficiency to more than 50%. Currently, steam plants have, by themselves, efficiencies that exceed 50%,⁸ and district heating can boost the overall efficiency to some 90%. This comes at considerable initial cost, so the economic benefits are only realizable in the long term. District heating requires the location of power plants in densely populated areas, consequently, it is inadvisable in the case of nuclear plants and large fossil-fueled installations. However, fuel cell plants (see Chapter 9), being noiseless and pollution free, can be placed in a downtown area.

Although the largest district heating system in the world is the one operated by Con Edison Steam Operations, active since 1882, a subsidiary of Consolidated Edison of New York, the technology is, in relative terms, much more popular in Europe.

American industry’s relative use of energy may decrease even in face of an expansion of this sector because of the progressive shift of emphasis from energy intensive industry, such as iron and steel, to more sophisticated activities that have a low energy demand per dollar produced.

1.10 The Efficiency Question

There are two ways in which an increase in efficiency can ameliorate the current energy problem. One can work towards using less energy to obtain a given effect or one can use less fuel to generate a given amount of energy. In either case, it is only worthwhile trying to improve the efficiency of processes that are, at the present state of technology, clearly inefficient. Not too much is gained in improving the efficiency of electric motors.⁹

An area in which efficiency can be improved by nearly one order of magnitude is illumination. About 10% of the energy used by residences go towards illumination. We are in a period of transition from the extremely inefficient incandescent bulbs to the compact fluorescent lamp, to the super efficient white LEDs.

In Table 1.7, Merit is defined as the product of the efficiency (expressed in percent) by the lifetime in hours. According to this arbitrary criterion, LEDs have the potential of being 4000 better than incandescent bulbs. Of course, a number of technical problems as well as the high cost of the LEDs must be addressed before they become the standard source of light.

Table 1.7 Relative merit of different light sources

† The actual efficiency of commercially available white LEDs is substantially less than the listed 22%, it is about 13%. However laboratory prototypes have demonstrated the efficiency in the table above.

Efficiency improvement will certainly have a great impact in the transportation sector, especially on the private transportation sector still heavily dominated by wasteful heat engines. We are still enamored of heavy, overpowered cars that operated with less than half the fuel efficiency possible with current technology. Thus, a cultural change would be desirable. The transition to more rational personal transportation has started with the introduction of hybrid cars, followed by the appearance of plug-in hybrids and perhaps electric or fuel cell cars, both of which promise to combine high efficiency with low pollution.

Surprisingly, the heat engine which has been among us (in a useful practical sense) since the middle of the 18th century, has continued to be improved at a steady pace. See Figure 1.14, based on data from the Energy Information Agency. For example, their efficiency grew from 22% in 1950 to 60% in 2010 a gain of an, incredible, 270%.

Figure 1.14 Evolution of steam engine efficiency.

To gain an idea of the significance of such a gain in efficiency, consider the following scenario. Of course, this scenario could not become reality because the necessary technology was not, then, available.

The installed capacity of thermal plants (including nuclear) was, in 1950, about 65 GW. If no new plants were built from that date on, but, if the old ones were updated improving their efficiency by 270%, then a total of 176 GW of new generating capacity would have been created.

emission. This would be equivalent to installing nearly 200,000 modern wind turbines.¹⁰

In Chapter 3, in which heat engines are discussed, we will introduce a few paragraphs explaining how this added efficiency was achieved and what additional efforts are being made to extend the efficiency gains even further.

The sources of added efficiency included:

1. Better design, especially of the shape of the turbine blades.

2. Operation with the working fluid in the supercritical regimen.

as working fluid instead of water.

4. Use of Brayton cycles instead of Rankine cycles.

To understand why supercritical fluids are used, it is necessary to know a few basic ideas about phase diagrams of pure substance, a subject taken up in Chapter 2 in which thermodynamics and allied areas of physics are explained.

1.11 The Ecology Question

We have shown that there is an almost unavoidable trend toward increasing energy utilization. We have also pointed out that at present the energy used is at least 85% of fossil origin. Finally, we have shown that the fossil fuel reserves seem ample to satisfy our needs for a good fraction of the next millennium. So, what is the problem?.

Most of the easily accessible sources of oil and gas have already been tapped. What is left is getting progressively more expensive to extract. Thus, one part of the problem is economical. Another is political—most of the fuel used by developed nations is imported (using the large American reserves is unpopular and politicians hesitate to approve such exploration). This creates an undesirable vulnerability. The major problem, however, is ecological. Fossil fuels are still the most inexpensive and most convenient of all energy resources, but their use pollutes the environment, and we are quickly approaching a situation in which we can no longer dismiss the problem or postpone the solution.

By far, the most undesirable gas emitted is carbon dioxide whose progressively increasing concentration in the atmosphere (from 270 ppm in the late 1800 to some 365 ppm