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Pre-combustion Carbon Dioxide Capture Materials
Pre-combustion Carbon Dioxide Capture Materials
Pre-combustion Carbon Dioxide Capture Materials
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Pre-combustion Carbon Dioxide Capture Materials

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Using inorganic solid adsorbents/sorbents is a promising approach for carbon dioxide (CO2) capture and is attracting intense attention from both academic and industrial fields.


Pre-combustion Carbon Dioxide Capture Materials presents a range of the different inorganic materials that can be used as pre-combustion CO2 adsorbents/sorbents with specific emphasis on their design, synthesis, characterization, performance, and mechanism. Dedicated chapters cover layered double hydroxide (LDH) derived adsorbents, MgO-based adsorbents, CaO-based sorbents and alkali ceramics based sorbents.


Edited and written by world-renowned scientists in each class of CO2 capture material, this book will provide a comprehensive introduction for advanced undergraduates, postgraduates and researchers wishing to learn about the topic.

LanguageEnglish
Release dateAug 21, 2018
ISBN9781788014922
Pre-combustion Carbon Dioxide Capture Materials

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    Pre-combustion Carbon Dioxide Capture Materials - Royal Society of Chemistry

    Pre-combustion Carbon Dioxide Capture Materials

    Inorganic Materials Series

    Series editors:

    Duncan W. Bruce, University of York, UK

    Dermot O'Hare, University of Oxford, UK

    Richard I. Walton, University of Warwick, UK

    Titles in the Series:

    1: Pre-combustion Carbon Dioxide Capture Materials

    How to obtain future titles on publication:

    A standing order plan is available for this series. A standing order will bring delivery of each new volume immediately on publication.

    For further information please contact:

    Book Sales Department, Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge, CB4 0WF, UK

    Telephone: +44 (0)1223 420066, Fax: +44 (0)1223 420247,

    Email: booksales@rsc.org

    Visit our website at www.rsc.org/books

    Pre-combustion Carbon Dioxide Capture Materials

    Edited by

    Qiang Wang

    Beijing Forestry University, P. R. China

    Email: qiangwang@bjfu.edu.cn

    Inorganic Materials Series No. 1

    Print ISBN: 978-1-78801-108-2

    PDF ISBN: 978-1-78801-339-0

    EPUB ISBN: 978-1-78801-492-2

    Print ISSN: 2472-3819

    Electronic ISSN: 2472-3827

    A catalogue record for this book is available from the British Library

    © The Royal Society of Chemistry 2018

    All rights reserved

    Apart from fair dealing for the purposes of research for non-commercial purposes or for private study, criticism or review, as permitted under the Copyright, Designs and Patents Act 1988 and the Copyright and Related Rights Regulations 2003, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry or the copyright owner, or in the case of reproduction in accordance with the terms of licences issued by the Copyright Licensing Agency in the UK, or in accordance with the terms of the licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page.

    Whilst this material has been produced with all due care, The Royal Society of Chemistry cannot be held responsible or liable for its accuracy and completeness, nor for any consequences arising from any errors or the use of the information contained in this publication. The publication of advertisements does not constitute any endorsement by The Royal Society of Chemistry or Authors of any products advertised. The views and opinions advanced by contributors do not necessarily reflect those of The Royal Society of Chemistry which shall not be liable for any resulting loss or damage arising as a result of reliance upon this material.

    The Royal Society of Chemistry is a charity, registered in England and Wales, Number 207890, and a company incorporated in England by Royal Charter (Registered No. RC000524), registered office: Burlington House, Piccadilly, London W1J 0BA, UK, Telephone: +44 (0) 207 4378 6556.

    For further information see our web site at www.rsc.org

    Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon, CR0 4YY, UK

    Contents

    Chapter 1 Layered Double Hydroxides-derived Intermediate-temperature CO2 Adsorbents

    Junya Wang, Yu Zhang, Naveed Altaf, Dermot O’Hare and Qiang Wang

    1.1 Introduction

    1.2 Influence of the Chemical Composition of LDHs

    1.3 Influence of Synthetic Conditions and Methods

    1.4 LDH-based Composites

    1.5 Influence of Doping with an Alkali Metal

    1.6 Influence of Other Co-existing Gases

    1.7 Adsorption Mechanism and Kinetics

    1.8 Techno-economic Assessment of LDH-derived CO2 Adsorbents in Applications

    1.9 Outlook and Future Perspectives

    1.10 Conclusions

    Acknowledgements

    References

    Chapter 2 MgO-based Intermediate-temperature CO2 Adsorbents

    Wanlin Gao, Luyi Sun and Qiang Wang

    2.1 Introduction

    2.2 MgO Adsorption Mechanism

    2.3 Parameters that Influence MgO Adsorbents' Performance

    2.3.1 Intrinsic Factors

    2.3.2 Extrinsic Factors: Influence of Water

    2.4 Further Improvements with Additives

    2.4.1 Dispersion on Porous Supports

    2.4.2 Preparation of MgO-based Mixed Oxides

    2.4.3 Modification with Molten Salts

    2.5 Applications

    2.6 Conclusions

    Acknowledgements

    References

    Chapter 3 CaO-based High-temperature CO2 Sorbents

    C. Courson and K. Gallucci

    3.1 CaO

    3.1.1 Uses of CaO

    3.1.2 Natural and Waste Sources of CaO

    3.1.3 Synthesis Methods of CaO

    3.2 Carbonation

    3.2.1 Thermodynamic

    3.2.2 Kinetic

    3.2.3 Modelling Approaches

    3.2.4 Sintering

    3.3 Preparation Routes for the Improvement of Sintering Resistance

    3.3.1 Pre-treatments

    3.3.2 Synthesis Methods

    3.3.3 Mixed Oxides

    3.4 Improvements of Other Characteristics

    3.4.1 Reactivation

    3.4.2 Attrition Resistance

    3.4.3 Influence of Sulfur Compounds

    3.5 Conclusion

    List of Symbols

    References

    Chapter 4 Alkaline Ceramics-based High-temperature CO2 Sorbents

    Elizabeth Vera, Hugo A. Lara-García and Heriberto Pfeiffer

    4.1 Introduction

    4.2 Alkaline Ceramics for CO2 Capture

    4.2.1 Lithium and Sodium Zirconates

    4.2.2 Lithium and Sodium Silicates

    4.2.3 Lithium Aluminates

    4.2.4 Lithium Cuprate

    4.2.5 Lithium Ferrites

    4.2.6 Lithium and Sodium Titanates

    4.2.7 Lithium and Sodium Cobaltates

    4.3 Alkaline Ceramics for CO2 Conversion Reactions

    4.3.1 CO Oxidation–Chemisorption

    4.3.2 Methane Reforming Processes

    4.4 Conclusions

    Acknowledgements

    References

    Chapter 5 System and Processes of Pre-combustion Carbon Dioxide Capture and Separation

    Xuancan Zhu, Yixiang Shi, Shuang Li, Ningsheng Cai and Edward J. Anthony

    5.1 Introduction

    5.1.1 Background

    5.1.2 Research Status

    5.1.3 Overview of the Chapter

    5.2 Development of the Adsorption Kinetic Model

    5.2.1 Introduction of CO2 Adsorbents

    5.2.2 Adsorption Mechanism of Potassium-promoted MgAlCO3-LDO

    5.2.3 Non-equilibrium Kinetic Model

    5.2.4 High-pressure Adsorption Kinetic Model

    5.2.5 Synthesis and Characterization of New Adsorbents

    5.3 Design of Adsorption–Desorption Reactor and Process

    5.3.1 High-pressure CO2 Adsorption Test by Fixed Bed

    5.3.2 CO2 Adsorption Test by Double Fixed Bed

    5.3.3 Modeling of Adsorption Column

    5.3.4 Modeling and Optimization of PSA Process

    5.3.5 Purification of Trace Amount of CO in H2-rich Gas

    5.4 System Integration and Operation of an Elevated-temperature CO2 Capture Pilot Plant

    5.4.1 Introduction of the Pilot Plant System

    5.4.2 Results Obtained by Varying Duty Operating Conditions

    5.4.3 Continuous Operation Results and System Stability Analysis

    5.4.4 CO2 Capture Energy Consumption Analysis

    Nomenclature

    Acknowledgements

    References

    Subject Index

    Preface

    Carbon dioxide (CO2) is one of the major greenhouse gases that contribute to global warming and anthropogenic climate change. Unfortunately, it is predicted that the atmospheric CO2 concentration will continue to increase in the next several decades because fossil fuels will still be the dominant energy source. In recent years, worldwide effort has been made to reduce CO2 emissions, among which capturing using solid adsorbents/sorbents has attracted intense attention from both academia and industry. I have been working on CO2 capture materials since 2009, and have witnessed nearly one-thousand papers per year being published in this field. With this rapid development, I believe that it was necessary to edit a book to summarize all the important progresses made with each type of CO2 capture material. Professor Dermot O'Hare, University of Oxford suggested that this could be part of the Royal Society of Chemistry's Inorganic Materials Series. He suggested two books entitled Pre-combustion Carbon Dioxide Capture Materials and Post-combustion Carbon Dioxide Capture Materials. I am confident that these works will benefit advanced undergraduates, postgraduates and researchers working in both academia and industry on this topic.

    This book is organized into five chapters and focuses on the intermediate- and high-temperature CO2 sorbents used in the pre-combustion CO2 capture processes, e.g., the sorption enhanced water gas shift (SEWGD) process, the sorption enhanced biomass reforming (SEBR) process, and the sorption enhanced steam reforming (SESR) process, etc. This book aims to present the full picture of various pre-combustion CO2 capture materials including layered double hydroxides-derived mixed metal oxides, MgO, CaO, and alkali/alkaline ceramics. The discussion of each type of sorbent starts with the fundamental mechanism for CO2 capture, followed by the preparation and modification of materials, and their capture capacity, kinetics, and recycling stability, etc. In the fifth chapter, we present research progress in the system and processes of pre-combustion CO2 capture and separation.

    The editor thanks all the contributors to this book, particularly Professor Dermot O'Hare (University of Oxford, UK), Associate Professor Luyi Sun (University of Connecticut, USA), Assistant Professor Claire Courson (University of Strasbourg, France), Professor Katia Gallucci (University of L'Aquila, Italy), Professor Heriberto Pfeiffer (Universidad Nacional Autónoma de México, México), Associate Professor Yixiang Shi and Professor Ningsheng Cai (Tsinghua University, China), Professor Ben Anthony (Cranfield University, UK) and all the students and researchers involved in each chapter.

    Also, I would like to express my special acknowledgement to Professor Duncan Bruce (University of York, UK), Professor Dermot O'Hare (University of Oxford, UK), and Professor Richard Walton (University of Warwick, UK), who accepted and supported this project, and to Connor Sheppard, Leanne Marle, Sylvia Pegg, and Robin Driscoll for all their support during the editing of this book. Finally, I thank the Royal Society of Chemistry for supporting this edition.

    Qiang Wang

    CHAPTER 1

    Layered Double Hydroxides-derived Intermediate-temperature CO2 Adsorbents

    Junya Wanga,b, Yu Zhangb, Naveed Altafb, Dermot O'Harec, Qiang Wang*b

    aFaculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, 650500, Yunnan, P. R. China

    bCollege of Environmental Science and Engineering, Beijing Forestry University, 35 Qinghua East Road, Haidian District, Beijing 100083, P. R. China

    cChemistry Research Laboratory, Department of Chemistry, University of Oxford, Mansfield Road, Oxford OX1 3TA, UK

    *E-mail: qiangwang@bjfu.edu.cn; qiang.wang.ox@gmail.com

    1.1 Introduction

    Carbon dioxide (CO2) is a major greenhouse gas that has triggered global warming and climate change.¹–³ Over the past two centuries, its concentration in the atmosphere has rapidly increased, mainly because of human activities such as fossil fuel burning.⁴–⁹ However, it is predicted that this trend of increasing atmospheric CO2 concentration with not be altered within the next several decades, because fossil fuels will still be the dominant energy source. Moreover, the energy demand will increase further by 53% by 2030.¹⁰ So development of technologies for CO2 capture and storage will become increasingly important.¹¹

    Concerns about the increasing concentration of greenhouse gases in the atmosphere have stimulated the study of CO2 capture by using solid adsorbents.¹²,¹³ LDHs-derived mixed oxides are considered to be one of the most promising adsorbents for CO2 capture at an intermediate-temperature range (200–400 °C), which require less energy in regeneration and show superior multicycle stability.¹⁴,¹⁵ In addition, they show fast adsorption/desorption kinetics and good performance in the presence of water,¹⁶–¹⁸ making them very attractive not only for pre-combustion CO2 capture but also for applications involving CO2 equilibria such as sorption enhanced water gas shift (SEWGS) and sorption enhanced steam reforming (SESR).¹⁹–²²

    LDHs, also known as hydrotalcite-like compounds or anionic clay, are composed of stacked positively-charged brucite-like layers with interlayer spaces containing charge-compensating anions and water molecules. The metal cations occupy the centers of octahedra whose vertexes contain hydroxide ions. The octahedra are connected by edge sharing to form an infinite sheet.²³ It has the composition [M1−x²+Mx³+(OH)2][An−]x/n·ZH2O, where M²+ and M³+ are divalent and trivalent cations, respectively, and An− is the anion that is intercalated in the interlayer for charge compensation.²⁴–²⁸ The general structure of LDHs is shown in Figure 1.1. Because the chemical composition of both the inorganic layers and the interlayer gallery anions can be precisely controlled, LDHs possess highly tunable properties and potentially can be used in a wide range of applications, such as for catalysts, fire retardant additives, polymer–LDH nanocomposites, CO2 capture, luminescent materials, and magnetic materials.²⁹–³⁵ LDHs have been investigated for decades as adsorbents as well.³⁶–³⁸ Owing to their high surface area and abundant basic sites at the surface, LDHs are considered to be favorable for adsorbing acidic CO2.¹⁰,³⁹ Fresh LDHs themselves do not possess any basic sites. However, upon thermal treatment, a LDH gradually loses interlayer water; with the temperature increasing, it dehydroxylates and decarbonates to a large extent, leading to the formation of a mixed oxide with a 3D network, with a larger surface area and good stability at high temperature.¹⁸,⁴⁰ Therefore, LDHs are significantly more active for CO2 removal after thermal decomposition, being transformed into basic mixed oxides (LDOs).¹¹

    Figure 1.1 Schematic structure of LDHs. In this diagram, M ²+ and M ³+ represent di- and tri-valent cations, which, with the –OH molecules, form the layered structure of the LDHs. The interlayer spacing is occupied with charge-compensating anions (A n − ) and water molecules. Reproduced from Adsorption , High temperature adsorption of CO 2 on various hydrotalcite-like compounds, 14 , 2008, 781–789, N. D. Hutson and B. C. Attwood, © Springer Science + Business Media, LLC 2008, with permission of Springer.

    Starting from the natural mineral (MgAl–CO3), a lot of work has been done on LDHs-derived CO2 adsorbents, which includes (1) influence of the chemical composition of LDHs, (2) influence of the synthetic conditions and method, (3) LDH-based composites, (4) influence of doping alkali metals, (5) influence of other co-existing gases, (6) adsorption mechanism and kinetics study, and (7) techno-economic assessment etc. Although several recent review papers have provided prolific insights into the progress in this area, most previous reviews have only discussed LDHs-derived CO2 adsorbents as a part of the papers. A detailed review focusing only on LDHs-derived compounds as CO2 adsorbents, addressing their pros and cons, and potential applications in industry is still needed.

    In this regard, the objective of this chapter is to review the currently available literature on adsorption of CO2 on LDHs-derived compounds, focusing on the aforementioned seven parts. In addition, based on the overview, the closing section will suggest future research efforts.

    1.2 Influence of the Chemical Composition of LDHs

    As mentioned in the introduction, LDHs are composed of stacked positively-charged brucite-like layers with interlayer spaces containing charge-compensating anions and water molecules.⁴¹,⁴² They are also very open to physicochemical manipulation, numerous combinations of structural cations (Mg²+, Co²+, Cu²+, Ca²+, Fe³+, Al³+ etc.) and interlayer charge-compensating anions (Cl−, NO3−, CO3²−, HCO3−, SO4²− etc.).⁴³ With a proper understanding of their composition–structure–property relationships, LDHs may conceivably be synthesized and tailored as effective high temperature adsorbents for CO2 separation and capture. Plenty of work has been done to study how substitution of cations and interlayer charge-compensating anions affects the CO2 adsorptive capacity of LDHs.⁴³,⁴⁴ Yong et al.⁴⁵ first investigated the effect of Al content in commercial LDHs on their CO2 capture capacity. The adsorption capacities of three kinds of commercial LDHs from CONDEA Chemie Gmbh company (PURAL MG30 (70% Al2O3), MG50 (50% Al2O3), and MG70 (30% Al2O3)) with different aluminium contents were tested at 300 °C and 1 bar. The results showed that the amounts of adsorbed CO2 increased with a decrease of aluminium content from 70% (MG30) to 50% (MG50). However, the amount of adsorbed CO2 on MG50 is slightly higher than that on MG70 although MG50 has a higher aluminium content. The reason given was that incorporated aluminium has two functions: (1) the density of the layer charge in LDHs increases with increasing aluminium content, which is favorable for the adsorption of CO2, (2) increasing the aluminium content leads to a decrease in the interlayer spacing of LDHs and a reduction in the number of high-strength CO2 adsorption sites in the LDHs. Later, Wang et al.⁴⁶ synthesized various XnY3−nAl-LDHs by a constant pH co-precipitation method with the (X²+ + Y²+)/Al³+ molar fixed at 3.0. Besides the CO2 capture capacity of different LDHs, the structural effects of cations on LDHs and derived oxides, the thermal decomposition behaviors of LDHs precursors, as well as the modeling of CO2 adsorption on mixed oxides have also been studied. The results revealed that the precursors MgAl–CO3 and CoAl–CO3 LDHs exhibit the typical X-ray diffractogram of LDHs, and slight differences were observed for samples CoMgAl–CO3 and CaCoAl–CO3 LDHs compared with MgAl–CO3 and CoAl–CO3 LDHs with the corresponding diffraction peaks being weaker, as well as the fact that MgCaAl–CO3 LDHs contains an impure phase CaCO3. However, after calcination, the precursor LDHs were decomposed, leading to various oxide derivatives e.g. MgAlO and MgCaAlO etc. The group found that the introduction of Co into LDHs promotes the formation of a spinel phase after calcination at 550 °C. The thermal decomposition behaviors of LDH precursors were tested during heating in air. Then, it was concluded that the thermogravimetric loss during heating involves two or three steps. The first stage occurs at 50–200 °C, mainly ascribed to the loss of surface-adsorbed and interlayer water molecules. Subsequently, the second stage takes place at 200–500 °C, including the dehydroxylation of layer hydroxyl groups and decomposition of interlayer carbonate, causing a collapse of the layer structure. The second stage for MgAl–CO3 LDHs occurs at 441 °C. When Co partially or fully replaces the Mg in LDHs, this stage takes place at much lower temperatures (337 and 247 °C for CoMgAl–CO3 LDHs and CoAl–CO3 LDHs, respectively). In contrast, the replacement of partial or all Mg with Ca leads to one more event at a much higher temperature. Furthermore, the CO2 capture capacity of the various LDHs-derived adsorbents were tested. The results showed that the CaCoAl system has the highest CO2 adsorption capability, which can reach 1.39 mmol g−1 of CO2 (i.e., 6.12 wt%) from a gas mixture (8% CO2 in N2) at 350 °C and 1 bar in a fixed-bed reactor within 20 min. Commonly, it is considered that CO2 adsorption on these oxides is more likely a chemisorption, which involves a number of steps, such as CO2 diffusing into the surface and pores, reacting with the active sites, and forming a product layer on the surface in the carbonate form. With the adsorption going on, it becomes more difficult for CO2 to diffuse into the inner pores/surface or penetrate the product layer to be adsorbed. The adsorbent is gradually deactivated. Therefore, the deactivated models have also been used in their study. The result showed that for all adsorbents except for CaCoAlO, both the initial adsorption rate constant (k0) and the deactivation rate constant (kd) are quite similar, with the average values of k0 and kd being 165 cm³ min g−1 and 0.57 min−1, respectively. However, the constant kd of CaCoAlO (212 cm³ min g−1) is much larger than the average (165 cm³ min g−1), which is consistent with its highest adsorption capacity for CO2.

    Moreover, Lwin et al.⁴⁷ studied the CuAl system for CO2 capture and tested the influence of the Cu–Al molar ratio, the influence of the adsorption temperature, as well as the adsorption kinetics. They synthesized CuAl–CO3 LDHs with a Cu–Al molar ratio between 1 and 3. The physically adsorbed moisture, intercalated water, bonded hydroxyls, and intercalated CO2 of LDHs were removed by thermal decomposition with heating to 600 °C, before the samples were subjected to CO2 flow. It was noticed that the adsorption capacities are high at low temperatures (100–400 °C) and decrease as the temperature increases. And the adsorption capacities are in the order Cu1Al1 > Cu2Al1 > Cu3Al1, with similar adsorption capacities for Cu1Al1 and Cu2Al1. However, above 400 °C, the adsorption capacity of Cu2Al1 slightly exceeds that of Cu1Al1. Thus, the optimum Cu–Al molar ratio for maximum adsorption capacity probably lies between 1 and 2. Moreover, the initial rates of adsorption on the fresh adsorbents at 600 °C were also calculated, which showed that the initial specific adsorption rate of Cu2Al1 is significantly higher than those of the other two. As per the result of the specific rates of CO2 adsorption on the fresh Cu2Al1 adsorbent at different temperatures, it can be seen that at low temperatures (<400 °C), the rate of adsorption only steadily increases with temperature. However, above 400 °C, the adsorption rate increases rapidly with temperature. Furthermore, through the calculating of activation energy values, they suggested that the physical adsorption dominates at low temperatures (<400 °C) and the chemisorption dominates at high temperatures (400 °C).

    Later on, the influence of trivalent cations of LDHs on CO2 capture was systematically investigated by Wang et al.⁴⁸ Four kinds of trivalent cations were investigated, which include Al, Fe, Ga, and Mn in the Mg-M-CO3 LDHs (M is the trivalent cation). They first examined the structural evolution of the four synthesized LDHs by thermal treatment. The results indicated that the dehydration and the dehydroxylation/decarbonation properties are highly dependent on the type of trivalent cation. The first stage (30–190 °C), which corresponds to the desorption of water, follows the order Mg3Al1 > Mg3Fe1 > Mg3Ga1 > Mg3Mn1. This suggests that the interlayer water has the highest stability in Mg3Al1, while it is the least stable in Mg3Mn1. However, at the second stage (200–500 °C), it showed a different order, which suggested that the dehydroxylation and decarbonation follows the order Mg3Al1 > Mg3Ga1 > Mg3Fe1 > Mg3Mn1. To get a deeper insight into the structure evolution of LDHs, the calcined samples were characterized by XRD analyses. The structural evolution for all LDHs also showed two stages. During the first stage, LDH structures gradually decomposed and transformed into amorphous phases, showing a decrease of basal spacing as the temperature was elevated. The upward shift of the d003 peak is mainly caused by desorption of interlayer H2O, leading to a shrinkage of the LDH layers. The temperature at which the LDH structure just disappeared was defined as Tct. Tct followed the order Mg3Al1 (400 °C) > Mg3Ga1 (300 °C) ≈ Mg3Fe1 (300 °C) > Mg3Mn1 (250 °C). In the second stage, the amorphous phase was gradually transformed into periclase MgO and spinel oxides. With increasing temperature, the two peaks of MgO gradually appeared in all four samples. They found that the two peaks became narrower at high temperatures for Mg3Al1 and Mg3Ga1, without the formation of any spinel oxides up to 700 °C. However, for Mg3Fe1 and Mg3Mn1, although there was only one phase at 400 °C (periclase MgO), a further increase of temperature led to the formation of MgFe2O4 for Mg3Fe1 and Mg2MnO4 for Mg3Mn1. Therefore, it can be concluded that the tendency of converting periclase MgO into spinel oxides follows the order of Mg3Mn1 > Mg3Fe1 > Mg3Ga1 > Mg3Al1. Because of the different thermal stabilities of each Mg-M-CO3 LDH, the calcination temperature effect on CO2 capture capacities was studied. CO2 adsorption experiments were performed by exposing the calcined LDHs to pure CO2, at 1 bar and 200 °C for 2 h. The optimal calcination temperature (Toc) is different for each LDH as shown in Figure 1.2. It indicates that the optimal calcination temperature is different for each LDH, following the order Mg3Al1 (400 °C) > Mg3Ga1 (350 °C) > Mg3Fe1 (300 °C) > Mg3Mn1 (250 °C). This phenomenon can be explained by the difference in their thermal stabilities. When the calcination temperature is too low, the LDH structures are not completely decomposed; when the calcination temperature is too high, MgO or even spinel oxides are formed. Also, the Toc value of each LDH was very close to the Tct, implying that the quasi-amorphous phases obtained by heating at the lowest temperature (Tct) have the highest CO2 capture capacities. Furthermore, the maximum CO2 capture capacity of each LDH was Mg3Al1 (0.41 mmol g−1), Mg3Fe1 (0.46 mmol g−1), Mg3Mn1 (0.42 mmol g−1), and Mg3Ga1 (0.27 mmol g−1). It is verified that calcination temperature is critical for each LDH. A very different calcination temperature is needed for each LDH to get the maximum CO2 capture capacity. Then, the effect of the adsorption temperature on CO2 capture capacity was further measured, as shown in Figure 1.3. It can be seen that low temperatures favor CO2 adsorption and the maximum CO2 capture took place at 200 °C for all LDHs. In Figure 1.3, it is clearly shown that the CO2 capture capacities decrease with an increase of adsorption temperature when the calcination temperature is not too high. However, the CO2 capture capacities increase with increasing adsorption temperature when the calcination temperature is sufficiently high (i.e., 550 °C for Mg3Ga1 and Mg3Fe1, and 400 °C for Mg3Mn1). This phenomenon is again related to the thermal stabilities. Keeping in mind the above, low-temperature calcination of LDHs leads to amorphous phases, on which the CO2 is mainly adsorbed physically. The adsorption strength is weak and, therefore, only a small amount of CO2 can be adsorbed at a high temperature, while samples calcined at a high temperature were already transformed into the MgO phase and chemical adsorption of CO2 takes place mainly. Therefore, all of the above have shown that trivalent cations in LDH can influence their CO2 capture capacity, which actually determines the structure evolution of LDH derivatives under thermal treatment.

    Figure 1.2 CO 2 capture capacities of Mg 3 Al 1 , Mg 3 Fe 1 , Mg 3 Ga 1 , and Mg 3 Mn 1 as a function of calcination temperatures. Reproduced from ref. 48 with permission from John Wiley and Sons, © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

    Figure 1.3 CO 2 adsorption temperature effect on (a) Mg 3 Al 1 , (b) Mg 3 Ga 1 , (c) Mg 3 Fe 1 , and (d) Mg 3 Mn 1 . Reproduced from ref. 48 with permission from John Wiley and Sons, © 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

    Subsequently, Huang et al.³⁴ first reported an investigation into the performance of LiAl2 LDHs intercalated with various anions, including CO3²−, NO3−, or Cl−, for CO2 capture. Both co-precipitation and gibbsite intercalation methods were used for the synthesis of LiAl2 LDHs in their study. The results of XRD validated that only the Li1Al2–CO3 LDH synthesized by the co-precipitation method was a pure LDH phase without any impurities. The other ones synthesized by the co-precipitation method showed the existence of a bayerite impurity, and all the LDHs synthesized by the gibbsite intercalation method showed the existence of gibbsite. Then, the effect of interlayer anions on the CO2 capture capacity of LiAl2 LDHs-derived adsorbents was examined. The CO2 capture capacity of LiAl2 LDHs synthesized by the co-precipitation method was in the order of LiAl2–CO3 (0.44–0.51 mmol g−1) > LiAl2–NO3 (0.16 mmol g−1) = LiAl2–Cl (0.16 mmol g−1). While for the LDHs synthesized by gibbsite intercalation, the CO2 capture capacity was 0.45, 0.41, and 0.30 mmol g−1 for calcined LiAl2–CO3, LiAl2–NO3, and LiAl2–Cl, respectively. It can be seen that the co-precipitation method resulted in a slightly higher performance for CO2 capture than the gibbsite intercalation method for LiAl2–CO3 LDHs.

    Besides the effects of interlayer anions and the synthesis method, the effect of the Li–Al molar ratio in the preparation solution was also investigated. LiAl2–CO3 was synthesized by the co-precipitation method with the Li–Al ratio from 1 : 3 in the preparation solution. The LiAl2–CO3 LDH synthesized with a preparation Li–Al ratio of 3 : 1 showed the highest CO2 capture capacity of 0.51 (mmol g−1), which is comparable to the most commonly used Mg3Al–CO3 LDH (0.50 mmol g−1). Moreover, the results in their study also indicated that LiAl2 LDHs-derived compounds can be used as CO2 adsorbents over a wide temperature range (60–400 °C), with a CO2 capture capacity of 0.94 and 0.51 mmol g−1 at 60 and 200 °C, respectively. Different cations in LDHs and their CO2 capture performance are recapitulated in Table 1.1.

    Table 1.1 Summary of LDHs with different cations and their performances in CO 2 capture

    In addition, the influence of charge-compensating anions in LDHs on CO2 capture capacity was also investigated. Yong et al.⁴⁵ profoundly studied the effect of anion type on the CO2 capture capacity of commercial LDHs (EXM696, EXM701, and EXM911 were provided by Süd-Chemie AG Company). In their study, they found that the amounts of adsorbed CO2 on LDHs containing CO3²− (EXM samples) were higher than those on LDHs containing OH− (MG samples). The main reasons for this are that (1) the carbonate ion CO3²− is larger than the hydroxide ion OH−, having a larger interlayer spacing (0.765 nm) compared with that of OH− (0.755 nm), and (2) the charge of the CO3²− is higher than that of the OH−. Then, the effect of the adsorption temperature of LDHs was also discussed. Two LDHs were used in their study to capture CO2 at room temperature (20 °C) and higher temperatures (200 and 300 °C), respectively. The results showed that the capture capacities at the three temperatures of both LDHs follow the order Q(300 °C) > Q(20 °C) > Q(200 °C). Furthermore, the decarbonation behaviors of LDHs at various temperatures were also discussed. When heated to 200 °C, LDHs become dehydrated, and the product retains a layered structure. A significant rearrangement of the octahedral brucite-type layer occurs with the migration of the M³+ cation out of the layer to tetrahedral sites in the interlayer, and the d spacings decrease progressively with increasing temperature. Because of the decrease in the d spacings, the LDHs have less void space in their interlayers and can accommodate less carbon dioxide gas. Meanwhile, the amounts of adsorbed CO2 on the surface of LDHs decrease with increasing temperature. In particular, the low-strength basic sites (bicarbonate) disappeared above 100 °C. Therefore, the adsorption capacities of LDHs at 200 °C are lower than those at 20 °C. At temperatures above 300 °C, the above unfavorable mechanism for CO2 adsorption is still present. However, the dehydroxylation between OH groups of contiguous layers and the decarbonation processes occur above 300 °C. The former produces a structure modification of the layers consisting of a change in the M³+ cation environment from an octahedral to tetrahedral coordination. The latter removes the carbonate anion as CO2 from the LDHs, which could partially destroy the layers, and increase the surface area and pore volume of the products. The evolution of the LDHs' structure described above is illustrated in Figure 1.4. The heat treatment process of the LDHs has two functions. One is micropore formation with the decomposition of the LDHs, which is intended to favor CO2 adsorption. The other has the opposite effect, such as causing the d spacings and the amounts of adsorbed CO2 on the surfaces of the LDHs to decrease with increasing temperature. Subsequently, Hutson et al.⁴³ investigated the effect of divalent cations and interlayer charge-compensating anions on the CO2 adsorption capacity of LDHs. They found that the MgAl–CO3 sample showed the highest initial adsorption rate and the highest CO2 adsorption capacity of 0.62 mmol g−1 at the end of time interval. MgAl–Fe(CN)6 had an initial adsorption rate close to that of MgAl–CO3 but had a lower total adsorption capacity than CaAl–CO3 at the end of the experiment. And MgAl–ClO4 had the lowest adsorption rate and total adsorption capacity of 0.11 mmol g−1, despite having the largest interlayer spacing and second largest average pore diameter. They also proved that the dominant means of physical adsorption involves interaction of CO2 with basic sites created by the decomposition of the LDH structure. There appears to be no relationship between the surface basicity and the chemisorption capacity. The irreversible chemisorption appears to be a carbonation/mineralization of the M²+ cations.

    Figure 1.4 Structure models for products in the different stages of calcination of LDHs: (a) the starting LDHs, (b) the dehydrated intermediate, and (c) the decomposed materials. Reprinted with permission from Z. Yong, V. Mata and A. E. Rodrigues, Ind. Eng. Chem. Res. , 2001, 40 , 204, Copyright 2001 American Chemical Society. ⁴⁵

    Moreover, Wang et al.⁴⁹ reported a detailed investigation into how charge-compensating anions and synthesis pH affect the structural properties and CO2 adsorption capacity of MgAl LDHs. A series of Mg3Al1-A (A = CO3²−, NO3−, Cl−, SO4²−, and HCO3−) LDHs were synthesized and investigated as CO2 adsorbents. The influence of the synthesis pH on the chemical composition and CO2 adsorption capacity of Mg3Al1–CO3 was also studied. Among various LDHs, Mg3Al1–CO3 showed the highest CO2 capture capacity (0.53 mmol g−1), which was much higher than other LDHs with HCO3−, NO3−, SO4²−, and Cl− anions (∼0.2 mmol g−1). The results indicated that the BET surface area of calcined LDHs seems be the main parameter that determines the CO2 adsorption capacity. Because the surface area of calcined Mg3Al1–CO3 (239 m² g−1) was much higher than the other calcined LDHs (<140 m² g−1), Mg3Al1–CO3 derivative was supposed to provide more adsorption sites for CO2. Besides, they considered that the morphology of the synthesized LDHs might also affect CO2 adsorption. The Mg3Al1–CO3 formed a spheroidal sand rose morphology. The size of the flower ball was approximately 400–450 nm, and the thickness of the petals was about 24–25 nm, which accounted for about 30–32 brucite-like sheets. However, all other LDHs formed a stone-like morphology, with particle sizes ranging from several to several-tenths of micrometers. The abundance of sand rose-like LDHs possesses an abundance of pores between petals, and thus favors CO2 diffusion as well as adsorption. However, stone-like LDHs were very big in size and were non-porous. Moreover, they proved that the anions have a great effect on the thermal stability, morphology, as well as the surface area of LDHs; they have a significant influence on the CO2 adsorption capacity of calcined LDHs. Furthermore, Mg3Al1–CO3 was studied using various synthesis pH values from 6.5 to 14. The finding was that the Mg–Al molar ratio increased from 0.5 to 3.1 with an increase in pH from 6.5 to 10. A further increase in pH up to 14 has little effect on the Mg–Al molar ratio. The BET surface area and pore size distribution were also influenced by synthesis pH. The average pore size increased with increasing pH values. Mg3Al1–CO3 synthesized at pH 10–12 showed the best performance for CO2 capture at high temperature. Therefore, it can be inferred that the anions affect the thermal stability and morphology, as well as the surface area of LDHs, consequently influencing the CO2 capture capacity.

    Wang et al.⁵⁰ first synthesized LDHs intercalated with long-carbon-chain organic anions (e.g. stearate) for CO2 capture. Compared with traditional LDHs, stearate-intercalated LDHs have a higher CO2 capture capacity, which can be meliorated to 1.25 mmol g−1. It is 2.5 times higher than that of traditional LDH-based adsorbents (0.5 mmol g−1). In order to know the reason, the XRD patterns of Mg3Al1–CO3 and Mg3Al1-stearate were compared (see Figure 1.5(a)). It can be seen that the characteristic diffraction peaks of LDHs were observed for both samples. By replacing CO3²− with C17H35COO− anions, the 003 peak shifted to a much lower value, from 11.3° for Mg3Al1–CO3 to 2.4° for Mg3Al1-stearate. This means that the interlayer distance increased from 0.78 nm for Mg3Al1–CO3 to 3.54 nm for Mg3Al1-stearate. After being thermally treated at 400 °C, both Mg3Al1–CO3 and Mg3Al1-stearate LDHs were transformed into amorphous mixed oxides (MgAlOx), with the features of periclase MgO (see Figure 1.5(a)). For Mg3Al1-stearate, the characteristic peaks of periclase MgO are broader and the intensities are much weaker than those derived from Mg3Al1–CO3. This suggests that the decomposition of C17H35COO− anions could result in a much lower degree of crystallinity and smaller particle size of MgAlOx. They also compared the thermal stabilities of the Mg3Al1–CO3 and Mg3Al1-stearate LDH (see Figure 1.5(b)). Figure 1.5(b) illustrates that both LDHs show a typical two-stage weight loss. At 700 °C, the weight loss of Mg3Al1-stearate is ca. 79.8 wt%, which is much higher than that of Mg3Al1–CO3 (43.2 wt%) because the molecular weight of C17H35COO− is much higher than that of CO3²−. Therefore, it is believed that the improved CO2 capture capacity is due to the following reasons: (1) the decomposition of long-carbon-chain anions leads to cracks and splits in the LDH plates and creates more surface basicity (O2−) sites; (2) the mixed metal oxide mixture produced has a lower degree of crystallinity; and (3) the quasi-amorphous structure formed is more stable than that from Mg3Al1–CO3. The schematic illustration of the structural changes and the CO2 capture by Mg3Al1–CO3 and Mg3Al1-stearate is shown in Figure 1.6.

    Figure 1.5 (a) XRD patterns of fresh and calcined Mg 3 Al 1 –CO 3 LDH and Mg 3 Al 1 -stearate LDH; (●) periclase MgO, (b) TGA analysis of Mg 3 Al 1 –CO 3 LDH and Mg 3 Al 1 -stearate LDH. Reproduced from ref. 50 with permission from the Royal Society of Chemistry.

    Figure 1.6 (a) The general schemes of the structural changes of Mg 3 Al 1 –CO 3 LDH and Mg 3 Al 1 -stearate LDH into amorphous mixed oxides. And (b) the comparison of the CO 2 capture capacities of Mg 3 Al 1 –CO 3 LDH and Mg 3 Al 1 -stearate LDH derived CO 2 adsorbents. Adapted from ref. 50 with permission from the Royal Society of Chemistry.

    Later on, Qin et al.⁵¹ devised a systematic investigation on the promoting effect of the carbon chain length of the intercalated carboxylic anions for the CO2 capture performance of MgA-organo LDHs. A series of organo-LDHs were successfully synthesized. Since the thermal stabilities of odd-carbon-chain monocarboxylic acids are relatively poor, only

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