Styring / Quadrelli / Armstrong Carbon Dioxide Utilisation

Closing the Carbon Cycle
1. Auflage 2014
ISBN: 978-0-444-62748-3
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 336 Seiten

Carbon Dioxide Utilisation: Closing the Carbon Cycle explores areas of application such as conversion to fuels, mineralization, conversion to polymers, and artificial photosynthesis as well as assesses the potential industrial suitability of the various processes. After an introduction to the thermodynamics, basic reactions, and physical chemistry of carbon dioxide, the book proceeds to examine current commercial and industrial processes, and the potential for carbon dioxide as a green and sustainable resource. While carbon dioxide is generally portrayed as a 'bad' gas, a waste product, and a major contributor to global warming, a new branch of science is developing to convert this 'bad' gas into useful products. This book explores the science behind converting CO2 into fuels for our cars and planes, and for use in plastics and foams for our homes and cars, pharmaceuticals, building materials, and many more useful products. Carbon dioxide utilization is a rapidly expanding area of research that holds a potential key to sustainable, petrochemical-free chemical production and energy integration. - Accessible and balanced between chemistry, engineering, and industrial applications - Informed by blue-sky thinking and realistic possibilities for future technology and applications - Encompasses supply chain sustainability and economics, processes, and energy integration

Autoren/Hrsg.

Styring, Peter

Quadrelli, Elsje Alessandra

Armstrong, Katy

Inhaltsverzeichnis

1;Front Cover;1
2;Carbon Dioxide Utilisation
Closing the Carbon Cycle;4
3;Copyright;5
4;Contents;6
5;List of Contributors;12
6;Preface;16
6.1;P.1 Utilisation;17
6.2;P.2 Closing the Carbon Cycle;19
6.3;P.3 The Multiple Roles of CDU;22
6.4;Acknowledgements;24
6.5;References;25
7;PART 1 - Introductory Concepts;26
7.1;Chapter 1 - What is CO2? Thermodynamics, Basic Reactions and Physical Chemistry;28
7.1.1;1.1 Introduction;28
7.1.2;1.2 Spectroscopy and its role in climate change;30
7.1.3;1.3 Phase behaviour and solvent properties;31
7.1.4;1.4 Kinetics and thermodynamics;33
7.1.5;1.5 Commercially important reactions of carbon dioxide;37
7.1.6;References;40
7.2;Chapter 2 - Carbon Dioxide Capture Agents and Processes;44
7.2.1;2.1 Carbon dioxide sources;44
7.2.2;2.2 Capture processes;45
7.2.3;2.3 Carbon dioxide capture agents;47
7.2.4;2.4 Future perspectives;53
7.2.5;2.5 Concluding remarks;56
7.2.6;References;56
7.3;Chapter 3 - CO2-Derived Fuels for Energy Storage;58
7.3.1;3.1 Introduction;58
7.3.2;3.2 The decarbonisation of electrical generation;60
7.3.3;3.3 The decarbonisation of transport;65
7.3.4;3.4 The decarbonisation of heat;67
7.3.5;3.5 Conclusion;68
7.3.6;References;69
7.3.7;Further Reading;69
7.4;Chapter 4 - Environmental Assessment of CO2 Capture and Utilisation;70
7.4.1;4.1 Introduction: Why do we need a reliable environmental assessment of CO2 utilisation?;70
7.4.2;4.2 Green chemistry and environmental assessment tools;71
7.4.3;4.3 Life cycle assessment;72
7.4.4;4.4 ISO standardisation of LCA;73
7.4.5;4.5 How to conduct an LCA for CO2 capture and utilisation?;74
7.4.6;4.6 Conclusions for LCA of CCU;80
7.4.7;Acknowledgement;80
7.4.8;References;80
8;PART 2 -
Contribution to Materials;82
8.1;Chapter 5 - Polymers from CO2—An Industrial Perspective;84
8.1.1;5.1 Introduction;84
8.1.2;5.2 Challenges in CO2 utilisation;84
8.1.3;5.3 Polymers based on CO2;85
8.1.4;5.4 Polymers based on CO2—direct approach;86
8.1.5;5.5 Polymers based on CO2—indirect approach;92
8.1.6;5.6 Industrial example: direct epoxide/CO2 copolymerization;92
8.1.7;5.7 Summary and outlook;94
8.1.8;References;94
8.2;Chapter 6 - CO2-based Solvents;98
8.2.1;6.1 Introduction;98
8.2.2;6.2 CO2 as a solvent;99
8.2.3;6.3 CO2-expanded liquids;107
8.2.4;6.4 CO2-responsive switchable solvents;112
8.2.5;6.5 Conclusions;117
8.2.6;References;118
8.3;Chapter 7 - Organic Carbonates;122
8.3.1;7.1 Introduction;122
8.3.2;7.2 Carbonates from cyclic ethers;123
8.3.3;7.3 Linear carbonates from alcohols;125
8.3.4;7.4 Cyclic carbonate from diols;130
8.3.5;7.5 Effect of drying agents;132
8.3.6;7.6 Oxidative carboxylation of alkenes;135
8.3.7;7.7 Industrial potential;136
8.3.8;References;138
8.4;Chapter 8 - Accelerated Carbonation of Ca- and Mg-Bearing Minerals and Industrial Wastes Using CO2;140
8.4.1;8.1 Introduction;140
8.4.2;8.2 Engineered weathering of silicate minerals;144
8.4.3;8.3 Carbonation of alkaline industrial wastes;152
8.4.4;References;160
9;PART 3 -
Energy and Fuels;164
9.1;Chapter 9 - Conversion of Carbon Dioxide to Oxygenated Organics;166
9.1.1;9.1 Introduction;166
9.1.2;9.2 Methanol production;168
9.1.3;9.3 Dimethyl ether;179
9.1.4;9.4 Other oxygenates;181
9.1.5;9.5 Concluding remarks;181
9.1.6;References;181
9.2;Chapter 10 - The Indirect and Direct Conversion of CO2 into Higher Carbon Fuels;186
9.2.1;10.1 The (inevitable) coupled nature of our energy and CO2 emission challenges;186
9.2.2;10.2 The concept of carbon-neutral liquid hydrocarbon fuels;188
9.2.3;10.3 The conversion or utilisation of CO2;189
9.2.4;Acknowledgement;205
9.2.5;References;205
9.3;Chapter 11 - High Temperature Electrolysis;208
9.3.1;11.1 Introduction;209
9.3.2;11.2 High temperature operation;210
9.3.3;11.3 Cell and stack configurations and balance of plant;212
9.3.4;11.4 Cell materials;213
9.3.5;11.5 Electrochemistry;219
9.3.6;11.6 SOC diagnostics;221
9.3.7;11.7 Electrolysis of carbon dioxide and co-electrolysis of carbon dioxide and steam;224
9.3.8;11.8 Conclusions;230
9.3.9;References;230
9.4;Chapter 12 - Photoelectrocatalytic Reduction of Carbon Dioxide;236
9.4.1;12.1 Introduction;236
9.4.2;12.2 Organizing principles of photoelectrochemical CO2 reduction;239
9.4.3;12.3 Photovoltaic/electrolyser duel module systems: Metal electrodes for CO2 conversion;243
9.4.4;12.4 Group III–V: GaP, InP, GaAs as photocathode for CO2 reduction;247
9.4.5;12.5 Group II–VI: CdTe, and Group IV: Si, SiC photoelectrodes;248
9.4.6;12.6 Titanium oxide photoelectrodes;249
9.4.7;12.7 Other oxides photoelectrode: Cu2O, CuFeO2, etc;250
9.4.8;12.8 Semiconductor with a molecular co-catalyst;251
9.4.9;12.9 Semiconductors decorated with metal electrocatalysts for CO2 reduction;252
9.4.10;12.10 Summary, conclusion and prospect;254
9.4.11;Acknowledgements;255
9.4.12;References;255
10;PART 4 -
Perspectives and Conclusions;260
10.1;Chapter 13 - Emerging Industrial Applications;262
10.1.1;13.1 Introduction;262
10.1.2;13.2 Scaleup;262
10.1.3;13.3 Technology readiness;264
10.1.4;13.4 Methanol pilot plants;266
10.1.5;13.5 CO2 reduction on a pilot scale;267
10.1.6;13.6 Reforming reactions on a pilot scale;267
10.1.7;13.7 Polymer pilot plants;268
10.1.8;13.8 Mineralization pilot plants;272
10.1.9;13.9 Summary;274
10.1.10;References;275
10.2;Chapter 14 - Integrated Capture and Conversion;278
10.2.1;14.1 Introduction;278
10.2.2;14.2 Routes to CDU;279
10.2.3;14.3 Integrated CO2 utilisation processes;280
10.2.4;References;293
10.3;Chapter 15 - Understanding and Assessing Public Perceptions of Carbon Dioxide Utilisation (CDU) Technologies;298
10.3.1;15.1 Introduction;298
10.3.2;15.2 What will the public think of CDU?;299
10.3.3;15.3 Assessing public opinions of CDU;303
10.3.4;15.4 Conclusion;306
10.3.5;References;307
10.4;Chapter 16 - Potential CO2 Utilisation Contributions to a More Carbon-Sober Future: A 2050 Vision;310
10.4.1;16.1 Context elements;310
10.4.2;16.2 Efficiency and new materials to complement CCS efforts;312
10.4.3;16.3 The massive attention on renewable energy injection;315
10.4.4;16.4 Bridges among CO2-to-fuel and specialty chemicals productions;322
10.4.5;16.5 When CO2 supply becomes the issue;323
10.4.6;16.6 Local solutions to global issues;323
10.4.7;16.7 Timescales to deployment;325
10.4.8;References;325
11;Index;328

Leseproben

Chapter 1

What is CO2? Thermodynamics, Basic Reactions and Physical Chemistry

Michael North     Green Chemistry Centre of Excellence, Department of Chemistry, The University of York, Heslington, York, UK

Abstract

This introductory chapter introduces the structural, physical and spectroscopic properties of carbon dioxide and shows how these are linked to its role in global warming. The phase behaviour of carbon dioxide is introduced including the accessibility of a supercritical phase. The kinetics and thermodynamics of reactions involving carbon dioxide are introduced to provide a theoretical basis for understanding the reactions of carbon dioxide and the limitations as to what catalysis can achieve. Finally, the commercially important chemical reactions of carbon dioxide are surveyed within this kinetic and thermodynamic framework.

Keywords

kinetics; thermodynamics; reactivity; phase-behaviour; structure

Chapter Outline

1.1 Introduction?3

1.2 Spectroscopy and its role in climate change?5

1.3 Phase behaviour and solvent properties?6

1.4 Kinetics and thermodynamics?8

1.5 Commercially important reactions of carbon dioxide?12

References?15

1.1. Introduction

Carbon dioxide (CO2) is a triatomic molecule with a molecular weight of 44Da. It is a gas at room temperature and pressure. At atmospheric pressure it sublimes directly from a solid to a gas at ?78°C. Carbon dioxide is a relatively inert gas which is neither explosive nor flammable and which does not support combustion. Therefore, it is widely used in fire extinguishers and fire suppression systems, though some care is needed especially in confined spaces as it is an asphyxiant and has a density (1.98kg/m3 at 0°C) greater than that of air. Carbon dioxide occurs naturally in the Earth's atmosphere as a result of volcanic eruptions, forest fires and plant and animal respiration. It is essential to the growth of green plants which use photosynthesis to convert carbon dioxide and water into sugars. These are key parts of the natural carbon cycle which controls the level of carbon dioxide in the Earth's atmosphere and hence the surface temperature of the planet.1 Prior to the start of the industrial revolution, atmospheric carbon dioxide levels were around 270ppm by volume.2

The carbon dioxide molecule has a linear structure in which each carbon–oxygen bond has a length of 116.3pm and is composed of a ?- and a ?-bond. The two ?-bonds are orthogonal to one another and like any carbon–oxygen bonds are polarised such that the carbon atom carries a partial positive charge (+0.592) and the oxygen atoms carry a partial negative charge (?0.296) due to the higher electronegativity of oxygen compared to carbon. Figure 1.1 shows various representations of carbon dioxide.

FIGURE 1.1 Representations of carbon dioxide.

The chemical reactivity of carbon dioxide is determined by the polarisation of the carbon oxygen bonds, and the chemistry is dominated by the reaction of carbon dioxide with nucleophiles which react at the central carbon atom (Scheme 1.1). The nucleophile may be a neutral species with a lone pair of electrons (e.g., an amine), may possess an electron-rich ?-bond (e.g., a phenolate) or may possess a carbon-metal ?-bond (e.g., a Grignard reagent). The other key feature of the chemistry of carbon dioxide is its coordination to metals. This is an important area as the coordination of carbon dioxide to a metal can significantly change both the electron distribution and molecular geometry within the carbon dioxide molecule, thus dramatically changing its chemical reactivity.

This is the basis of many metal-induced and metal-catalysed reactions of carbon dioxide. The area is however complicated by the numerous ways in which carbon dioxide can coordinate to one or more metals due to its ability to coordinate through either carbon or oxygen and to bridge between metal atoms. As shown in Figure 1.2, there are at least 13 known coordination geometries in carbon dioxide metal complexes.3a–3d,4 If just the monometallic complexes are considered, an electron deficient metal will coordinate to one of the oxygen atoms ?O1) and this does not change the geometry of the carbon dioxide, but will withdraw electron density from it, thus making the carbon atom more susceptible to attack by nucleophiles. In contrast, metals with loosely held electrons may coordinate to the carbon atom of carbon dioxide ?C1) which both makes the carbon atom less electron deficient and hence less susceptible to attack by nucleophiles: this also changes the overall geometry of the CO2 unit from linear to bent.

SCHEME 1.1 Reaction of carbon dioxide with nucleophiles.

FIGURE 1.2 Carbon dioxide metal complex geometries.

1.2. Spectroscopy and its role in climate change

The carbon dioxide molecule has three vibrational modes: two stretches (symmetric and anti-symmetric) and a bend (Figure 1.3). For gaseous carbon dioxide, the symmetric stretch (1286–1388cm?1) does not involve a change in the molecular dipole moment and hence it is infrared inactive, but Raman active. The anti-symmetric stretch (2349cm?1) and bend (667cm?1) do involve a change in the molecular dipole moment and hence are infrared active.4 The 13C NMR resonance of carbon dioxide in non-polar solvents occurs at 126ppm.4

The infrared active vibrations of carbon dioxide are directly responsible for its role as a greenhouse gas. The Earth's atmosphere is transparent to visible light coming from the sun which strikes the Earth's surface and is reemitted as infrared radiation. The main components of the Earth's atmosphere (oxygen and nitrogen) are also transparent to infrared radiation. However, carbon dioxide (and other atmospheric gases such as water vapour, methane and nitrous oxide) adsorb some of the infrared radiation, trapping it within the Earth's atmosphere, resulting in global warming.5 Carbon dioxide is by no means the most potent greenhouse gas; however it does have a much higher atmospheric concentration than other greenhouse gases and so is responsible for about three quarters of global warming.6 As the concentration of carbon dioxide in the atmosphere increases, so the amount of infrared radiation trapped increases. In 2013, the atmospheric concentration of carbon dioxide reached 400ppm by volume,7 an increase of 130ppm or 48% since the start of the industrial revolution. This increase in atmospheric carbon dioxide is believed to be due to mankind's activities (anthropogenic carbon dioxide) in burning fossil fuels (coal, oil and gas) to produce energy. The resulting increased carbon dioxide emissions cannot be balanced within the natural carbon cycle, so that the concentration of carbon dioxide in the atmosphere builds up. Each 188million tonnes of carbon dioxide emitted due to fossil fuel burning raises the atmospheric carbon dioxide concentration by 1ppm by volume.

FIGURE 1.3 Carbon dioxide vibrations.

1.3. Phase behaviour and solvent properties

The p-T phase diagram for carbon dioxide is shown in Figure 1.4. The triple point is at 5.1bar. This is the lowest pressure at which liquid carbon dioxide can exist and is the reason why carbon dioxide sublimes at atmospheric pressure. The critical point of carbon dioxide is at 73.8bar and 31°C Above this temperature and pressure carbon dioxide forms a supercritical fluid which will expand to fill a container (like a gas), but which has a density (like a liquid). Above this point there is no way to distinguish between the gas and liquid.

Compared to other common chemicals, the supercritical region of carbon dioxide occurs at relatively accessible temperatures and pressures. As a result, liquid or supercritical carbon dioxide has attracted considerable interest as a green solvent for chemical reactions,8a,8b,9 chromatography10 and extractions.11 One of the large scale commercial uses of supercritical carbon dioxide is in the decaffeination of coffee beans.8a,8b Each year 18million tonnes of carbon dioxide are used as a solvent.4 For the fine chemicals and pharmaceuticals industries, solvent is often the largest source of waste in a process.12a,12b The use of supercritical carbon dioxide can significantly reduce this waste and the associated carbon dioxide emissions. The savings come not from the use of supercritical carbon dioxide itself as this will eventually be vented to atmosphere, but from not having to produce and eventually incinerate the conventional solvent.

FIGURE 1.4 Carbon dioxide phase diagram.

The polarity of supercritical carbon...