New and Future Developments in Catalysis. Activation of Carbon Dioxide

639 Pages·2013·47.456 MB·English

by  Steven L. Suib (Eds.)

NEW AND FUTURE DEVELOPMENTS
IN CATALYSIS
NEW AND
FUTURE
DEVELOPMENTS
IN CATALYSIS
ACTIVATION OF CARBON
DIOXIDE
Edited by
Steven L. Suib
Department of Chemistry and Chemical Engineering
and Institute of Materials Science, The University of Connecticut,
Storrs, CT 06269-3060
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Introduction
This book concerns activation of carbon and fuels from CO. Both homogeneous and
2
dioxide using either homogeneous or hetero­ heterogeneous catalysts are discussed. The
geneous catalysis. The potential threat of car­ use of carbon dioxide to produce hydrogen
bon dioxide as a Greenhouse gas that can which can be used as a fuel is one avenue of
cause breakdown on the ozone layer and current thought and experimentation. Some
enhanced heating of the earth has been recog­ of the studies reported here consider the fun­
nized in recent years. Some causes of this damental mechanisms of activation of carbon
enhanced production of carbon dioxide are dioxide as well as fundamental experimental
from human activities involving combustion studies on pristine surfaces as model surfaces
of hydrocarbon fuels. In recent years there has that can be used.
been renewed interest in finding processes to Some approaches rely on specific strate­
chemically activate the carbon dioxide mole­ gies to produce valuable chemicals and fuels
cule, which is extremely stable. Finding eco­ such as the formation of CC bonds from
nomical ways to activate carbon dioxide is a CO or the detection of initial intermediates
2
major focus of many researchers throughout in the reduction of CO. Some approaches
2
the world. involve use of a variety of different methods
Several of the world’s experts in this area of activation including thermal, photochemi­
have contributed to this book. Their level of cal, ultrasonic cavitation, microwave, electro­
experience and recent research activity in chemical, and others. Many of these studies
this area are extensive. Many of these authors are in their infancy stage with experiments
have provided unique approaches to the being designed to show what is possible and
field of activation of carbon dioxide and the amount of energy need to carry out such
have given their interpretation of the funda­ transformations.
mental problems associated with activating Another approach is to use carbon dioxide
carbon dioxide as well as practical ways to as a reagent to promote specific reactions.
carry out chemical transformations of CO . Promoters can be of various types depending
2
Considerable recent progress has been made on the reaction conditions. Mechanistic stud­
in many key areas regarding activation of ies from first principles are discussed and can
carbon dioxide and these approaches are provide insight into how one might go about
discussed here. choosing various methods to activate carbon
Catalytic processes for the activation of car­ dioxide. One major area where carbon diox­
bon dioxide are limited by the extent of con­ ide is being studies is in the formation of syn­
version as well as the extreme conditions that thesis gas. Finding the right catalysts to
are sometimes used in order to activate this enhance the rates of reaction in these systems
molecule. Researchers are at the stage where is a key factor in many of these studies.
practical and economical methods are being The adsorption of carbon dioxide with var­
proposed rather than solely finding funda­ ious substrates is another key focus of resear­
mental ways to produce valuable chemicals chers from around the world. Much emphasis
ix
x INTRODUCTION
in this area has been put on porous materials and solvents that might be used, the source
that can trap carbon dioxide. Comparing vari­ of energy for the activation, and potential
ous porous materials and their limits on disposal of side products, catalysts, and
adsorption is being done to find ideal materi­ recovery of solvents. The area of activation
als that can adsorb carbon dioxide and then of carbon dioxide is a continually growing
potentially release this when needed for chem­ field of research and there are some clear
ical reactions. Adsorption is a key step in all pathways that might be pursued in the vari­
catalytic reactions over solid substrates and ous chapters of this book.
fundamental studies along these lines are
underway.
Finally, the environmental aspects of acti­
Acknowledgments
vation of carbon dioxide are also discussed
in many of the chapters of this book. SLS thanks the US Department of Energy Basic Energy
Sciences Program and Dr. Raul Miranda as well as Dr.
Certainly all aspects of these types of reac­
Maria Burka of the National Science Foundation, CBET
tions need to be environmentally friendly
Program for significant ideas about this book and their
such as the nature of catalysts, substrates, support of catalysis research.
Contributors
Naveed Ahmed Department of Chemistry, Jian Gao State Key Laboratory and Institute of
Graduate School of Science, Chiba University, Elemento-Organic Chemistry, Nankai
Yayoi 1-33, Inage-ku, Chiba 263-8522, Japan University, Weijin Rd. 94, Tianjin 300071, P.R.
Mohd Bismillah Ansari Laboratory of Nano- China
Green Catalysis and Nano Center for Fine Qingfeng Ge Department of Chemistry and
Chemicals Fusion Technology, Department of Biochemistry, Southern Illinois University,
Chemistry, Inha University, Incheon 402–751, Carbondale, IL 62901, USA
South Korea Rainer Glaser Department of Chemistry,
Masahiko Arai Division of Chemical Process University of Missouri, Columbia, MO 65211,
Engineering, Faculty of Engineering, Hokkaido USA
University, Sapporo 060-8628, Japan Liang-Nian He State Key Laboratory and
Armando Borgna Institute of Chemical and Institute of Elemento-Organic Chemistry,
Engineering Sciences (ICES), A*STAR, 1 Pesek Nankai University, Weijin Rd. 94, Tianjin
Road, Jurong Island, Singapore 627833, 300071, P.R. China
Singapore Yuichiro Himeda National Institute of Ad -
U. Burghaus Department of Chemistry and vanced Industrial Science and Technology,
Biochemistry, NDSU Dept. 2735, PO Box 6050, Tsukuba Central 5-2, 1-1-1 Higashi, Tsukuba,
Fargo, ND 58108-6050, USA Ibaraki 305-8565, Japan
Paula O. Castello-Blindt Department of Narcís Homs Departament de Química
Chemistry, University of Missouri, Columbia, Inorgànica and Institut de Nanociència i
MO 65211, USA Nanotecnologia, Facultat de Química,
Jirˇí Cˇejka J. Heyrovský Institute of Physical Universitat de Barcelona, Martí i Franquès
Chemistry, Academy of Sciences of the Czech 1-11, 08028 Barcelona, Spain
Republic, v.v.i., Dolejškova 3, 182 23 Prague 8, Catalonia Institute for Energy Research (IREC),
Czech Republic Jardins de les Dones de Negre 1, 08930
Parag A. Deshpande Department of Chemical Barcelona, Spain
Engineering, Indian Institute of Science, Zhaomin Hou Organometallic Chemistry
Bangalore 560012, India Laboratory and Advanced Catalysis Research
Luca Di Felice Department of Chemical Group, RIKEN Center for Sustainable Resource
Engineering and Chemistry, Eindhoven Science, 2-1 Hirosawa, Wako, Saitama
University of Technology, Den Dolech 2, 351-0198, Japan
Helix Building 5612 AZ Eindhoven, The Yasuo Izumi Department of Chemistry, Grad-
Netherlands uate School of Science, Chiba University, Yayoi
Shin-ichiro Fujita Division of Chemical 1-33, Inage-ku, Chiba 263-8522, Japan
Process Engineering, Faculty of Engineering, Xinli Jia School of Chemical and Biomedical
Hokkaido University, Sapporo 060-8628, Engineering, Nanyang Technological Univer-
Japan sity, Singapore 637459, Singapore
xi
xii Contributors
Hongtao Jiang Zhejiang University of Michael North School of Chemistry, Newcastle
Technology, Hangzhou, Zhejiang, China University, Bedson Building, Newcastle upon
Arjan W. Kleij Institute of Chemical Research Tyne NE1 7RU, UK
of Catalonia (ICIQ), Av. Països Catalans 16, Sang-Eon Park Laboratory of Nano-Green
43007–Tarragona, Spain & Catalan Institute Catalysis and Nano Center for Fine Chemicals
of Research and Advanced Studies (ICREA), Fusion Technology, Department of Chemistry,
Pg. Lluis Companys 23, 08010–Barcelona, Inha University, Incheon 402–751, South Korea
Spain Pilar Ramírez de la Piscina Departament de
Raymond Lau School of Chemical and Química Inorgànica and Institut de Nanociéncia
Biomedical Engineering, Nanyang Techno- i Nanotecnologia, Facultat de Química,
logical University, Singapore 637459, Singapore Universitat de Barcelona, Martí i Franquès 1-11,
Huiquan Li Institute of Process Engineering, 08028 Barcelona, Spain
Chinese Academy of Sciences, Beijing, China Chenggong Sun Energy and Sustainability
An-Hua Liu State Key Laboratory and Institute Research Division, Faculty of Engineering,
of Elemento-Organic Chemistry, Nankai University of Nottingham, University Park,
University, Weijin Rd. 94, Tianjin 300071, P.R. Nottingham NG7 2RD, UK
China Jamil Toyir Université Sidi Mohamed Ben
Dapeng Liu School of Chemical and Biomedical Abdellah, Faculté Polydisciplinaire, B.P 1223,
Engineering, Nanyang Technological Univer- Taza, Morocco
sity, Singapore 637459, Singapore B. Viswanathan National Centre for Catalysis
Institute of Chemical and Engineering Sciences Research, Indian Institute of Technology
(ICES), A*STAR, 1 Pesek Road, Jurong Island, Madras, Chennai 600 036, India
Singapore 627833, Singapore Hui Wang Department of Chemical and
Haitao Liu Institute of Process Engineering, Biological Engineering, University of
Chinese Academy of Sciences, Beijing, China Saskatchewan, Saskatoon, Saskatchewan,
Canada 1-306-966 2685
Hao Liu Energy and Sustainability Research +
Division, Faculty of Engineering, University of Wan-Hui Wang National Institute of Advanced
Nottingham, University Park, Nottingham NG7 Industrial Science and Technology, Tsukuba
2RD, UK Central 5-2, 1-1-1 Higashi, Tsukuba, Ibaraki 305-
8565, Japan
Licheng Liu Innovation Research Center for
Fuel Cells, The University of Electro- Yanhui Yang School of Chemical and Biomed-
Communications, Chofu, Tokyo, Japan ical Engineering, Nanyang Technological
Univer sity, Singapore 637459, Singapore
Ruixia Liu Division of Chemical Process
Engineering, Faculty of Engineering, Hokkaido Jian Yin Department of Chemistry, University
University, Sapporo 060-8628, Japan of Missouri, Columbia, MO 65211, USA
Giridhar Madras Department of Chemical Hiroshi Yoshida Division of Chemical Process
Engineering, Indian Institute of Science, Engineering, Faculty of Engineering, Hokkaido
Bangalore 560012, India University, Sapporo 060-8628, Japan
Motoharu Morikawa Department of Chemistry, Sameen Zaidi Department of Chemical and
Graduate School of Science, Chiba University, Biological Engineering, University of
Yayoi 1-33, Inage-ku, Chiba 263-8522, Japan Saskatchewan, Saskatoon, Saskatchewan,
Canada 1-306-966 2685
Petr Nachtigall Department of Physical and +
Macromolecular Chemistry, Faculty of Science, Liang Zhang Organometallic Chemistry Labo-
Charles University Prague, Hlavova 2030, ratory and Advanced Catalysis Research
128 43 Prague 2, Czech Republic Group, RIKEN Center for Sustainable Resource
Contributors xiii
Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Arnošt Zukal J. Heyrovský Institute of Physical
Japan Chemistry, Academy of Sciences of the Czech
Wenbin Zhang Energy and Sustainability Republic, v.v.i., Dolejškova 3, 182 23 Prague 8,
Research Division, Faculty of Engineering, Czech Republic
University of Nottingham, University Park,
Nottingham NG7 2RD, UK
C H A P T E R
1
Catalytic Processes for
Activation of CO
2
Narcís Homsa,b, Jamil Toyirc,
and Pilar Ramírez de la Piscinaa
aDepartament de Química Inorgànica and Institut de Nanociència
i Nanotecnologia, Facultat de Química, Universitat de Barcelona,
Martí i Franquès 1-11, 08028 Barcelona, Spain
bCatalonia Institute for Energy Research (IREC), Jardins de les Dones de
Negre 1, 08930 Barcelona, Spain
cUniversité Sidi Mohamed Ben Abdellah, Faculté Polydisciplinaire,
B.P 1223, Taza, Morocco
1.1 INTRODUCTION
CO can be considered a carbon source rather than just a greenhouse gas (GHG) that needs
2
to be mitigated. As a result of tough policies on GHG emissions, CO has turned out to be a
2
strategic carbon source, available as free or even with a financial return if adequate technol-
ogy is applied for CO capture and recycling. From this perspective, an attractive opportunity
2
is emerging for a new CO-based economy. The chemical recycling of CO and its reuse in the
2 2
production of fuels or other chemicals is attractive from both an environmental perspective
and in terms of fossil source independency. CO is released as a by-product in the chemical
2
and petrochemical industry and in fermentation processes and currently, new technologi-
cal possibilities based on membranes and absorbents are opening up for its separation and
capture. High purity CO is available from such sources; indeed, some such emissions are
2
already used in the production of chemicals such as CO from the ammonia industry which is
2
fed to urea plants or CO from fermentation which is recycled into the beverage industry after
2
appropriate cleaning. Moreover, large-scale emissions of CO come from power plants fueled
2
by natural gas and from the cement industry; in these cases undesired impurities must be
taken into account before the CO becomes useful. However, these sources can be considered
2
1
Activation of Carbon Dioxide © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/B978-0-444-53882-6.00001-2
2 1. CATALYTIC PROCESSES FOR ACTIVATION OF CO
2
an opportunity for large-scale recycling of CO. In what follows we will consider different
2
options for the reuse of CO by means of chemical recycling.
2
We must bear in mind that CO is classified as a stable, almost inert molecule. To
2
activate CO , it is necessary to overcome its considerable Gibbs energy of formation:
2
CO2 (cid:31)G◦298.15K =−394.4kJmol−1. Nevertheless, CO2 use is thermodynamically possible via
numerous reactions involving its reduction or its incorporation into other compounds.
The reduction of CO2 by the cleavage of the CO bond(s) and the formation of new CH
or CC bond(s) can be accomplished using a reductant. In this case, the action of an appro-
priate catalyst can convert CO into a potential energy vector. This recycling pathway requires
2
a large input of energy and usually H as the reductant, and leads to fuels such as methane
2
and methanol. In this context, two aspects must be taken into account: the production of H
2
and the energy source. If the energy comes from renewable sources and the H does not come
2
from fossil fuels, does the overall process merit further interest. Nowadays, we can engage
optimized electrolysis of water to supply the H, thus avoiding the fossil fuel starting mate-
2
rial. The use of non-constant wind energy or electrical energy produced at night can be used
to obtain H , thereby matching the necessity to store such excess energy. In fact, storage of
2
H itself is necessary; one nice way to accomplish this is to incorporate the hydrogen into a
2
liquid fuel. Then, since the products obtained from the catalytic hydrogenation of CO can
2
be directly used as fuels, overall this process could be seen as a means of electrical energy
storage and transport. However, the recycling of CO to fuels implies its immediate release
2
into the environment.
The incorporation of CO into chemicals as a C building block is the other approach to
2 1
its reuse. In this case, lower energy input is required since the whole CO molecule is used
2
without the need to cleave the CO bond(s). However, to accomplish a desired reaction, the
action of a catalyst is also usually necessary. In this CO recycling pathway, different param-
2
eters need to be taken into account to determine the viability of a proposed process. The
amount of CO fixed and the overall energy balance of the complete chemical route, together
2
with the value of the product produced, could indicate how feasible this process is. Large-
scale production of highly valued polymers could be performed using recycled CO , thus
2
also diminishing the use of fossil resources. In this way, if highly stable long-life materials
are produced, the CO storage could be very long term and therefore the release of CO into
2 2
the environment could be very slow.
In recent years, extensive research has been carried out into these aspects of CO reuse
2
and numerous publications have appeared [1–12]. This chapter therefore presents recent
advances in the conversion of CO into fuels and desirable chemical products by using
2
heterogeneously catalyzed processes, which are summarized in Figure 1.1.
The chapter is divided in different sections. After the Introduction, the second section is
dedicated to the reactions of CO with hydrogen; particular attention is paid to large-scale
2
processes that produce synfuels: methanol, dimethyl ether (DME), methane and higher
hydrocarbons and alcohols. Then, CO -reforming processes of methane and alcohols, and
2
dehydrogenation processes using CO are presented in Section 1.3. Catalytic processes based
2
on CO insertion into organic compounds to form carbonates or carboxylic acids are dis-
2
cussed in Section 1.4. In the last part, future trends in the catalytic conversion of CO are
2
presented with a particular focus on processes that aim to produce strategic chemicals or
fuels using renewable energy sources.