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Michele Aresta · Iftekhar Karimi ·
Sibudjing Kawi Editors
An Economy
Based on
Carbon Dioxide
and Water
Potential of Large Scale Carbon Dioxide
Utilization
An Economy Based on Carbon Dioxide
and Water
Michele Aresta Iftekhar Karimi
Sibudjing Kawi
Editors
An Economy Based
on Carbon Dioxide
and Water
Potential of Large Scale Carbon Dioxide
Utilization
123
Editors
Michele Aresta Iftekhar Karimi
IC2R srl, Lab H124, Tecnopolis Department of Chemical and Biomolecular
Valenzano, Italy Engineering
National University of Singapore
Singapore, Singapore
Sibudjing Kawi
Department of Chemical and Biomolecular
Engineering
National University of Singapore
Singapore, Singapore
ISBN 978-3-030-15867-5 ISBN 978-3-030-15868-2 (eBook)

https://doi.org/10.1007/978-3-030-15868-2
Library of Congress Control Number: 2019936294
© Springer Nature Switzerland AG 2019

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
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Preface
The Carbon Dioxide Problem
Surface (biomass) and sub-surface (fossil-C such as coal, oil, gas) C-based assets
have been, and will be for long time yet, used as source of energy and goods by
humans. The use of all such materials causes the formation of CO2, which is
emitted into the atmosphere. The intensity of the emission of CO2 has continuously
grown and parallels the growth of both the population and average standard of life.
(Figs. 1 and 2).
This has caused the continuous accumulation of atmospheric CO2 which has
reached 408 ppm these days with respect to 275 ppm of the preindustrial era. The
atmospheric level of CO2 is the “warning light” for the “health” of our planet.
A correlation exists between the consumption of energy—the CO2 emission—the
accumulation in the atmosphere and the increase of the planet temperature (Figs. 3
and 4) that may cause non-return catastrophic events. Whether CO2 is the direct
actor or is an “indicator” of the impact caused by human activities on the atmo-
sphere, is in question. As a matter of fact, humans are using C-based resources in a
“highly inefficient” way: the efficiency of conversion of chemical energy (fossils or
biomass) into other forms of energy (electrical, thermal, mechanical, etc.) ranges
around 27–35%. This means that 73–65% of the original chemical energy is
released to the atmosphere in the form of heat, often at high temperature, causing its
direct heating. As the emission of CO2 is related to the amount of C-based fuels
burned or goods used, it becomes an easy “witness” of the impact humans are
causing on Earth (even if not the direct cause). However, there is a general fear that
continuing to accumulate CO2 into the atmosphere (or continuing with an inefficient
use of natural resources) may increase the temperature of our planet. Although CO2
is a greenhouse gas (GHG), its atmospheric concentration is much lower than that
of other GHGs, e.g. water vapour. Is the atmospheric CO2 that causes planet heating
or the released heat or both? A question rises: Supposed that we capture all the
produced CO2, but continue to heat the atmosphere with inefficient conversion of
chemical energy (C-based energy sources) into other forms of energy, shall we
“cool down” our planet? The most effective solution would be to reduce the use of
C-based fuels (that will imply the reduction of CO2 emission) and the release of
v
vi Preface
Fig. 1 Growth of world population
Fig. 2 CO2 emission
heat to the atmosphere. This will require a great effort in terms of more efficient
technologies in the use of primary C-based sources of energy, covering the entire
chain of production of electric energy, heating systems, industrial plants and
transport sector: our whole life! This will take long time and demand huge eco-
nomic means. As for now, the policy is to reduce the emission of CO2 into the
atmosphere, will or will not such practice be the solution to the climate change
(CC), shifting from fossil-C (that has produced a net increase of the atmospheric
CO2-level) to renewable-C and to perennial C-free energy sources.
How to avoid CO2, thus?
Preface vii
Fig. 3 Energy consumption
Fig. 4 Increase of average temperature
The agreed target (ONU 2018 and previous International Agreements) is to stay
below 2° rise of the average temperature of our planet with respect to 1990. We are
already 1.5° above; therefore, we must urgently slow down the use of fossil carbon
in order to stay within the target. Defossilization of energy is the necessary action,
and the proposal is to advance in such direction in next years. From now to 2050,
fossil-C should slowly but steadily be replaced by quasi-zero-C emission energy
sources. Alternatives are the use of solar, wind, geothermal, hydro-energy sources
(SWGH, perennial energy sources). The question is whether or not such sources
will provide energy with the requested density and intensity for powering industrial
sites and other intensive energy users (megalopolis). (see P. Moriarty, D. Honnery,
viii Preface
What is the global potential for renewable energy? Renewable and Sustainable
Energy Review, 2012, 16, 244–252). On the other hand, the use of biomass will
cover a minor part of the energy needs limited by the regeneration rate. The pro-
duction rate of CO2 is much higher (around 6–15 gCO2 m−2 s−1 from the com-
bustion of several kinds of wood-see Tran, H.C.; White, R.H. Fire and Materials,
1992, 16, 197–206.) than the fixation of CO2 by photosynthesis (the best values are
observed in microalgae (see Adamczyk, M.; Lasek, J.; Skawinska, A. Appl Bio-
chem Biotechnol, 2016, 179, 1248–1261), better fixing agents than terrestrial plants,
that are in the range 0.1–1.7 gCO2 l−1 day−1 or 0.00057–0.0098 gCO2 m−2 s−1).
Therefore, the combustion rate is from 1000 to 10,000 times faster than the
C-fixation by photosynthetic microorganisms and microalgae. Will nuclear come
back? This is not excluded, if safe production of electricity will be developed. Our
future looks quite problematic and to what extent energy-poor countries in Asia,
America and Africa will rise their standard of life is an open question, as it is not
easy to state whether Northern America, Europe, Japan will have all to restate their
habitudes. Shall we necessarily go towards a global lower energy consumption?
When this will occur? In the meanwhile, attention is devoted to reduce the CO2
emission into the atmosphere.
Measures for the Reduction of the CO2 Atmospheric Level
The technologies for reducing the use of fossil-C and the emission of CO2 into the
atmosphere can be categorized as reported below.
• Higher efficiency in the conversion of chemical energy (fossil-C and biomass)
into other forms of energy: thermal, electrical, mechanical, etc. As said above,
the average efficiency ranges today around 27–35%; therefore, 73–65% of the
original chemical energy is released to the atmosphere in the form of heat,
causing its direct heating. Improving the efficiency of the actual energy system
is possible using both upstream and downstream technologies, but the economic
cost is often quite high. In practice, power stations, industrial processes,
transportation means should all be restyled and made adequate to the target of
reducing the loss of energy in the form of heat. As a lower profile strategy, new
power and industrial plants should all be built according to new efficiency
criteria (e.g. all power plants should be built as IGCC), with much higher
CAPEX. Heat could be recovered (when and where it makes sense) and used in
a range of diverse low-temperature applications (in part this is already done,
even if with rare-spot applications). The efficiency of primary energy conversion
could be increased by 10–20 points, according to the different sectors. An
improvement of the actual system is, thus, possible but it will take long time and
demand a lot of economic resources.
• Efficiency in the utilization of the different forms of energy, avoiding misuses.
This is the easiest route to C-saving and should be implemented by each single
person. The implementation of virtuous practices can produce reduction of
energy used, and thus produced, with reduction of conversion of fossil-C and
CO2 emission with a possible target of 5–10%.
Preface ix
• Decarbonization of energy, by using perennial primary sources, alternative to

fossil fuels, such as SWHG. Such change is ongoing, and solar-, wind- and
geo-power are being efficiently used, even if still at a moderate global intensity
(5–8 % of global consumption) and leopard-spot distribution. It must be
emphasized that perennial sources have a different availability on our planet and
regional solutions must be implemented. Conversely, fossil-C (coal, oil, gas) is
easily transportable and can reach any point on our planet: this is a plus in
favour of existing fossil-C-based technologies. The moment being, anyway it is
worth to emphasize that virtuous countries exist, which produce large amounts
of their energy from SWHG (https://www.climatecouncil.org.au/11-countries-
leading-the-charge-on-renewable-energy/) as reported in Table 1.
It is worth to emphasize that if the energy sector can be decarbonized, the
chemical, polymer, pharmaceutical, cosmetic, materials industry will not.
Therefore, C-based goods will continue to exist and most likely the use of
fossil-C will be continued for long time yet in the future. As a matter of fact, the
international programme 205050 foresees 50% reduction of emissions with
respect to 1990 (for USA with respect to 2005) for EU and G20 countries by
2050. Afterwards, the reduction should continue at a rate of 1.5% per year.
• Use of renewable carbon, such as biomass. Renewable carbon has a different
abundance on Earth and can find a different utilization. Biomass (land and
aquatic) already finds application in several fields: from energy to chemicals and
materials production. Because of the relative abundance/scarcity, even biomass
has an odd usability and its transport is not energetically and economically
efficient. Even in this case, fossil-C is a winning option for its higher energy
density.
Table 2 says that liquid fuels are the best options for energy storage and
transportation. Therefore, the conversion of electricity produced via SWGH into
liquid fuels by combining CO2 reduction and water oxidation is a convenient way
for storing and transporting energy.
Table 1 Use of energy sources alternative to fossil-C in some virtuous countries

Country Actual use of SWHG for electricity generation Perspective use of SWHG
Sweden 100% 2050
Costa Rica 99% (2015) C-neutral 2021
Nicaragua 54% 90% 2021
Scotland 97% of household electricity
Germany 36.1+ % average with some >85% spot
Uruguay 95%
Denmark 42% 100% (2050)
China 1000 coal mines closed in 2018
Morocco 50% 2020
Kenya 51% (2015) 70% (2020)
x Preface
Table 2 Energy density of a Energy carrier MJ/kg

variety of energy carriers
Diesel 36
Gasoline 34
Coke 30
Brown coal 18
Methanol 17
Bio-oil from algae 13
H2(liquid, 20 MPa) 9
H2(compressed) 2
Battery (lead) 0.33
Battery (lithium) 2.8
Capture of produced CO2 from point-continuous sources or from the atmo-

sphere. Capture can be applied either to point-continuous-fixed sources (industries
or power plants) or even everywhere if the source is the atmosphere. If practised at
reasonable economic and energetic costs, capture will make available large amounts
of CO2 that can be either disposed (CCS) or converted into chemicals, materials and
fuels (CCU). The separation of CO2 from flue gases from power stations or
industrial processes (Table 3) requires an amount of energy, which depends on the
composition of the flue gas and the use one wishes to make of separated CO2 that
drives its purity. The separation is a process that requires energy, and in the actual
energy system implies the use of fossil-C. It has been calculated by DoE-USA that
recovering CO2 and disposing it in land reservoirs 40 km away from the power
station where it is generated (a particularly rare and favourable case) consumes 25%
of the produced electric energy. Such amount increases with the distance of ship-
ping and the nature of disposal site: it may reach 40%+. Consequently, the capture
and housing of CO2 expand the extraction of fossil-C because additional energy is
necessary for such end-of-pipe operation. Modern power generation technologies
(such as IGCC) proceed to the decarbonization of fossil fuels before combustion.
This means that fossil fuels are converted into CO2 and H2 and the latter is used for
clean energy generation, but not zero-C emission as CO2 is anyway produced even
if in the precombustion phase.
Table 3 CO2 emission from Industrial sector MtCO2/y produced

industrial sectors
Cement >1000
Oil refineries 850–900
Iron and steel ca. 900
Fermentation >200
Ethene and other 155–300
petrochemical processes
Ammonia 160
LNG sweetening 25–30
Ethene oxide 10–15
Preface xi
In the short term, it may make sense to recover CO2 from industrial sources that
may provide more pure CO2 than flue gases from power stations. Table 3 shows
that ca. 3 500 Mt/y of quite pure CO2 is available, which covers ca. 10% of the total
emission. The advantage of recovering–converting CO2 on-site brings to a closed
loop. Obviously, this approach is very proficient for sites where several industrial
activities are present and an efficient recovery of CO2 is possible: clustering process
is a way to optimize the energy and waste system. And this can be an interesting
option for the future of our industry and the energy sector.
Recovery from the atmosphere (medium–long term) has the advantage of not
requiring an industrial site or a power station as source. Interestingly, the atmo-
sphere can provide also water vapour: this means that co-processing atmosphere-
sourced CO2 and water vapour will make possible to produce Syngas and thereafter
energy-rich products (fuels). Such practice is very suggestive of Nature and can be
implemented everywhere on our planet, making possible a local production of
necessary fuels and chemicals completely decoupled from the existence in situ of
natural fossil resources or emitters, with great benefit for non-industrialized coun-
tries which are not even rich of fossil-C.
An Economy Based on CO2 and Water: it is a vision today. Will science and
technology be able to make it a reality? Yes, but the correct conditions for the use
of perennial energies must be developed and investment in research is necessary
at the correct level, with the integrated cooperation of academy, industry and
governments.
It is an investment in the future of humankind and our planet.
This book makes the point on where we are and where we have to go for
exploiting such option.
After presenting the potential and bottlenecks of large-scale CCU (Chap. 1), the
capture (Chap. 2) and the technological applications (Chap. 3), various aspects of
utilization are discussed in detail, namely carbonation of basic natural or industrial
matrices (Chap. 4), conversion into energy-rich products (Chaps. 5 and 6), elec-
trochemical and photo-electrochemical conversion (Chap. 7) and Plasma tech-
nologies (Chap. 8). Bio-based routes are discussed in Chaps. 9–11, highlighting the
integration of biotechnologies and catalysis. Chapter 12 makes a techno-economic
and energetic analysis of selected CO2-based processes. At the end, the perspective
use of CCU is presented.
Michele Aresta
IC2R srl, Lab H124, Tecnopolis
Valenzano, Italy
Contents
1 Large Scale Utilization of Carbon Dioxide: From Its Reaction

with Energy Rich Chemicals to (Co)-processing with Water to
Afford Energy Rich Products. Opportunities and Barriers . . . . ... 1
Michele Aresta and Francesco Nocito
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 CCS Versus CCU: The Amount Issue . . . . . . . . . . . . . . . . . . . 2
1.3 CO2 Conversion Options: The Energy Issue . . . . . . . . . . . . . . . 2
1.4 CCU and Resources Conservation . . . . . . . . . . . . . . . . . . . . . . 6
1.5 CCU and Innovation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.6 CCU and Sustainability of the Chemical and Polymer
Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.7 Integration of Technologies: Biotechnologies and Catalysis . . . . 18
1.8 CCU, Clustering of Processes and the Energy Sector . . . . . . . . 21
1.9 Miscellanea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.10 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
2 Capture of CO2 from Concentrated Sources
and the Atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 35
Xiaoxing Wang and Chunshan Song
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 36
2.2 Development Progress of Supported PEI Sorbents for CO2
Capture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.2.1 Effect of Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.2.2 Effect of PEI-Type . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2.3 Effect of Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.3 CO2 Sorption Mechanism Over Supported PEI Sorbents . . . . . . 46
2.4 CO2 Sorption Kinetics Over Supported PEI Sorbents . . . . . . . . 51
2.5 Regenerability and Stability of Supported PEI Sorbents . . . . . . 55
2.6 Large-Scale Process Development Using Supported
PEI Sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 60
2.7 Summary and Prospects . . . . . . . . . . . . . . . . . . . . . . . . . . ... 62
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 64
xiii
xiv Contents
3 Technical and Industrial Applications of CO2 . . . . . . . . . . . . .... 73

Jan Vansant and Peter-Wilhem Koziel
3.1 On-Site Industrial Large Scale Utilization of Gaseous CO2 .... 74
3.2 CO2 Liquefaction and Conditioning
for On- or Off-site Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.2.1 CO2 Production for the Merchant Market . . . . . . . . . . 75
3.2.2 Product Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.3 Carbon Dioxide Merchant Market . . . . . . . . . . . . . . . . . . . . . . 76
3.3.1 Food Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.3.2 Carbonated Beverages . . . . . . . . . . . . . . . . . . . . . . . . 83
3.3.3 Chemical Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
3.3.4 Metal Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
3.3.5 Agriculture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.3.6 Rubber and Plastics Processing . . . . . . . . . . . . . . . . . . 89
3.3.7 Other Uses as Solvent . . . . . . . . . . . . . . . . . . . . . . . . 89
3.3.8 Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91
3.3.9 Nuclear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
3.3.10 Well Re-injection . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
3.3.11 Cylinder Filling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.3.12 Other Applications (Not Using Large Quantities
of L-CO2 Yet) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
3.4 CO2 Used as Dry Ice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.4.1 Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
3.4.2 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
3.4.3 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3.5 Volume of the CO2 Merchant Market . . . . . . . . . . . . . . . . . . . 102
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4 Mineral Carbonation for Carbon Capture and Utilization . ...... 105
Tze Yuen Yeo and Jie Bu
4.1 Background and Key Concepts in Mineral Carbonation ...... 106
4.1.1 The Chemistry of Mineral Carbonation . . . . . . ...... 106
4.1.2 The Rates and Mechanisms of Mineral
Carbonation . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 109
4.1.3 The Thermodynamics of Mineral Carbonation . ...... 112
4.1.4 Raw Materials for Mineral Carbonation . . . . . . ...... 116
4.2 Overview of Basic Process Designs for Mineral
Carbonation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
4.2.1 Pressure Carbonation . . . . . . . . . . . . . . . . . . . . . . . . . 120
4.2.2 Chemically-Assisted Carbonation . . . . . . . . . . . . . . . . 123
4.2.3 Other Carbonation Processes . . . . . . . . . . . . . . . . . . . . 127
4.3 Techno-economic Aspects of Mineral Carbonation . . . . . . . . . . 129
4.3.1 The CO2 Penalty . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
Contents xv
4.3.2 The Economics of Mineral Carbonation . . . . . . . . . . .. 133

4.3.3 Integrated Mineral Carbonation Processes . . . . . . . . .. 136
4.4 Synergy Between Mitigation and Adaptation Actions Against
Climate Change, via Mineral Carbonation . . . . . . . . . . . . . . .. 140
4.4.1 A Brief Overview of Singapore’s Circumstances . . . .. 140
4.4.2 A Pilot Scale Mineral Carbonation Plant
in Singapore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 142
4.5 Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . .. 145
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 146
5 Catalytic CO2 Conversion to Added-Value Energy Rich C1
Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 155
Jangam Ashok, Leonardo Falbo, Sonali Das, Nikita Dewangan,
Carlo Giorgio Visconti and Sibudjing Kawi
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
5.2 CO2 Hydrogenation to Methane . . . . . . . . . . . . . . . . . . . . . . . . 156
5.2.1 Thermodynamic Consideration . . . . . . . . . . . . . . . . . . 157
5.2.2 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
5.2.3 Reaction Pathway and Kinetics . . . . . . . . . . . . . . . . . . 161
5.2.4 Engineering Challenges . . . . . . . . . . . . . . . . . . . . . . . 162
5.3 CO2 Hydrogenation to CO (Reverse Water Gas Shift
Reaction) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.3.1 Thermodynamic Considerations . . . . . . . . . . . . . . . . . 164
5.3.2 Catalyst Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
5.3.3 Mechanistic Considerations . . . . . . . . . . . . . . . . . . . . . 169
5.4 CO2 Hydrogenation to Methanol . . . . . . . . . . . . . . . . . . . . . . . 172
5.4.1 Catalyst Considerations . . . . . . . . . . . . . . . . . . . . . . . 175
5.4.2 Engineering Challenges . . . . . . . . . . . . . . . . . . . . . . . 177
5.4.3 Status of Industrial Development . . . . . . . . . . . . . . . . . 178
5.5 CO2 Hydrogenation to Formic Acid . . . . . . . . . . . . . . . . . . . . . 179
5.5.1 Thermodynamic Considerations . . . . . . . . . . . . . . . . . 179
5.5.2 Catalytic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
5.5.3 Reaction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 182
5.5.4 Technological Challenges . . . . . . . . . . . . . . . . . . . . . . 184
5.6 CO2-Methane Reforming to Syngas . . . . . . . . . . . . . . . . . . . . . 185
5.6.1 Reaction Thermodynamics . . . . . . . . . . . . . . . . . . . . . 186
5.6.2 Catalysts for DRM . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.6.3 Reaction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.6.4 Reactor Systems for DRM . . . . . . . . . . . . . . . . . . . . . 190
5.6.5 Minimizing Catalyst Deactivation in DRM . . . . . . . . . 191
5.7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
xvi Contents
6 Use of CO2 as Source of Carbon for Energy-Rich

Cn Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 211
Jiang Xiao, Xinwen Guo and Chunshan Song
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
6.2 CO2 Hydrogenation to Hydrocarbons . . . . . . . . . . . . . . . . . . . . 214
6.2.1 Co-Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . 214
6.2.2 Fe-Based Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
6.2.3 Fe-Based Bimetallic Catalysts . . . . . . . . . . . . . . . . . . . 221
6.2.4 Multifunctional Catalysts . . . . . . . . . . . . . . . . . . . . . . 223
6.2.5 Reaction Pathways and Mechanisms of C–C
Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 227
6.3 CO2 Hydrogenation to Higher Alcohols . . . . . . . . . . . . . . . . .. 230
6.3.1 Plausible Reaction Pathways . . . . . . . . . . . . . . . . . . .. 230
6.3.2 Early Exploration on HAS from CO2
Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 232
6.3.3 Recent Progress in Fe-, Cu- and Noble Metal-Based
Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 232
6.4 Summary and Future Perspective . . . . . . . . . . . . . . . . . . . . . .. 234
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 236
7 Electrochemical and Photoelectrochemical Transformations
of Aqueous CO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 239
Aubrey R. Paris, Jessica J. Frick, Danrui Ni, Michael R. Smith
and Andrew B. Bocarsly
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
7.2 Electrochemical CO2 Reduction . . . . . . . . . . . . . . . . . . . . . . . . 243
7.2.1 Heterogeneous Catalytic Systems . . . . . . . . . . . . . . . . 243
7.2.2 Homogeneous Catalytic Systems . . . . . . . . . . . . . . . . . 251
7.2.3 Hybrid Catalytic Systems . . . . . . . . . . . . . . . . . . . . . . 257
7.3 Photoelectrochemical CO2 Reduction . . . . . . . . . . . . . . . . . . . . 260
7.3.1 Heterogeneous Catalytic Systems . . . . . . . . . . . . . . . . 260
7.3.2 Homogeneous Catalytic Systems . . . . . . . . . . . . . . . . . 267
7.3.3 Hybrid Catalytic Systems . . . . . . . . . . . . . . . . . . . . . . 270
7.4 Miscellaneous CO2 Reduction Systems . . . . . . . . . . . . . . . . . . 273
7.4.1 Photoanode-Driven Systems . . . . . . . . . . . . . . . . . . . . 273
7.4.2 Diamond . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
8 Plasma-Based CO2 Conversion . . . . . . . . . . . . . . . . . . . . . . . ..... 287
Annemie Bogaerts and Ramses Snoeckx
8.1 Plasma, the Fourth State of Matter . . . . . . . . . . . . . . . . . ..... 288
8.2 Plasma and Its Unique Feature for Energy-Efficient CO2
Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 289
8.3 Plasma Reactor Types for CO2 Conversion . . . . . . . . . . ..... 291
Contents xvii
8.3.1 Dielectric Barrier Discharge (DBD) . . . . . . . . . . . . . . . 292

8.3.2 Microwave (MW) Plasma . . . . . . . . . . . . . . . . . . . . . . 293
8.3.3 Gliding Arc (GA) Discharge . . . . . . . . . . . . . . . . . . . . 294
8.3.4 Other Plasma Types Used for CO2 Conversion . . . . . . 295
8.3.5 Plasma Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
8.4 Overview of Plasma-Based CO2 Conversion . . . . . . . . . . . . . . 298
8.4.1 Pure CO2 Splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . 300
8.4.2 CO2 + CH4: Dry Reforming of Methane . . . . . . . . . . . 306
8.4.3 CO2 + H2O: Artificial Photosynthesis . . . . . . . . . . . . . 312
8.4.4 CO2 + H2: Hydrogenation of CO2 . . . . . . . . . . . . . . . . 315
8.5 Plasma Technology in a Broader Perspective of Emerging
Technologies for CO2 Conversion . . . . . . . . . . . . . . . . . . .... 317
8.6 Conclusion and Future Research Directions . . . . . . . . . . . .... 318
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 320
9 Bioelectrochemical Syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Suman Bajracharya, Nabin Aryal, Heleen De Wever and Deepak Pant
9.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
9.2 Bioelectrosynthesis from CO2 . . . . . . . . . . . . . . . . . . . . . . . . . 328
9.2.1 Biocatalysts for CO2 Reduction . . . . . . . . . . . . . . . . . 331
9.2.2 Interaction of Biocatalysts with Electrode for CO2
Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338
9.2.3 Electrodes Material Development for CO2 Reductions
in Bioelectrosynthesis . . . . . . . . . . . . . . . . . . . . . . . . . 340
9.3 Progress in Microbial Electrosynthesis . . . . . . . . . . . . . . . . . . . 342
9.4 Integrated Concepts for Bioelectrosynthesis Improvement . . . . . 344
9.4.1 Gas Diffusion Biocathodes . . . . . . . . . . . . . . . . . . . . . 344
9.4.2 Product Concentration and Separation . . . . . . . . . . . . . 345
9.4.3 Product Diversification via Chain Elongation . . . . . . . . 346
9.4.4 Bioanode-Biocathode Integration . . . . . . . . . . . . . . . . . 347
9.4.5 Metabolic Engineering of Biocatalysts . . . . . . . . . . . . . 347
9.4.6 Integration with Anaerobic Digestion . . . . . . . . . . . . . 348
9.4.7 Integration with Syngas Fermentation . . . . . . . . . . . . . 348
9.5 Techno-Economic Considerations for Upscaling
of Bioelectrosynthesis from CO2 . . . . . . . . . . . . . . . . . . . . . . . 349
9.6 Future Outlook and Challenges . . . . . . . . . . . . . . . . . . . . . . . . 350
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
10 Enhanced Biological Fixation of CO2 Using Microorganisms . . . . . 359
Fuyu Gong, Huawei Zhu, Jie Zhou, Tongxin Zhao, Lu Xiao,
Yanping Zhang and Yin Li
10.1 Exploring Natural Carbon Fixation Processes . . . . . . . . . . . . . . 361
10.2 Characterization of Photosynthetic Pathways and Enhancing
CO2 Fixation in the Calvin Cycle . . . . . . . . . . . . . . . . . . . . . . 364
xviii Contents
10.3 Applying the Wood–Ljungdahl Pathway for CO2 Fixation .... 368
10.4 Introducing Other Natural Carbon Fixation Pathways into
Heterotrophs for CO2 Sequestration . . . . . . . . . . . . . . . . . .... 368
10.5 Designing and Constructing Novel Synthetic CO2
Pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 369
10.6 Characterizing and Engineering Energy Supply Patterns
for Carbon Fixation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370
10.7 Challenges of Biological Carbon Fixation . . . . . . . . . . . . . . . . 372
10.8 Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 373
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 374
11 Enhanced Fixation of CO2 in Land and Aquatic Biomass . . ..... 379
Angela Dibenedetto
11.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 380
11.2 Generalities About the Production and Nature of Aquatic
Biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
11.3 Products From Microalgae . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
11.3.1 Fuel Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385
11.3.2 Non-fuel Products . . . . . . . . . . . . . . . . . . . . . . . . . . . 389
11.4 Commercial Production of Microalgae . . . . . . . . . . . . . . . . . . . 395
11.5 Economic Evaluation of Microalgae . . . . . . . . . . . . . . . . . . . . 396
11.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
12 Technoenergetic and Economic Analysis of CO2 Conversion ..... 413
Suraj Vasudevan, Shilpi Aggarwal, Shamsuzzaman Farooq,
Iftekhar A. Karimi and Michael C. G. Quah
12.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 413
12.2 Overall Scheme for CCU . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
12.2.1 Sources of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . 415
12.3 Potential Fuels/Products from CCU with Zero Emissions . . . . . 417
12.3.1 Fuels/Products from Solar Hydrogen . . . . . . . . . . . . . . 417
12.3.2 Products from Fossil-Fuel Hydrogen . . . . . . . . . . . . . . 419
12.3.3 Break-Even Production Cost . . . . . . . . . . . . . . . . . . . . 422
12.4 Case Study: Singapore . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
12.4.1 CO2 Emissions Scenario . . . . . . . . . . . . . . . . . . . . . . . 423
12.4.2 Scenarios for Solar Hydrogen . . . . . . . . . . . . . . . . . . . 423
12.4.3 Scenarios for Hydrogen from Fossil Fuels . . . . . . . . . . 425
12.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
13 Perspective Look on CCU Large-Scale Exploitation . . . . . . . . . . . . 431
Michele Aresta
Large Scale Utilization of Carbon
Dioxide: From Its Reaction with Energy 1
Rich Chemicals to (Co)-processing
with Water to Afford Energy Rich
Products. Opportunities and Barriers
Michele Aresta and Francesco Nocito
Abstract
This chapter makes the analysis of the possible routes for large scale CO2
utilization (CCU). Processes that convert CO2 into chemicals, materials and fuels
are discussed, as they are part of the strategy for reducing the CO2 emission into
the atmosphere. Technical uses of CO2, which do not imply its chemical
conversion, are discussed in Chap. 3, while mineralization and carbonation
reactions for the production of inorganic materials are treated in Chap. 4. Here,
the catalytic synthesis of organic products with a market close to, or higher than,
1 Mt/year is discussed, presenting the state of the art and barriers to full
exploitation. Minor applications are summarized, without a detailed analysis as
their contribution to CO2 reduction is low, even if they can favour the
development of a sustainable chemical industry with reduction of the
environmental impact. Energy products (C1 and Cn molecules) are discussed
for some peculiar aspects in this chapter, as their catalytic production will be
extensively presented in following chapters where the potential of using CO2
and water as source of fuels is analysed for its many possible applications setting
actual limits and future perspectives. A comparison of Carbon Capture and
Storage-CCS and CCU is made, highlighting the pros and cons of each
technology.
M. Aresta (&)
IC2R srl, Lab H124, Tecnopolis, via Casamassima km 3, 70010 Valenzano, Italy
e-mail: michele.aresta@uniba.it
F. Nocito
Department of Chemistry and CIRCC, University of Bari, 70126 Bari, Italy
© Springer Nature Switzerland AG 2019 1

M. Aresta et al. (eds.), An Economy Based on Carbon Dioxide and Water,
https://doi.org/10.1007/978-3-030-15868-2_1
2 M. Aresta and F. Nocito
1.1 Introduction
The capture of CO2 from power plants and industrial processes is a way to avoid that
it enters the atmosphere, as announced in the Preface. The concentration of CO2 in
flue gases from power stations, that represent the largest point-source, averages 14%:
it can be lower, depending on the quality of the fuel used. Industrial processes, as
detailed in the Preface, emit CO2 at concentrations that can reach 90%+ in fer-
mentation units. CO2 can also be recovered directly from the atmosphere, the most
abundant source of carbon dioxide on our planet and the most diluted (408 ppm,
[1]). Technical aspects of capture of CO2 from the various sources are discussed in
Chap. 2. Once captured, CO2 can be either disposed or used. Disposal of CO2 is not
discussed in this book: only a brief comparison with the utilization option is made,
highlighting pros and cons of both. In this chapter, an analysis of the various options
of CO2 conversion is made, highlighting the potential of such technology to reduce
the atmospheric level of CO2. Various categories of reactions are presented,
according to their energetic content. The conversion into chemicals and polymers [2]
is discussed in detail, while the conversion into C1 or Cn energy products is analysed
from a general point of view highlighting the importance of the use of CO2 and water
in their synthesis, while their chemistry is discussed in ad hoc chapters of this book.
1.2 CCS Versus CCU: The Amount Issue
As said above, one of the approaches to control the atmospheric CO2 level is its
capture from point-continuous sources or from the atmosphere (see Chap. 2). Once
captured, CO2 can be either disposed (CCS) or used (CCU). Table 1.1 makes a
comparison of the two approaches, highlighting the pros and cons. One of the main
discussion topics when comparing CCS and CCU, is the amount of CO2 that can be
disposed. Besides, the energy penalties and the residence time are key issues. The
two alternative strategies are quite different, as shown in Table 1.1.
We shall not discuss CCS in this paper, will devote instead our attention to the
effective and efficient CO2 conversion into chemicals, materials and fuels, targeting
avoidance of large volumes of CO2. We shall also make an exam of the potential
impact on the chemical industry, and eventually on the energy sector, of a full
exploitation of technologies based on CO2 utilization. Mineralization of CO2, i.e. its
conversion into inorganic carbonates is discussed in Chap. 4. Benefits of CO2
utilization in technological uses in which it is used as technical fluid but not
converted into other chemicals, are discussed in Chap. 3.
1.3 CO2 Conversion Options: The Energy Issue
The chemical utilization of CO2 can be categorized into three classes [3], as shown
below.
1 Large Scale Utilization of Carbon Dioxide … 3
Table 1.1 CCS and CCU at glance

CCS strength Issues Entry CCU strength Issues
TRL = 8–9 TRL TRL = 4–9
Injection Sites are not Ubiquity A CO2 When used,
technologies ubiquitary conversion-plant can compounds give
are well known be built in any place back CO2
Some Presently, Amount used 220 Mt/y are used. Only polymers may
5 Mt/year are disposal is permanence Some processes are have a sequestration
disposed; sites mainly for old of 150 y (urea, time of decades.
may be EOR. Doubts aspirine, inorganic CCU is not for
characterized exist about carbonates) storing CO2 but for
by a different the cycling-C
permanence permanence
and diffusion
in new sites
Transportation Safety of Safety CO2 is not toxic. It Concentration above
is practiced on pipelines in represents the ideal 10% volume in air
a large scale in civil areas is a substitute of may cause asphyxia.
industrial areas bottleneck phosgene or CO
CCS is for CCS is apt to Expected CCU is circular Value chains and
long time linear innovation economy: it is clustering-processes
disposal. Better economy and ideally used in a may optimize CCU
knowledge of produces solar-wind-geo
disposal sites additional (SWG) energy-frame
may increase CO2 during
safety storage
CCS has a CCS fails to Fossil-C versus CCU can turn on Formation of CO2 is
sense in a be Perennial SWG air-CO2 without much faster than
fossil-C based implemented energy frame fossil-C extraction: some fixation
energy frame. in a frame of emitted CO2 can be processes
It makes sense large scale recycled into
in the very SWG chemicals, materials,
short time and exploitation fuels continuously
will loose
power in future
CCS is said to Disposal of Perspective 7–10 Gt/year of CO2 Integration of
be able to store CO2 is not amount of CO2 can be converted into technologies and
all CO2 zero CO2- avoided a variety of system approach is
generated in generation. compounds and necessary
the combustion The real fuels, in a frame of
of C-based potential SWG exploitation.
materials on must be CCU is the future
the earth verified
(continued)
Table 1.1 (continued)

CCS strength Issues Entry CCU strength Issues
CCS needs A loss of Energy Reactions of CO2 Making fuels needs
energy for usable energy requirement with electron-rich hydrogen that must
shipping and is the effect: species are come from water
housing CO2. from 25 to 50 exoergonic.
Energy cost +% Reduction reactions
depends on the are endoergonic
distance btw
source-disposal
Popular A lot of Popular CO2 is in the air and Information still
acceptance of information acceptance used by Nature for needs to be spread
CCS has been must be making million around for clarifying
randomly delivered to products: this is basic concepts and
enquired. common under the eyes of avoid confusion
Attitude of people before everybody. The (CO vs. CO2!)
people must be their response industrial
deciphered to exploitation needs to
through larger accept/reject be illustrated
enquiries CCS can be
sound
As mentioned Disposal sites Research The knowledge of Co-processing of
above, the require still a needed the reactivity of CO2 CO2 and water
storage lot of under different under solar
technology is investigation conditions is quite irradiation is a must
well known for knowing good, even if new for the future
with spent their catalysts can be avoiding hydrogen
gas-wells. The long-term discovered and new production
injection storage, processes that may
technology is leakage and allow to implement a
well known by diffusion. larger scale
oil-gas This is a conversion
industry. The prerequisite
knowledge of for safety
new sites must
be developed
to high level
before use
Capture is a prerequisite for both technologies, the purity of CO2 may be distinct for CCS and
CCU
A. Conversion into chemicals in which the –CO2– entity is preserved by

incorporation of the entire moiety into a new molecule without C–C bond forma-
tion. In such case, the oxidation state of the C-atom remains equal to +4. Such
processes may be low in energy as, in general, the CO2 molecule reacts with
electron rich co-reagents such as amines-RR′R″N, or O-containing species: O2−,
OH−, OR−, or similar systems. Exoergonic carbonation of inorganic bases belongs
to this Class.
B. Carboxylation of organic substrates.

Carboxylation reactions, in which a C–C bond os formed and the oxidation state
of C goes down to +3 from +4 can be categorized as: (i) reactions in which CO2
reacts with energy rich molecules such as olefins, alkynes, dienes (conjugated and
cumulated) to afford specialty chemicals such as lactones, pyrones, esters, among
others; (ii) insertion of CO2 into C–H bonds with formation of acids. The former
(see Sect. 9) occurs under quite mild conditions and can be exploited in a energy
system based on fossil-C, the latter (1.1) are quite common in Nature and are of
great interest for Industry.
RH þ CO2 ! R CO2 H ð1:1Þ
Today, the introduction of a carboxylic moiety –CO2– into an organic substrate

occurs via “oxidation” of an alkyl group (in general a methyl, –CH3) (1.2a) or
partial destruction of an aromatic ring (1.2b) or even by hydrolysis of a cyanide
moiety (1.3).
oxidant
RCH3 ! RCO2 H ð1:2aÞ
CO2H
oxidant (1.2b)
cat
CO2H
ð1:2aÞ
RCN þ 2H2 O ! RCO2 H þ NH3 ð1:3Þ
Reactions (1.2a), (1.2b) are often characterized by low selectivity and, thus, by a
low Carbon Utilization Fraction (CUF). In reaction (1.2b) two atoms of carbon are
lost as CO2 over ten. The direct carboxylation would avoid such loss as reaction
(1.1) has a CFU = 1. Reaction (1.3) uses toxic species. Cyanides are produced
through complex routes with high E-factor (ratio of waste to target useful product).
The bottleneck in (1.1) is the activation of the C–H bond. Thermal processes seem
less suited than photochemical [4] ones to such end. In fact, recently several
examples of photochemical reactions can be found in the literature [5], that are
overwelming thermal examples.
C. Conversion into chemicals in which the C-atom has a lower oxidation state
than +3: from +2 to −4. The energy content of the resulting chemical depends on a
series of factors, among which the oxidation state of the C-atom of the species into
which CO2 is converted, the number of C–H bond formed, the number of C–C bond
formed. Table 1.2 shows the thermodynamic properties of some molecules derived
from CO2 upon hydrogenation. It is evident that there is not a (linear) relationship
between the change of the oxidation state with respect to CO2 (Column 3) and the
change of Free Gibbs energy (Column 7) moving from CO2 to CH4. Acetylene has
peculiar properties and methanol and ethene (in the two latter the oxidation state is
−2) have different energy content.
Considering a series of compounds having similar structural properties (for
example compounds #7–9 in Table 1.2 in which the C atom has a sp3 geometry), it
is possible to find a correlation between the difference in DG between the reduction
product and original CO2 (1.4) and the variation of the oxidation state of the C-atom
(Fig. 1.1).
DG ¼ DGfðnewmoleculeperCatomÞ DGfðCO2 Þ ð1:4Þ
In all such conversions two actors play a key role: energy and hydrogen. Both must
be delivered to the reactive system for the conversion of CO2 may occur and cannot
be sourced from fossil-C: energy must come from perennial sources (SWHG) and
hydrogen from waste biomass and sea- or process- waters, in order to not aggravate
the drinking-water world problem.
This is the limiting factor for the conversion of CO2 into energy products, with
recycling of large masses of C in the form of CO2.
1.4 CCU and Resources Conservation
The utilization of CO2 as building block or source of carbon means recycling carbon,
mimicking Nature. This is a virtuous practice that reduces the transfer offossil-C to the
atmosphere, supports the sustainability of the chemical industry (and transport sector)
and preserves fossil-C resources for next generations. The consumption of fossil-C
today ranges around 11.5 [7] −12.5 Gtoe/year [8] with a forecast of reaching 25 Gtoe
in 2035. In a Business as Usual (BAU) this means that the CO2 emission will rise from
37 to over 70 Gt/year! The daunting figure is that the estimated fossil-C reserves (coal,
oil and gas) are today quantified at 941 Gtoe. According to the BP forecast [9], at the
actual rate of consumption of fossil-C, humanity have crude oil available until year
2066, natural gas until year 2068, and coal until year 2169. Such figures are impres-
sive! We hopefully rely on the fact that the knowledge we have of the real reserves of
fossil-C is not absolutely certain and complete and, thus, on the fact that new
coal-oil-gas sites can be discovered or deeper sites not reached so far can be exploited.
With a perspective availability of fossil-C of ca. 150 years, recycling carbon (equiv-
alent to use renewable carbon) becomes a compulsory practice for saving natural
resources. Therefore, using (atmospheric) CO2 for making chemicals and fuels, as
Nature does, is an ethical problem, before being scientific or technical. However, one
could ask at what cost recycling can be done and whether or not recycling carbon is
sustainable.
1
Table 1.2 Thermodynamic properties [6] of some molecules derived from CO2 upon hydrogenation
Compound Formal oxidation state of C DOx ¼ nox;X nox;CO2 DH° (kJ/mol) DS° (J/mol) DG° (kJ/mol) DG° (kJ/mol C) #
CO2 +4 0 −393.51 213.6 −457.2 −457.2 1
CO +2 −2 −110.53 197.6 −169.4 −169.4 2
CH2O 0 −4 3
C2H2 −1 −5 226.7 200.8 166.9 88.45 4
Large Scale Utilization of Carbon Dioxide …
CH3OH −2 −6 −238.7 126.8 −276.5 −276.5 5

C2H4 −2 −6 52.3 219.5 −13.1 −6.55 6
C3H8 −2.7 −6.7 −103.8 269.9 −184.2 −61.4 7
C2H6 −3 −7 −84.7 229.5 −153 −76.5 8
CH4 −4 −8 −74.8 186.2 −130.3 −130.3 9
7
Correlation Nox vs Energy

0
-8.5 -8 -7.5 -7 -6.5
-20
Δenergy/kJ mol-1
-40
-60
-80
-100
-120
-140
ΔNox
Fig. 1.1 Correlation DNox/DEnergy for some reduced forms of CO2
Biomass
Biomass
Biomass
Biomass
<1750 1750 ++ Last two centuries Our days Future
Fig. 1.2 Sources of energy and goods in the human history: past and future
Figure 1.2 presents the history of energy and goods sources for humans (food is
not considered). Until ca. 1750, biomass was practically the only real source of
energy and goods (materials, fibers). With the industrial revolution and the
exploitation of coal-mines first, and oil- and gas-fields later, fossil carbon has
increased its role as source of energy and goods competing and winning over
biomass. Today, we are moving back to the use of SWGH and renewable-C, aiming
at reducing the use of fossil-C. Perennial sources and biomass may become the
main sources of energy and goods in 30 years from now, with a significant
reduction of the extraction of fossil-C. For this change may occur at a significant
extent, it is necessary that economic and environmental costs of innovative pro-
cesses are affordable. As a matter of fact, the solar(wind)-H2 price should be close
to that of reforming-H2 (ca. 1.3–1.5 US$/kg): today it is some three times higher.
The US Department of Energy has specified that the solar-to-hydrogen commer-
cialization target is a energy conversion efficiency preferably >10% to compete with
gasoline [10]. Presumably, a comparable solar-to-fuel conversion cost is necessary
for photocatalytic or photovoltaic (PV) plus electrocatalytic CO2 reduction may
become a commercial reality. Installed PV is increasing at a high rate: from 51 GW
in 2015, to 305 in 2017, 969 in 2025 [11]. By 2040, it is foreseen that the
worldwide installed power of PV will rise to over 3000 GW and the cost of
PV-materials will decrease to a level that will make PV able to produce low cost
electrons and H2, comparable with reforming-H2.
1.5 CCU and Innovation
A key role CCU can play in the industrial sectors is innovation. The use of CO2 may
introduce new synthetic methodologies, more direct than those on stream today.
Innovation in synthesis means an overall reduction of: reaction steps, use of fossil-C
based materials, waste production, process energy, separation energy. The tangible
benefits with CCU are: safer working conditions, raw material diversification, reduc-
tion of carbon footprint, lower environmental impact (reduction of not only GHG
emission, but also reduced burden on other categories such as human toxicity, soil and
water toxicology, air pollution, acidification, etc.), lower overall industrial waste
production (with subsequent lower CO2 emission in waste treatment) and less toxic,
resource saving. Innovative processes based on CO2 are those which while reducing the
C-footprint, do not increase the impact on other environmental categories. This is a very
important point: targeting only CO2 reduction without taking care of emissions which
can negatively impact other environmental categories is not an acceptable solution.
Therefore, the LCA of new processes should take into account at least five impacts
categories, namely: Climate Change Potential-CCP, Human toxicity, Soil ecotoxicity,
Air Pollution, Water pollution. Reducing CCP, while increasing the other categories
does not represent an acceptable solution, because for reducing the latter impacts
energy will be used and this will cause CO2 emission. Claiming inexistent benefits does
not support CCU. Moreover, we believe that soon the way LCA will be carried out [12]
will increase its complexity, moving from single product-process to cluster of processes
and cascades of products, including waste management.
CO2 is the alternative to either phosgene (COCl2, a toxic species, LC50 = 3
ppm) [13] or CO (poisonous gas) [14]. In both cases, the use of CO2 will generate
safer conditions for workers, with less risk and a positive impact on Capital
Expenditure (CAPEX), as a lower investment in safety will be necessary, assuring
longer life to plants with lower Operative Expenditure (OPEX) (less corrosion of
plants). Today, safe conditions when using phosgene require the insulation of a
plant in a dome connected to air treatment plants: a procedure that has strong impact
on both CAPEX and OPEX. The great advantage of phosgene is its high reactivity
that allows reactions to be carried out at room temperature, or nearby. Such high
reactivity has an energetic and environmental cost, linked to the production of
energy intensive and strongly impactant CO and Cl2 used for making phosgene
[15]. Phosgene is banned in several countries today and cannot be transported: it
can only be produced and used in situ. Such limitations are making the use of
phosgene strongly problematic in some geographic areas and demand for effective
substitutions. CO2 is the ideal candidate and the new synthetic methodologies are
really welcome and meet the industrial interest.
CO is used in the synthesis of methanol, in FT processes, in carbonylation
reactions at the rate of ca 173 GWth/year in 2017 and an estimate of
239.5 GWToe/year in 2023 [16] and its use is expected to continue to grow.
Substituting CO2 to CO may mean the use of up to 50% excess hydrogen (methanol
synthesis) that is possible only if H2 produced from water using perennial energy
sources is used: the use of fossil-H2 is a non sense as maximization of H2 pro-
duction (1.5a) is based on WGS reaction (1.5b) that releases CO2.
C þ H2 O ! CO þ H2 ð1:5aÞ
CO þ H2 O ! H2 þ CO2 ð1:5bÞ
Therefore, while the substitution of COCl2 with CO2 would be immediately pos-
sible, supposed we have the right technologies, the substitution of CO will take
place in coming years when PV-H2 will have a large production and a cost com-
parable to reforming-H2.
The above are just two examples more will be discussed in coming paragraphs.
Such innovative methodologies also address the raw material diversification target.
The use of CO2, as said above, allows the substitution of fossil-C, implementing the
reduction of carbon footprint of industrial synthetic methodologies and lowering the
environmental impact of the chemical industry.
The utilization of CO2 even lowers the overall industrial waste production by
implementing more direct syntheses. Such new processes produce less toxic waste
because toxic reagents are avoided. (vide infra) All above benefits, coupled to
resource saving, make the CO2 chemistry much wished at the industrial level.
A point of interest is that CO2 is produced in several industrial processes
(Table 3 in Preface) that deliver purer streams than power plants. Therefore, the use
of industrial CO2 can be convenient also because it is produced at chemical sites
where it would be easily converted, saving shipping costs. As a matter of fact,
clustering chemical processes can favour CO2 recovery and use in situ, maximizing
the use of resources and minimizing energy expenditure (see Sect. 1.8).
1.6 CCU and Sustainability of the Chemical and Polymer

Industry
It is worth to emphasize that if the energy industry can be decarbonized, the

chemical and polymer industry can not. In our everyday life we mainly (85–90%)
use products based on chemicals and materials produced via catalytic processes,
with a minor share of natural products. In any case, all products are C-based. Even
if bio-based products will be promoted and will increase their share on the market,
carbon will always be around: we can imagine change its source, not to substitute it.
All biomass is produced from CO2, therefore our future will increase the use of
CO2, either directly by developing CO2-based processes or by letting Nature fix
CO2 and using catalysis for converting biomass [17]. In this paragraph a few cases
of reagent/raw material substitution will be discussed, relevant to making more
sustainable the chemical industry shifting from fossil-C to CO2. We shall not enter
into the detailed mechanistic studies, this is not the scope of this paper. More
specialized books ([18] and references therein) and papers ([19] and references
therein) can be found in the scientific literature which deal with such aspect. Here
we shall highlight the aspects that make the CO2-based chemistry economically and
environmentally appealing, while empowering sustainable processes. Energy
products such as methane, methanol, long-chain hydrocarbons will not be treated in
detail. They will be discussed in Sect. 8. The key aspects, which will be discussed
here are relevant to the use of CO2 as building-block substituting fossil-C. Only
chemicals with a market close or higher than 1 Mt/year will be considered. When
necessary, if hydrogen will be needed, it is intended that it will be produced from
water by electrolysis using SWGH energies as primary sources.
HCO2H, formic acid, has a market of ca. 800 kt/year and an annual growth esti-
mated at 4.95% by 2027 [20] with a key utilization in sectors shown in Fig. 1.3. Its use
as H2-carrier/storage (vide infra) may increase its market to tens Mt/year. Formic acid
is made through routes based on CO, produced via reforming of coal or methane. Its
direct synthesis from CO2 and H2 (1.6a) is highly wished and attempted since long
time. Such reaction has some thermodynamic limitations (DG° = + 6 kcal/mol)
H2g þ CO2g ! HCO2 H1 ð1:6aÞ
H2g þ CO2g þ RR0 NH ! RR0 H2 þ HCO2 ð1:6bÞ
RR0 NH2þ HCO2 þ HX ! HCO2 H þ RR0 NH2 þ X ð1:7Þ
due to the negative entropic contribution (two gases are converted into a liquid)
which can be won by carrying out the reaction in presence of amines, HNRR′ in
organic solvents [with production of ammonium formates, HCO2 +H2NRR′,
(1.6b)] or inorganic bases, MOH in water (with formation of HCO2M). In all such
cases the reaction has a negative DG° (ca. −30 kcal/mol), but salts (ammonium or
Group 1 metals) more than the free formic acid are formed. The production of free
Fig. 1.3 Global formic acid

market, by application, 2016
(%)
HCO2H requires the reaction of the salts with inorganic acids with formation of
equimolar amounts of inorganic waste (1.7). On the other hand, some catalysts have
been developed so far (1.6b) for the synthesis of formates which are almost ready
for industrial application [21]. Attempts to shift from salts to the free acid (use of
SC-CO2 [22] or water as reaction solvents [23]) are undergoing. Should they
succeed, the direct synthesis of formic acid from CO2 and water (as source of H2)
will be ready for exploitation.
Carboxylic acids, R-CO2H are synthetized either through routes based on CO
(acetic acid, CH3CO2H, ca. 6 Mt/year) or via oxidative processes or hydrolysis of
cyanides (1.2a)–(1.2b) [19]. The two latter routes are not very efficient for their low
CUF and have a large environmental impact. The direct synthesis based on CO2
(1.8) is highly wished, but demands the C–H activation, a not easy process.
RðArÞH þ CO2 ! RðArÞCO2 H ð1:8Þ
Process innovation is necessary in this field and the use of radiation chemistry more
than thermal processes may represent a solution [5, 6]. The production of long chain
carboxylic acids from hydrocarbons and CO2 would represent an interesting route
to biodegradable surfactants with great environmental benefit. Surfactants have a
market of several Mt/year and are expected to grow at a rate of 3.54%/year [24].
Direct carboxylations are quite appealing for the high level of innovation and the
environmental benefits due to quasi-zero organic waste production and significant
reduction of CO2 emission.
Acrylic acids market [25] is built up by several derivatives, such as: Acrylic
Esters (Methyl Acrylate, Ethyl Acrylate, Butyl Acrylate, Ethyhexyl Acrylate),
Acrylic Polymers (Acrylic Elastomers, Super Absorbent Polymers, Water Treat-
ment Polymers, Ammonium Polyacrylate, Cyanopolyacrylate) and End Use (Dia-
pers, Surface Coatings, Adhesives & Sealants, Plastic Additives, Water Treatment).
It amounts at ca. 6.6 Mt/year (2017) with a perspective annual growth of 7.6%/year
and an estimated global market of 8.2 Mt by 2020. The production of acrylic acid is
today based on the non-selective oxidation of propane to propene and of the latter to
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He would face anything rather than once more be balked in learning
what to him was almost as much as life itself.
With the aid of Neram and Ashati, he cut down one of the smaller
trees near the river bank and began the work of hollowing out a
portion of the trunk in the form of a small canoe.
It was hard work and slow, even with the aid of his companions, who
were skilled in that kind of work, and when the evening shadows fell
along the banks of the River of Death the canoe was only half done.
Impatient as he was, Bomba was forced to wait till morning for the
completion of the work.
At the break of dawn Bomba was at work again. Ashati helped him,
while Neram went off in search of jaboty eggs so that they could
conserve their remaining supply of meat.
Some time later he returned, triumphantly displaying six large eggs.
“There were more there, but I could not carry them,” he said, as he
built a fire with which to prepare breakfast. “I saw a tapir, too, but
could not kill him because I had gone out without my bow and
arrows.”
“Foolish one to hunt without weapons,” reproved Ashati, looking up
for a moment from his work. “Ashati would know better.”
“The next time Ashati shall do the hunting,” returned Neram, and
went on stolidly with his preparations.
By the time the sun was high in the heavens the crude canoe was
finished. A paddle was then fashioned from a sapling, that for all its
slenderness was strong enough to breast the current of even that
raging river.
Their temporary captive had explained to Bomba that he must
launch his boat at some little distance up the river, where the current
was not so strong. From there he could let himself go with the
rushing waters until he came to a place where the waters widened
out and were not so tumultuous.
When he reached this portion of the stream, the native had said, he
would see at a distance a long island, the shape of a finger,
extending into the river. After he had reached and passed this on the
eastern side, he would find himself in a place more easily navigable
for his small craft.
Up this calmer stretch of water Bomba had been directed to paddle
until he should come in sight of Snake Island, half hidden behind a
jutting point of the mainland.
Bomba had taken it for granted that Ashati and Neram would
accompany him. There was room for the three of them, and there
would be less danger of capsizing if the canoe were well weighted
down.
But though they helped him willingly to carry the canoe to the portion
of the river where it would be safe to launch it, they seemed so
terrified when Bomba spoke of his eagerness to reach Snake Island
that the lad stared at them with amazement.
“You are afraid to go?” he asked.
Poor Ashati and Neram flinched before his accusing gaze and hung
down their heads. For a long moment there was silence, and then
Ashati answered:
“This Sobrinini is a witch and her island is full of snakes. If she is a
witch, she can make the snakes do her bidding. Did not the caboclo
say that to go there was to die?”
Bomba pondered for a while, staring at his companions. He had not
their superstition, but he could put himself in their places and
understand their feelings.
“You have not the reason to seek out Sobrinini that I have,” he
conceded. “Perhaps that is what makes me blind to dangers that you
see. Bomba will go alone. You stay here till I get back.”
At this they cast themselves at his feet, crying out that they would go
with him in spite of their dread of Sobrinini and her island of snakes.
But Bomba would not accept such a sacrifice on their part, and
persisted in setting off alone.
They dropped the canoe into the water, and almost before Bomba
had time to get into it the current caught the frail bark and sent it
dancing out upon the swirling waters like a feather caught in the
wind.
The jungle boy needed all his skill to keep the tossing craft on an
even keel and set a straight course down the river. When he could at
last look back, he could see Neram and Ashati standing on the bank
like bronzed statues, looking after him. He knew that in their hearts
they never expected to see him again.
On he went down the river, the canoe caught now by one current,
now by another, sometimes dipping to one side at so sharp an angle
that it seemed it must capsize, then righting itself and dancing on
again over the frothing black water—a frail barrier between Bomba
and destruction.
Once the canoe was caught in the iron grip of a cross-current and
rushed at a furious speed toward the rocks that at that point lined the
shore.
Bomba had need of all his strength. Putting all his force upon the
paddle, he grazed the murderous rocks by the fraction of an inch,
and slid lightly, gently into a stretch of calmer water.
The most dangerous part of his water journey was now over. All he
had to do now was to avoid the rocks that at places pushed their
heads above the water and the snags formed by parts of the trunks
of trees that had grown on what was dry ground before the stream
had extended its borders and swallowed them up.
But there were other “snags” too—living snags! The rough, gnarled
bodies of great alligators that swam or floated lazily about, their
backs just showing above the surface. Many were wholly or half
asleep, others turned red and evil eyes on the solitary boatman as
he sped by. Bomba, remembering his last experience with the
ferocious brutes, shuddered to think of what would happen to him if
by some evil chance his canoe should be overturned.
He found the island that was shaped like a finger, and worked his
craft about the further end of it, heading upstream as the native had
directed.
This was more tedious work than his progress downstream had
been, but far less perilous. Bomba paddled with a will, his heart
beating high with hope as he thought that every stroke was bringing
him nearer to Sobrinini and the secret whose answer he was so
eager to know.
If he shared to some extent the fears that had taken such strong
possession of Ashati and Neram in regard to Sobrinini and her island
of snakes, his eagerness to learn from the lips of the old witch
woman those facts about his parentage that had been so long
denied him drove all other feelings from his mind.
But as time passed and still each bend of the river failed to disclose
any island answering to the description given by the native, Bomba
became anxious and quickened the long, sweeping strokes of his
paddle.
Could the native have deceived him? Was the fellow chuckling at
that very moment at the way he had deceived the white boy who had
waylaid him?
Bomba hardly thought so. The man had spoken under the fear of
death, if he spoke falsely. He knew how indefinite was the native
idea of distance. He had heard Casson say in the old days that when
a caboclo said a place was “not far” he might mean just beyond a
bend of the road or twenty miles away.
Bomba’s first uneasiness came with the lengthening of the evening
shadows. Even if the native had not misled him and his course was
the true one, Bomba did not relish the idea of approaching the island
in the dark, or even at early dusk.
But even as these thoughts troubled his mind and the shadows grew
deeper, he rounded another bend of the river and saw before him the
object of his search. He could not be mistaken. The position and
shape of the island were exactly as the native had described them.
As Bomba, with quickened pulse, drove his canoe among the heavy
rushes that half concealed the land from anyone upon the river, the
sound of singing came to him.
It was not one of the tribal songs of natives with which he was
familiar.
It was singing such as he had never heard before, and the voice of
the singer was so thin and eerie and unearthly in that solitary spot
that Bomba felt the hair rise on his scalp.
“Sobrinini!” muttered the lad, and with a trembling hand parted the
bushes from before his eyes.
CHAPTER XVII
AMID WRITHING SERPENTS
The sight that met Bomba’s eyes was horrible beyond anything he
had ever seen or imagined.
At the extreme end of the island, in mud that oozed about her
ankles, an old withered crone was performing a weird dance, singing
to herself as she did so in a language that was strange to Bomba.
But that was not the part of the performance that held Bomba
spellbound, horror-stricken.
It was the snakes, the ropes of slimy, hideous reptiles that the old
woman wound about her arms, her waist, her neck, even her face,
as she danced faster and ever faster to the strains of her weird, high-
pitched song.
It was then that fear entered into Bomba, a fear such as had never
been felt by him when he battled with the wild beasts of the jungle.
Then he had fought with things of flesh and blood, with something he
could understand. But what he saw now seemed to be tinctured by
the supernatural. His flesh crawled. The scene was revolting and
horrible beyond description.
This must be Sobrinini, this hag that played with and fondled and
petted these hissing reptiles that wound their coils about her body.
She must be a witch, as the native had claimed. How otherwise
could she do a thing like this and remain unharmed?
And if she was a witch—and to Bomba’s primitive, half-taught mind
this did not seem at all impossible—she might have it within her
power to lay a spell upon him, if she wished. Perhaps she might turn
him into one of those very snakes that hissed and writhed about her.
At the thought, Bomba was tempted to flee from the spot. But
something in him, stronger even than his fear, drew him resistlessly
toward that weird figure on the river bank.
He worked the canoe in as far toward the island as he dared and
wedged it tightly among the rushes, trusting that they would hold it
for him until he returned.
He found that the water was shallow, and silently slipped into it and
waded toward the bank. Dread of the piranhas, a dangerous, sharp-
toothed fish, such as infest all the waters of the jungle, hurried
Bomba’s steps so that he was not as cautious in his approach to
Sobrinini as he would otherwise have been.
Although he made for the shore at some distance from the old
woman, so that he might choose his own time for drawing near her
after she had finished with the demon-like dance, he slipped, when
he tried for a footing in the slimy ooze of the river bank, and came
down with a heavy splash.
The sound startled Sobrinini. The weird song died on her withered
lips and she stood staring. The tropic night had fallen now, but a full
moon had risen, and by the light of it Bomba could be seen as he got
to his feet and gained the bank.
At sight of him, a shrill yell pealed from the lips of the old woman,
which brought dark figures running to her from all directions. Bomba
saw one rise up in front of him as though conjured from the earth by
magic. He turned to avoid the outstretched arms of this apparition,
did not see the hole that yawned at his feet, and fell into a nest of
writhing snakes.
He was so paralyzed with horror that he could not move. Perhaps it
was to that that he owed his life. For as the snakes, most of which
had been dozing in the slimy ooze at the bottom of the pit, recovered
from their surprise and coiled to attack, Sobrinini pushed through the
crowd at the edge of the hole and began to sing.
It was a lilting, rhythmic tune, and at the first notes of it the hideous
reptiles surrounding Bomba began to sway to the sound and one
after another slipped over the edge of the pit and slithered away into
the darkness.
Bomba climbed out, with the gray mud plastered over him. Still
shaken at the narrowness of his escape from a terrible death, the lad
drew himself up beside Sobrinini.
The ring of natives, male and female, closed in upon Bomba and the
old witch woman as the sound died on the lips of Sobrinini. Several
of the group carried flaring torches, and by this flickering light the
scene seemed as unreal and fantastic as a dream.
As Sobrinini saw Bomba before her, she turned upon him with a look
so fierce and malignant that the lad involuntarily drew away from her.
“You scared my snakes!” she cried accusingly. “For that you should
be burned by fire and flung into the river for the alligators to feast on
your flesh. It was for their sakes, not yours, that I saved your life,
wicked one. My snakes must not be frightened, my little pets—ha,
ha, ha!” and she went off into such a fit of horrible merriment that
Bomba’s heart froze within him.
If at that moment he could have reached his canoe by any means
and left that fearful place behind him forever, he might have yielded
to the temptation.
But it was too late now. The ring of natives surrounded him, and
even if he succeeded by a bold dash in forcing his way through
them, there was little chance of escape. They would reach him and
drag him back before he could get the canoe clear of the bushes and
head for the open stream.
The impulse to flee lasted but a moment. The next, Bomba pulled
himself together and was his cool, courageous self once more.
Sobrinini had worked herself into a frenzy of fury. She danced about
Bomba in a hideous way, shaking her shriveled fists in the air and
mouthing horribly.
Now she came close to the lad and pushed her wrinkled face in his.
She raised an arm above her head as though to strike him. Bomba
stood unflinching.
She paused suddenly, arrested apparently by something she saw in
his face.
“Ah!” she cried. “Bring the torches nearer.”
The command rang out in a strikingly clear voice and instantly there
was a stir among the natives. Evidently she was accustomed to
being obeyed without question.
One great sullen fellow came forward and thrust his flaring torch
almost in Bomba’s face.
Sobrinini peered closely at the lad for a moment, and then shrank
back with a piercing scream.
“You!” she cried, again coming close and staring at him wildly. “How
came you here? Are you a ghost, Bartow?”
Into Bomba’s heart came a swift feeling of amazement.
What was the meaning of this? Like an echo of the words came the
memory of Jojasta’s cry as Bomba had bent above him when he was
pinned beneath the fallen column. Jojasta had called him Bartow and
thought he was a ghost.
He took a step toward Sobrinini, who was still staring at him fearfully.
“What mean you?” he cried.
Seeing the terror into which their priestess had been thrown, a
strange wild singing rose from the native women as they wove in and
out in fantastic mazes, evidently designed to ward off the evil
portent.
The bony fingers of Sobrinini closed on Bomba’s arm. Her voice was
shrill and urgent, as she said in his ear:
“Come with me, Bartow. Ghost or not, come with Sobrinini.”
As in a nightmare, his mind in a tumult of conflicting emotions,
Bomba allowed himself to be led away.
They passed through dank, long grass that sprang from the marshy
ground, and in some places grew as high as Bomba’s head. Once
he felt the slimy body of a snake beneath his foot and leaped aside,
only to feel his foot brush another.
“Be not afraid of the snakes. They are my pets and will not harm
anyone that is with Sobrinini,” crooned the old crone at his side.
She knew her way well, for she moved along the winding trail without
ever looking down, keeping her fascinated gaze on Bomba’s face.
Twice Bomba started to ask her what she meant by calling him
Bartow and a ghost, but twice he was halted by a bony, shriveled
finger on his lips and a croaking cry:
“Hush! Speak not, Bartow, or you will break the spell and shatter it
into a thousand tinkling fragments.”
She went on, muttering to herself, until at last they came to a large
wooden building. A flickering light from its gaping windows threw
grotesque shadows upon the ground.
Bomba felt a dread of entering the place. Like the wild things of the
jungle, he felt safer in the open. But Sobrinini’s hand was upon his
arm, and she dragged him through the doorway. Her manner grew
ever more feverish and wild. She seemed possessed by a terrible
excitement. Bomba did not venture to dispute her will.
He found himself in a strange place, the like of which he had never
seen before. Tearing his glance from the withered mask that was the
face of Sobrinini, he looked about him.
Torches flickered and flared in crude receptacles fastened to the
walls and lighted up the bare and desolate room.
Rows of crude chairs stood upon the uneven wooden floor, and
above these, halfway to the patched and leaking roof, a tiny balcony
had been constructed. At either end of this was a small compartment
with rounded front, meant to represent an opera box, though this of
course Bomba could not know.
At the extreme front of the big room was a raised platform, meant to
serve as a stage of this dismal imitation of an opera house.
As Bomba gazed about him, surprised and bewildered, Sobrinini left
his side, and with a horrid simulation of youth skipped to the
platform.
Then she turned and made him a low bow, a hideous smirk cracking
the wrinkles of her withered face.
“Come closer, Bartow. Come closer, dear Bartow! Do!” she urged, in
a voice at first soft and coaxing, but that ended in a shrill cackle. “I
will give you a good seat, Bartow—the best seat in the house—in the
first row center. You can hear me better there than from a box.
Come!” she cried, as he hesitated, her simpering giving place to a
terrible frown. “Why do you stand there blinking at me like a fool? Do
not rouse my wrath, Bartow! The wrath of Sobrinini is a terrible thing,
as no one should know better than you.”
Bomba came forward quickly, alarmed by the swift change in the old
crone’s manner. But she simpered and smirked again when he
approached, and, skipping lightly from the platform, forced him with a
playfulness that Bomba found scarcely less terrifying than her wrath
into one of the crazy chairs close to the stage.
“Now I will sing to you!” she cried, and sprang up again upon the
platform.
Bomba watched with a strange fascination while the old woman
danced and sang in a strange language unknown to him. The lilting
songs, even when sung by that cracked and ruined voice, struck a
responsive chord in the boy and filled him with emotions that he
could neither analyze nor understand.
He did not know that that voice, when in its prime, had thrilled great
audiences that included emperors and kings and had given the
singer a reputation as wide as the civilized world.
Suddenly Sobrinini paused, and fixing Bomba with a strange intent
gaze, sang in a voice that had magically lost most of its raucous
quality and for the moment had become the faint, sad echo of
something that had been supremely beautiful—sang a tender,
haunting melody that touched some almost forgotten memory in
Bomba’s heart and filled him with an exquisite pain.
Somewhere, long since, he had heard that melody! But when and
where?
Slowly the music drew him step by step toward that fantastic figure
on the stage.
“Tell me!” he cried imploringly. “Tell me, Sobrinini, was that my
mother’s song?”
CHAPTER XVIII
THE MYSTERY DEEPENS
For an instant the fierce, bright eyes of the old hag softened. Her
bony fingers hovered over Bomba’s hair, as though they would have
stroked it.
Then she threw back her head and laughed, a harsh, cackling laugh
that caused Bomba to wince and shrink back as from the sharp
thrust of a knife.
“Eh, Bartow, you would have a joke with Sobrinini, my fine one,”
croaked the old crone, wagging her finger in Bomba’s face and
leering at him in a way she meant to be facetious. “No, no, Bartow—
or Bartow’s ghost—that was not your mother’s song, but the song of
your wife——”
“My wife!” the words broke from Bomba impetuously. “What mean
you, Sobrinini?”
“Ah, you would still have your joke with Sobrinini, eh?” The old
woman leaned forward again and tapped him on the arm with her
skinny finger. “But you cannot forget that song, Bartow, the song
your wife sang after Bonny was born.”
But when Bomba would have questioned her further, she pushed
him away from her and began to sing again.
“La la la! la la la!” she sang.
It was the gay and vibrant melody that poor Casson had tried to sing.
Bomba could do nothing but stand in bewildered silence and watch
the old woman as she danced and sang, whirling about the poor
stage with a nimbleness that was amazing in one of her age.
Confusedly, he tried to think of the things she had said to him, but
beneath the wild spell of that performance he could reason nothing
out, and could only stare dazedly at this wreck of what had once
been a great genius.
What would happen to him, Bomba wondered, when the woman
tired of dancing and perhaps found out that he was not Bartow or
Bartow’s ghost as she thought him then, but only Bomba, a boy of
the jungle.
With one last twirl and a deep bow to an imaginary audience,
Sobrinini brought her weird performance to an end. She grinned
toothlessly at the staring boy, and skipped lightly to the edge of the
platform.
“Ha, Bartow, like you Sobrinini in the dance that charmed all Paris?”
she chirped, patting Bomba’s shoulder coquettishly. “Sobrinini has
not lost her art. How say you, Bartow?”
Bomba felt that he must keep her in good humor with him if he were
to gain that information about himself for which he had risked so
much. He had already learned something—or guessed something.
Perhaps he could learn more.
“I like your dance,” he told her gravely. “But I like best the song that
Bartow’s wife sang when—when——”
“When Bonny was born?” prompted the old woman, and without
waiting for a reply began to hum again that tender melody that had
found its way to the depths of Bomba’s heart.
It thrilled the boy again more strangely than before. When the song
was done, emotion conquered Bomba’s caution, and he flung out his
hands to Sobrinini, begging her to tell him what she knew about
Bartow, about Bartow’s wife, about the child that she had called
Bonny.
But Sobrinini drew back from him, quick suspicion glinting in her
eyes.
“No, no! Not now, Bartow, not now! It is another joke that you play on
Sobrinini. No, no! To-night you will sleep here and to-morrow I will
pay back your jokes with some of my own. Come! I will show you
where you are to sleep.”
So saying, and mumbling to herself as she had before, the
demented woman led him out of the strange room with the chairs
and platform that had so bewildered the boy and down a long, dark
passage.
There Sobrinini paused and clapped her hands sharply.
As though by magic, a figure appeared out of the darkness before
them.
“A torch!” croaked Sobrinini. “A torch to drive the shadows back into
the night. Bring a torch. Make haste.”
The figure disappeared and in a few seconds returned with a light.
The features of the slave seemed savage and sinister in the
flickering illumination.
“Give it to me! Give it to me!” cried Sobrinini irritably. “Now, slave,
begone!”
Instantly the figure vanished again, and Bomba looked about him
apprehensively. For a moment he had the fantastic notion that the
shadows all about him were filled with ghostly figures that appeared
and disappeared by magic and made no noise.
But Sobrinini stalked before him, flaring torch in hand. Bomba
followed her into a room so small that the farthest corners were
made bright by the wavering light of the torch.
As Bomba entered the place he had a strange feeling that he had
seen it before, had been in it before, had once looked about him as
he was now looking at the few articles of furniture and the pictures
on the walls.
But even while he felt this so strongly that it seemed almost uncanny,
Bomba knew that it could not be so and that it was impossible he
had ever enacted this scene or anything like it before.
In all his wild life in the jungle, he had never seen anything like that
strange object in one corner of the room, raised from the floor by
posts and covered with a cloth. If Bomba had been told that the
strange object was a bed, he would have been no better informed
than before. As far as he could remember, he had never slept in
anything like that in his life.
While he was taking in the various features of the room, Sobrinini
deposited the torch in a socket on the wall and turned again to
Bomba.
“Bartow,” she said, and there was that softened light in her wild eyes
that had appeared there while she was singing the tender lullaby that
Bartow’s wife had crooned to Bonny, “this is where you sleep while
you remain with Sobrinini on her island. Good-night, Bartow, or
Bartow’s ghost, and pleasant dreams!”
Then she turned and, noiselessly as a ghost or a shadow, glided
from the room.
Bomba stood where she had left him, motionless.
What was that strange feeling that made his heart swell within him
until he could not bear the pain of it, that made him reach out wildly,
beseechingly, for some vague, beautiful thing that he had never
known, or only dimly remembered?
What was it that suddenly made him feel his loneliness and
desolation more keenly than he had ever felt it in his life, as though
he had been given for a moment a glimpse of something warm and
friendly and sweet, only to have the curtain fall again and leave him
in his solitude, more utterly alone than he had ever been before?
What was it that drew him haltingly, almost fearfully, across the tiny
room to stop beneath a picture on the wall and, with his hungry eyes
upraised, stare at it intently?
Bomba could not tell. He only knew that within him there was a
growing tumult of emotions, fear, hope, doubt, and a longing so
fierce that it was pain.
Into the jungle lad’s upturned, pleading face the beautiful eyes in the
picture looked steadily and gravely down. It was a lovely face, girlish
and sweet, with soft hair waved back from a broad, low forehead and
with eyes one knew were soft and dark. The lips turned up at the
corners, half-smiling.
Bomba had never seen that beautiful pictured face before, as far as
he could remember. Then how was it that those great eyes looking
into his, those sweet lips parted as though to speak to him, touched
a chord in him that had never before resounded, and increased a
thousandfold his longing for that vague and beautiful thing that he
had never known?
She was even fairer than the woman with the golden hair. Yes, much
more fair and sweet.
Suddenly Bomba’s eyes were full of tears, and he heard himself
crying in a voice that shook:
“Mother! Mother!”
With both hands upraised toward the beautiful face, Bomba slid
slowly to the floor and lay there, his frame shaking with
unaccustomed sobs.
Softly, weirdly, tenderly, there floated to the lad, as though from a
great distance, the strain of that sweet melody, the song that
Bartow’s wife had sung to Bonny.
Long after the lullaby had died away Bomba remained there,
motionless, crouched beneath the picture, one arm before his eyes.
CHAPTER XIX
A STARTLING INTERRUPTION
Worn out by the exciting adventures and fierce emotions of the day,
Bomba fell asleep. When he awoke the chill gray of early dawn was
stealing in at the window of the little room.
He was still on the floor beneath the picture. But he would not have
sought the bed in any event. It represented to him something so
strange that he would probably have been unable to sleep in it. The
hard floor on which he now lay or the earth of the jungle or his own
hammock was far more restful and sleep compelling.
At first, only half awake, Bomba had difficulty in remembering the
events of the day before and why he was in the place where he
found himself. He sprang to his feet, rubbed his eyes, and looked
about him.
His eyes fell upon the picture of the beautiful lady, and memory
returned to him.
That tender, sweet melody sung by Sobrinini! Bomba had never
heard it till lately, as far as he could remember, and yet felt that he
had known it always. He wondered at the power it had exercised
over him. It had tugged at his heart as though it would pull it out by
the roots.
Perhaps, he thought, this was the work of Sobrinini. Was she not a
witch? Certainly, everything he had witnessed since his arrival at the
island tended to that conclusion. The mortal fear in which her
servitors stood of her would seem to indicate the possession of
some supernatural power. Had she woven a spell about him, made
him seem to remember things that had never happened?
Yet this spell, if spell it was, had not been a malignant one. It had
made him strangely happy. The tears that had been forced from him
were tears of joy in the main, and even the melancholy that attended
them had been tender and sweet.
And this emotion had been so rare in the boy’s lonely life that it
brought a rush of gratitude toward Sobrinini. He was not afraid of the
weaver of spells and the charmer of serpents. He stood in awe of
her, but the predominant feeling was of friendship and pity for her
demented condition.
And there was something else that made a tie between them. She
had known Bartow and Bartow’s wife and Bonny. How much that
name sounded like Bomba!
In the dim light of the growing dawn, Bomba came close to the
beautiful pictured face on the wall and studied it wistfully. He could
see love in those eyes as they looked at him. He would ask Sobrinini
for that picture. Perhaps she would give it to him.
He dwelt on it, until every feature was engraved on his memory.
From that time on, he would always be able to see that face, even
when his eyes were closed.
Reluctantly at last he turned away. He had work to do, and time was
pressing. He must find out from Sobrinini what he had come to learn.
And then he must hurry on in pursuit of the captives of Nascanora.
He must be at hand when the party passed the point in the river
where Ashati and Neram were still waiting for him.
He would seek out Sobrinini at once and demand from her an
answer to the questions that tormented him. He would find out who
Bartow was and why he, Bomba, had twice been taken for Bartow or
Bartow’s ghost.
With these thoughts in mind and forgetful of the fact that he had had
nothing to eat since the afternoon of the day before, Bomba strode
into the passage and found his way back to the strange room with
the chairs and platform where Sobrinini had sung to him.
The place looked changed to him now. It was not so weird nor
mysterious now that the torches had flickered out and dawn had
replaced the shadows of the night.
If Bomba had expected to find Sobrinini there, he was disappointed.
The great bare hall was deserted, and though he stopped and
listened intently, there was no sign of life anywhere.
Then suddenly there came to him from a distance the sound of
singing. First Sobrinini’s voice—he could not be mistaken in it now—
then other voices joining in a sort of weird chant that chilled the lad’s
blood yet drew him irresistibly toward the point from which the sound
was coming.
Slowly he emerged from the building and found himself enveloped in
a swirling, gray mist.
Yet the sound of the chant served him as a guide, and he went on
and on, now coming closer to the singers, then seeming to draw
away from them as the voices receded.
At last, when he was beginning to think that Sobrinini had again laid
a spell on him and that the voices were ghostly voices, to be heard
by none but himself, he saw a dark form emerge from the mist and
after it another and another.
Bomba stood still and watched. The natives were dancing, flinging
their arms about wildly and intoning their weird chant, now harsh and
loud, now soft like the sighing of the wind through the trees.
It was like a dance of ghosts, and it was not alone the chill damp of
the air that struck cold to Bomba’s heart. He felt as though he were
in some other world, and that an evil one. He had never longed for
the warmth and brightness of the jungle sun as he did at that
moment.
But as the natives danced on, as tireless apparently as the ghosts
that Bomba half-thought them, the mist began to clear and the sun
struck through, causing the moisture upon the dark bodies of the
dancers to glisten.
Then, in the center of the ring, Bomba beheld Sobrinini, whirling
wildly in a mad dance, long, gray locks streaming about her, and in
each upflung hand the head of a great snake, while the bodies of the
reptiles coiled about her arms and neck.

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An Economy Based on Carbon Dioxide

and Water Potential of Large Scale

Hydrothermal Reduction of Carbon Dioxide to Low-Carbon

Carbon Dioxide and Organometallics 1st Edition Xiao-

Fundamentals and Applications of Supercritical Carbon

Energy Technology 2016 Carbon Dioxide Management and

Electrochemical Reduction of Carbon Dioxide Overcoming

Carbon Dioxide Emission Management in Power Generation

Energy Technology 2017: Carbon Dioxide Management and

Carbon Dioxide Thermodynamic Properties Handbook :

ISBN 978-3-030-15867-5 ISBN 978-3-030-15868-2 (eBook)

Library of Congress Control Number: 2019936294

© Springer Nature Switzerland AG 2019

The Carbon Dioxide Problem

Fig. 1 Growth of world population

Fig. 2 CO2 emission

Fig. 3 Energy consumption

Fig. 4 Increase of average temperature

• Decarbonization of energy, by using perennial primary sources, alternative to

Table 1 Use of energy sources alternative to fossil-C in some virtuous countries

Table 2 Energy density of a Energy carrier MJ/kg

Capture of produced CO2 from point-continuous sources or from the atmo-

Table 3 CO2 emission from Industrial sector MtCO2/y produced

1 Large Scale Utilization of Carbon Dioxide: From Its Reaction

3 Technical and Industrial Applications of CO2 . . . . . . . . . . . . .... 73

4.3.2 The Economics of Mineral Carbonation . . . . . . . . . . .. 133

6 Use of CO2 as Source of Carbon for Energy-Rich

8.3.1 Dielectric Barrier Discharge (DBD) . . . . . . . . . . . . . . . 292

Michele Aresta and Francesco Nocito

© Springer Nature Switzerland AG 2019 1

1.2 CCS Versus CCU: The Amount Issue

1.3 CO2 Conversion Options: The Energy Issue

Table 1.1 CCS and CCU at glance

Table 1.1 (continued)

A. Conversion into chemicals in which the –CO2– entity is preserved by

B. Carboxylation of organic substrates.

RH þ CO2 ! R CO2 H ð1:1Þ

Today, the introduction of a carboxylic moiety –CO2– into an organic substrate

RCN þ 2H2 O ! RCO2 H þ NH3 ð1:3Þ

DG ¼ DGfðnewmoleculeperCatomÞ DGfðCO2 Þ ð1:4Þ

1.4 CCU and Resources Conservation

CH3OH −2 −6 −238.7 126.8 −276.5 −276.5 5

Correlation Nox vs Energy

Fig. 1.1 Correlation DNox/DEnergy for some reduced forms of CO2

<1750 1750 ++ Last two centuries Our days Future

1.5 CCU and Innovation

1.6 CCU and Sustainability of the Chemical and Polymer

It is worth to emphasize that if the energy industry can be decarbonized, the

H2g þ CO2g ! HCO2 H1 ð1:6aÞ

H2g þ CO2g þ RR0 NH ! RR0 H2 þ HCO2 ð1:6bÞ

RR0 NH2þ HCO2 þ HX ! HCO2 H þ RR0 NH2 þ X ð1:7Þ

Fig. 1.3 Global formic acid

RðArÞH þ CO2 ! RðArÞCO2 H ð1:8Þ

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