Hydrogen Production Technologies E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Wissenschaft und neue Technologien
- Serie: Advances in Hydrogen Production and Storage (AHPS)
- Sprache: Englisch
Provides a comprehensive practical review of the new technologies used to obtain hydrogen more efficiently via catalytic, electrochemical, bio- and photohydrogen production. Hydrogen has been gaining more attention in both transportation and stationary power applications. Fuel cell-powered cars are on the roads and the automotive industry is demanding feasible and efficient technologies to produce hydrogen. The principles and methods described herein lead to reasonable mitigation of the great majority of problems associated with hydrogen production technologies. The chapters in this book are written by distinguished authors who have extensive experience in their fields, and readers will have a chance to compare the fundamental production techniques and learn about the pros and cons of these technologies. The book is organized into three parts. Part I shows the catalytic and electrochemical principles involved in hydrogen production technologies. Part II addresses hydrogen production from electrochemically active bacteria (EAB) by decomposing organic compound into hydrogen in microbial electrolysis cells (MECs). The final part of the book is concerned with photohydrogen generation. Recent developments in the area of semiconductor-based nanomaterials, specifically semiconductor oxides, nitrides and metal free semiconductor-based nanomaterials for photocatalytic hydrogen production are extensively discussed.
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Contents
Cover
Title page
Copyright page
Preface
Part 1: Catalytic and Electrochemical Hydrogen Production
Chapter 1: Hydrogen Production from Oxygenated Hydrocarbons: Review of Catalyst Development, Reaction Mechanism and Reactor Modeling
1.1 Introduction
1.2 Catalyst Development for the Steam Reforming Process
1.3 Kinetics and Reaction Mechanism for Steam Reforming of Oxygenated Hydrocarbons
1.4 Reactor Modeling and Simulation in Steam Reforming of Oxygenated Hydrocarbons
References
Chapter 2: Ammonia Decomposition for Decentralized Hydrogen Production in Microchannel Reactors: Experiments and CFD Simulations
2.1 Introduction
2.2 Ammonia Decomposition for Hydrogen Production
2.3 Ammonia-Fueled Microchannel Reactors for Hydrogen Production: Experiments
2.4 CFD Simulation of Hydrogen Production in Ammonia-Fueled Microchannel Reactors
2.5 Summary
Acknowledgments
References
Chapter 3: Hydrogen Production with Membrane Systems
3.1 Introduction
3.2 Pd-Based Membranes
3.3 Fuel Reforming in Membrane Reactors for Hydrogen Production
3.4 Thermodynamic and Economic Analysis of Fluidized Bed Membrane Reactors for Methane Reforming
3.5 Conclusions
Acknowledgments
References
Chapter 4: Catalytic Hydrogen Production from Bioethanol
4.1 Introduction
4.2 Production Technology Overview
4.3 Catalyst Overview
4.4 Catalyst Optimization Strategies
4.5 Reaction Mechanism and Kinetic Studies
4.6 Computational Approaches
4.7 Economic Considerations
4.8 Future Development Directions
Acknowledgment
References
Chapter 5: Hydrogen Generation from the Hydrolysis of Ammonia Borane Using Transition Metal Nanoparticles as Catalyst
5.1 Introduction
5.2 Transition Metal Nanoparticles in Catalysis
5.3 Preparation, Stabilization and Characterization of Metal Nanoparticles
5.4 Transition Metal Nanoparticles in Hydrogen Generation from the Hydrolysis of Ammonia Borane
5.5 Durability of Catalysts in Hydrolysis of Ammonia Borane
5.6 Conclusion
References
Chapter 6: Hydrogen Production by Water Electrolysis
6.1 Historical Aspects of Water Electrolysis
6.2 Fundamentals of Electrolysis
6.3 Modern Status of Electrolysis
6.4 Perspectives of Hydrogen Production by Electrolysis
Acknowledgment
References
Chapter 7: Electrochemical Hydrogen Production from SO
2
and Water in a SDE Electrolyzer
7.1 Introduction
7.2 Membrane Characterization
7.3 MEA Characterization
7.4 Effect of Anode Impurities
7.5 High Temperature SO
2
Electrolysis
7.6 Conclusion
References
Part 2: Bio Hydrogen Production
Chapter 8: Biomass Fast Pyrolysis for Hydrogen Production from Bio-Oil
8.1 Introduction
8.2 Biomass Pyrolysis to Produce Bio-Oils
8.3 Bio–Oil Reforming Processes
8.4 Future Prospects
References
Chapter 9: Production of a Clean Hydrogen-Rich Gas by the Staged Gasification of Biomass and Plastic Waste
9.1 Introduction
9.2 Chemistry of Gasification
9.3 Tar Cracking and H
2
Production
9.4 Staged Gasification
9.5 Experimental Results and Discussion
9.6 Conclusions
References
Chapter 10: Enhancement of Bio-Hydrogen Production Technologies by Sulphate-Reducing Bacteria
10.1 Introduction
10.2 Sulphate-Reducing Bacteria for H
2
Production
10.3 Mathematical Modeling of the SR Fermentation
10.4 Bifurcation Analysis
10.5 Process Control Strategies
10.6 Conclusions
Acknowledgment
Nomenclature
References
Chapter 11: Microbial Electrolysis Cells (MECs) as Innovative Technology for Sustainable Hydrogen Production: Fundamentals and Perspective Applications
11.1 Introduction
11.2 Principles of MEC for Hydrogen Production
11.3 Thermodynamics of MEC
11.4 Factors Influencing the Performance of MECs
11.5 Current Application of MECs
11.6 Conclusions and Prospective Application of MECs
Acknowledgments
References
Chapter 12: Algae to Hydrogen: Novel Energy-Efficient Co-Production of Hydrogen and Power
12.1 Introduction
12.2 Algae Potential and Characteristics
12.3 Energy-Efficient Energy Harvesting Technologies
12.4 Pretreatment (Drying)
12.5 Conversion of Algae to Hydrogen-Rich Gases
12.6 Conclusions
References
Part 3: Photo Hydrogen Production
Chapter 13: Semiconductor-Based Nanomaterials for Photocatalytic Hydrogen Generation
13.1 Introduction
13.2 Semiconductor Oxide-Based Nanomaterials for Photocatalytic Hydrogen Generation
13.3 Semiconductor Sulfide-Based Nanomaterials for Photocatalytic Hydrogen Generation
13.4 Metal-Free Semiconductor Nanomaterials for Photocatalytic Hydrogen Generation
13.5 Summary and Prospects
Acknowledgments
References
Chapter 14: Photocatalytic Hydrogen Generation Enabled by Nanostructured TiO2 Materials
14.1 Introduction
14.2 Photocatalytic H
2
Generation
14.3 Main Experimental Parameters in Photocatalytic H
2
Generation Reaction
14.4 Types of TiO
2
Nanostructures
14.5 Conclusions and Outlook
Acknowledgments
References
Chapter 15: Polymeric Carbon Nitride-Based Composites for Visible-Light-Driven Photocatalytic Hydrogen Generation
15.1 Introduction
15.2 General Comments on g-C
3
N
4
and its Basic Properties
15.3 Synthesis of Bulk g-C
3
N
4
15.4 Functionalization of g-C
3
N
4
15.5 Photocatalytic Hydrogen Production Using g-C
3
N
4
15.6 Conclusions
References
Index
End User License Agreement
Guide
Cover
Copyright
Contents
Begin Reading
List of Tables
Chapter 1
Table 1.1
Summery of SRM reaction over various metal-oxide supported catalyst.
Table 1.2
Summary of SRE over noble metal catalysts.
Table 1.3
Summary of SRE over Co-based catalysts.
Table 1.4
Summary of SRE over Ni-based catalysts.
Table 1.5
Summary of SRE over perovskite-based catalysts.
Table 1.6
Promoting of metal supported catalyst using transition metals.
Table 1.7
Summary of bimetallic catalyst systems for SRE process.
Table 1.8
Summary of SRG over Ni-based catalysts.
Chapter 2
Table 2.1
Specific and volumetric energy densities of common fuels and power sources. (Reprinted with permission from [10]; Copyright © 2013 Elsevier)
Table 2.2
Life-cycle costs of hydrogen production for ammonia decomposition and other hydrogen production technologies. (Adapted from [27])
Table 2.3
Best performance and recommended operating conditions for the Ni- and Ru-based microchannel reactors. (Reprinted with permission from [87]; Copyright © 2015 Elsevier)
Table 2.4
Comparison of global performance of microstructured reactors for pure NH3 decomposition. (Reprinted with permission from [87]; Copyright © 2015 Elsevier)
Table 2.5
Summary of governing equations for modeling the free-fluid and porous catalyst computational domains. (Reprinted with permission from [52]; Copyright © 2014 Elsevier)
Chapter 3
Table 3.1
Ceramic layers deposited onto different ceramic and metallic porous supports.
Table 3.2
Permeation data of some conventional supported membranes.
Table 3.3
Set of assumptions used for the simulation of the reactor systems. (Reprinted with permission from [85]; Copyright © 2014 Elsevier)
Table 3.4
Overview of the techno-economical assessment and comparison of the conventional fired tubular reformer with and without carbon capture, MA-CLR and FBMR concepts. (Reprinted with permission from [1]; Copyright © 2016 Elsevier)
Chapter 5
Table 5.1
The turnover frequency (TOF;
mol H
2.
(mol metal)
–1
(min)
–1
) and apparent activation energy (E
a
;
kJ/mol
) values of reported catalysts used in hydrogen generation from the hydrolysis of AB. TOF values were given for the hydrolysis of AB at room temperature.
Table 5.2
Lifetime (TTO) of various catalysts in hydrolysis of ammonia borane at room temperature. The surface area, TOF values and the average particle size of the catalysts are also given for comparison.
Table 5.3
Reusability of the reported catalysts used in hydrogen generation from the hydrolysis of AB at room temperature (TOF values indicate the catalytic activity of the catalysts for the first use).
Table 5.4
Recyclability of the reported catalysts used in hydrogen generation from the hydrolysis of AB at room temperature (ammonia borane was added into the reaction solution without separating the catalyst from the reaction mixture).
Chapter 6
Table 6.1
Thermodynamic voltage
E
(
T
) and electrolysis efficiency at atmospheric pressure and different operating temperatures.
Table 6.2
Comparison of main water electrolysis technologies [13].
Table 6.3
EI-250 type electrolyzer performances.
Table 6.4
Comparison of alkaline and PEM water electrolysis technologies.
Chapter 7
Table 7.1
Summary of proton exchange membranes discussed in this work.
Table 7.2
Summary of values obtained by the electrical equivalent model for N117 at 80 °C [41].
Chapter 8
Table 8.1
Structural compounds and chemical composition of biomass and bio–oils produced.
Table 8.2
Summary of different bio–oil reforming processes.
Chapter 9
Table 9.1
Reaction conditions and results for the two-stage gasification of different feedstocks.
Table 9.2
Effects of type and amount of activated carbon on producer gas composition.
Table 9.3
Effect of temperature on producer gas composition in two-stage gasification.
Table 9.4
Effect of gasifying agent on producer gas composition.
Table 9.5
Comparison of two-stage and three-stage gasifiers.
Table 9.6
NH
3
and H
2
S contents in the producer gases from three-stage gasification.
Chapter 10
Table 10.1
Summary of the values obtained for the tuning of the selected controller applied in the biologic-only hydrogen production system using heuristic criteria from Section 10.5.
Table 10.2
Summary of the values obtained for the tuning of the selected controller applied to the biologic-photochemical hydrogen production system using heuristic criteria from Section 10.5.
Table 10.3
Comparison of the biohydrogen productivities by
Desulfovibrio
bacteria reported in the literature versus the ones obtained by applying enhancement techniques.
Chapter 11
Table 11.1
Electrochemically active bacteria (EAB) used in MECs.
Table 11.2
Summary of reported anode electrode materials used in MECs.
Table 11.3
Summary of cathodic electrode materials and catalysts used in MECs. Included are key performance parameters of MEC tests; hydrogen production rate (HPR), cathodic hydrogen recovery (RCAT), overall energy efficiency or recovery (
h
E
+
S
).
Table 11.4
Summary of membranes/separators reported in previous MEC studies.
Table 11.5
Summary of the value-added products from MECs platform.
Chapter 12
Table 12.1
The compositions of some representative macro- and microalgae species.
Table 12.2
Assumed SCWG conditions and syngas composition for system evaluation.
Table 12.3
Hydrogen separation and hydrogenation conditions.
Table 12.4
Conditions of conventional thermal gasification and compositions of produced syngas [55].
Chapter 13
Table 13.1
Rate of hydrogen generation obtained by using different morphologies of TiO
2
materials.
Table 13.2
Multi-metal sulfide nanomaterials for photo catalytic hydrogen production.
Table 13.3
Photocatalytic properties of g-C
3
N
4
-based complex system.
Chapter 14
Table 14.1
Some composite TiO
2
photocatalysts for photocatalytic hydrogen generation.
Chapter 15
Table 15.1
Summary of the experimental conditions, hydrogen evolution rates, apparent quantum efficiencies and enhancement factors for different g-C
3
N
4
-based composites published in 2016 (indexed in WOS; bibliographical survey updated on August 31).
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Scrivener Publishing 100 Cummings Center, Suite 541J Beverly, MA 01915-6106
Publishers at Scrivener Martin Scrivener ([email protected]) Phillip Carmical ([email protected])
Advances in Hydrogen Production and Storage
Series Editors: Mehmet Sankir and Nurdan Demirci Sankir
Scope: Energy is one of the most important issues for humankind. Increasing energy demand, regional limitations, and serious environmental effects of the conventional energy sources provide the urgent need for new, clean, and sustainable energy. Advances in Hydrogen Production and Storage emphasizes the basics of renewable energy and storage as well as the cutting edge technologies employed for these applications. The series focuses mainly on hydrogen generation, photoelectrochemical solar cells, fuel cells and flow batteries.
Submission to the series: Please send book proposals to Mehmet Sankir [email protected]
Hydrogen Production Technologies
Edited by
Mehmet Sankir
Nurdan Demirci Sankir
This edition first published 2017 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA © 2017 Scrivener Publishing LLC For more information about Scrivener publications please visit www.scrivenerpublishing.com.
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Library of Congress Cataloging-in-Publication Data ISBN 978-1-119-28364-5
Preface
Energy is one of the most important issues for humankind. Increasing energy demand, regional limitations and serious environmental effects of conventional energy sources have brought about the need for new, clean and sustainable energy. This book series has been planned as a presentation of the basics in the areas of renewable energy and storage as well as the cutting-edge new technologies for these applications. Hydrogen Production Technologies is the first volume of the series due to the undeniable importance of hydrogen as a clean energy carrier. Hydrogen has been gaining more attention in both transportation and stationary power applications. Fuel cell-powered cars are on the roads and the automotive industry is demanding feasible and efficient technologies to produce hydrogen. There are various ways to produce hydrogen in a safe and cost-effective manner. This volume covers the new technologies used to obtain hydrogen more efficiently via catalytic, electrochemical, bio- and photohydrogen production and as such is a valuable component in the research area of hydrogen production. The principles and methods described herein lead to reasonable mitigation of the great majority of problems associated with hydrogen production technologies. The book is edited to be useful as a text for university students at both introductory and advanced graduate levels and as a reference text for researchers in universities and industry. The chapters are written by distinguished authors who have extensive experience in their fields. Besides researchers in the engineering area, those in the energy, materials science and chemical engineering fields have been focusing on new materials and production technologies in order to generate hydrogen in an efficient and cost-effective way. Hence a multidisciplinary approach is taken to covering the topics of this book. Readers will absolutely have a chance to compare the fundamental production techniques and learn about the pros and cons of these technologies.
The book is organized into three parts. Part I shows the catalytic and electrochemical principles involved in hydrogen production technologies. It should be clear from this part that the fundamentals and modern status of water electrolysis, ammonia decomposition, methane reforming, steam reforming of hydrocarbons and biethanol, hydrolysis of ammonia borane and also SO2 electrolyzer are of great importance. Therefore, their various aspects are discussed such as catalyst development, thermodynamics and kinetics of reaction mechanisms, reactor and mathematical modeling, novel membrane structures, and advanced nanoparticles. Part II is devoted to biohydrogen production. This part is designed to be a good introduction to gasification and fast pyrolysis of biomass, dark fermentation, microbial electrolysis and power production from algae. It specifically presents various catalytic formulations as well as reactor designs to overcome catalytic deactivation due to coking. In addition to gasification of wood, dried sewage sludge, and plastic waste, newly developed staged gasifiers with fewer impurities are discussed. Moreover, there is a discussion of dark fermentation using sulphate-reducing bacteria from the genus Desulfovibrio utilized in hydrogen production. Part II also addresses hydrogen production from electrochemically active bacteria (EAB) by decomposing organic compound into hydrogen in microbial electrolysis cells (MECs). Lastly, highly efficient harvesting of energy from algae in the forms of hydrogen and enhanced process integration reducing exergy destruction are demonstrated. The last part of the book is concerned with photohydrogen generation. Recent developments in the area of semiconductor-based nanomaterials, specifically semiconductor oxides, nitrides and metal-free semiconductor-based nanomaterials for photocatalytic hydrogen production are extensively discussed. Moreover, Part III also includes pristine and doped TiO2 nanostructures for fast hydrogen production during photocatalytic water splitting. Finally, an earth abundant catalyst for water splitting is presented as a very promising narrow band gap visible-light photocatalyst.
Since the findings range over many useful topics specifically discussed in the book, readers from diverse fields such as chemistry, physics, materials science and engineering, mechanical and chemical engineering and also energy-focused engineering programs can benefit from this comprehensive review of the hydrogen production technologies.
Series Editors Mehmet Sankır, PhD and Nurdan Demirci Sankır, PhD Department of Materials Science and Nanotechnology Engineering TOBB University of Economics and Technology Ankara, Turkey January 1, 2017
Part ICATALYTIC AND ELECTROCHEMICAL HYDROGEN PRODUCTION
Chapter 1Hydrogen Production from Oxygenated Hydrocarbons: Review of Catalyst Development, Reaction Mechanism and Reactor Modeling
Mohanned Mohamedali, Amr Henni and Hussameldin Ibrahim*
Clean Energy Technologies Research Institute (CETRi), Process Systems Engineering, Faculty of Engineering and Applied Science, University of Regina, Canada
*Corresponding author:[email protected]
Abstract
Hydrogen is viewed as a clean and efficient fuel for future energy generation, with an enormous amount of research being pursued to study the various routes for the production, storage, and application of hydrogen fuel. To date, diverse approaches have been employed for the production of hydrogen-rich fuel through catalytic processes using nonrenewable materials as well as sustainable feedstocks. This review of the recent literature, is intended to provide an outlook on the catalyst development, reaction mechanism and reactor modeling studies of hydrogen production using catalytic steam reforming of oxygenated hydrocarbons with focus on methanol, ethanol, and glycerol feedstocks. Various attempts to optimize the catalyst performance, including the utilization of various noble and transition active metals as well as oxide support materials, are extensively discussed. Tremendous effort has been dedicated to develop a reaction mechanism for the reforming of oxygenated hydrocarbons, with no consensus to date on the exact reaction pathway due to the complex nature of the reforming process. This review provides insights into the fundamental understanding of the reaction mechanism and the contribution of the active metals and support on the observed kinetics. Moreover, the previous literature on the modeling and simulation of the hydrogen production process is also reviewed.
Keywords: Hydrogen production, oxygenated hydrocarbons, catalyst development, reaction kinetics, reaction mechanism, reactor modeling
1.1 Introduction
The global reliance on fossil fuels as the main energy source for power generation, transportation, and as a feedstock for chemical industries is widely increasing with the discoveries of new fossil fuel reserves and the technological advancement in their production and application. According to the recent annual energy outlook released in 2014 by the International Energy Agency (IEA), fossil fuels are projected to supply more than 80% of the world total energy by 2040. However, fossil fuel-based energy generation has increased the concentration of greenhouse gas emissions to an alarming level of 400 ppm in 2013 [1]. The continued increasing levels of anthropogenic greenhouse gases in the atmosphere will ultimately cause further weather changes, resulting in severe impacts on life on earth; therefore, combating climate change requires sustainable development of green technologies and policies to mitigate climate change. In accordance with the Paris Climate Conference (COP21) of 2015, several countries have pledged to reduce their emission levels to possibly achieve a 2 °C scenario (2DS) and cut the emissions to 60% by 2100, corresponding to cumulative CO2 emissions of 1000 GtCO2. In order to achieve such objectives a portfolio of low-carbon technologies has to be deployed to reach the 2DS, consisting of energy efficiency, fuel switching, and renewable energies. According to the 2016 energy technology perspective report issued by the IEA, the contribution toward the reduction of the cumulative CO2 emissions in the 2DS over the period 2013 to 2050 is estimated to be 38% from electricity efficiency, 12% for carbon capture and sequestration (CCS), and around 32% should come from the deployment of renewable energy sources. To establish clean energy for the future, the development of low carbon energy supply is urgently required. Among the possible alternatives, hydrogen has the potential to provide an ideal energy carrier that can meet the increasing global demand for energy and efficiently replace the existing fossil fuels [2, 3]. Hydrogen can provide an energy of 122 kJ/g, which is almost three times higher than hydrocarbon fuels [4], and is projected to contribute 34% of the total renewable resources in 2050 [5]. The application of hydrogen in the transportation and power generation sectors is receiving growing interest from both the technological and the policy-making aspects [6–8]. The contribution of hydrogen as a fuel for the transportation sector is mainly driven by the great achievements in fuel cell technology and the development of internal combustion engines that uses hydrogen fuel [9–12]. Fuel cell-based engines have three times higher efficiency than conventional gasoline engines due to the excellent characteristics of hydrogen as an energy carrier [13], in addition to the outstanding performance of hydrogen as a transportation fuel [14]. Hydrogen fuel being a gas at normal temperature and pressure, as compared to liquid hydrocarbon fuels, presents a major challenge for safe storage and transportation [15, 16]. Traditional storage schemes require energy-intensive techniques and have great safety concerns; however, the latest developments in the methods and technologies of the materials used for hydrogen storage are promising for realizing the hydrogen economy. Several review papers have described the current status and future trends in hydrogen storage materials [15, 17, 18]. Hydrogen can be produced from various energy sources using different processes, which could be categorized into renewable and nonrenewable resources. Hydrogen production from fossil fuel derivatives, such as methane and coal through gasification and thermocatalytic processes, is considered the major source for nonrenewable hydrogen production, representing more than 95% of the hydrogen produced to date [19]. In addition to being nonrenewable, hydrogen produced from fossil fuel resources contributes to global warming by releasing CO2 during the production process. On the other hand, biomass is considered as a sustainable route for hydrogen production with less net CO2 produced due to the fact that the CO2 released from the conversion of biomass has already been naturally captured from the atmosphere. In addition to the most widely used thermochemical technology, other methods, such as the electrolysis of water, have also been used for hydrogen production, with a major drawback of being highly energy intensive and having a low efficiency of around 25% [20, 21]. Other technologies, such as the photobiological techniques, are also reported based on the photosynthetic stimulation of some types of bacteria to release hydrogen; however, the sluggish release rate of hydrogen is considered a major challenge for these technologies [22–24]. Several review papers are available that give a detailed overview of the different hydrogen generation technologies [14, 25, 26]. Dincer et al. [27] followed a comparative assessment approach to evaluate several hydrogen production schemes such as natural gas reforming, electrolysis, coal and biomass gasification. The assessment criteria included environmental, economic and social impacts of these various methods. It was concluded that for the case of Turkey, biomass gasification has the best energy efficiency, whereas electrolysis methods were found to be less attractive when the hydrogen cost is considered.
This chapter aims at reviewing the sustainable and environmentally friendly hydrogen production from the steam reforming of oxygenated hydrocarbons, with a special focus on methanol, ethanol and glycerol, to recapitulate the state of the art in this field, and summarize the research conducted in the past five years (2012 to 2016) in order to get deep insights into the promising future for these technologies. The literature pertaining to the catalyst development for the steam reforming process, reaction mechanism, reactor modeling and simulations is thoroughly reviewed following a comparative analysis approach whenever possible.
1.2 Catalyst Development for the Steam Reforming Process
The catalyst development is considered the heart of sustainable hydrogen production through the steam reforming of oxygenated hydrocarbons. The hydrogen production rate, purity, and the selectivity of the reforming process are significantly impacted by the characteristics of the catalyst used. This crucial role of the catalyst has been highlighted by the numerous research projects conducted over the past years to understand the fundamentals of the catalytic process, and to develop highly efficient catalysts that can increase the overall conversion, improve hydrogen yield and prolong their lifetime [28, 29]. There are certain catalytic traits that need to exist for an efficient catalyst to be used in the steam reforming hydrogen production. These characteristics are prominently dependent on the nature of the oxygenated hydrocarbon feed (i.e., methanol, ethanol or glycerol) as well as the feed purity (i.e., crude versus pure) [30]. However, there are general requirements for catalytic surfaces such as: (1) the activity for C-C bond cleavage to produce CO, CO2, and CH4, (2) steam reforming of intermediates to produce hydrogen, and (3) the ability to produce free oxygen while preventing coke formation as well as C-O bond creation [31, 32]. Based on the contribution in the catalytic reforming reaction, there are three distinct parts of the catalyst: the active metal, the support, and the metal-support interactions. Control of the interaction between the metal and support is essential to improve the dispersion of the active sites and consequently achieve a better reaction rate and hydrogen yield. It was found that it is not only the nature of the individual support and metal sites that affects the reforming reaction but rather the interface that plays a vital role as reported recently [33]. In the following section we will thoroughly review and summarize the work that been performed over the past five years in the development of active metals and support materials for the catalytic transformation of oxygenated hydrocarbons to hydrogen. As stated earlier, this review chapter will focus on methanol, ethanol and glycerol as models for the oxygenated hydrocarbon feed; thus, accordingly, this section will be discussed in light of these three contexts.
1.2.1 Catalyst Development for the Steam Reforming of Methanol (SRM)
A very good review paper by Sá et al. [29] has been published which summarizes the development on catalysts used for the SRM process reported before 2010. In this section we will mainly present the latest work conducted after 2010 to provide the most recent perspective in order to keep up to date with the rapid progress in the research related to the catalyst development for the SRM process. The most common catalyst for SRM is Cu-based catalyst. Tremendous effort has been dedicated to understanding the catalytic reforming over Cu-based catalysts and to prepare efficient catalysts with high dispersion, high surface area, and small particle sizes. Several approaches are available to accomplish these objectives such as investigating novel synthesis methods [34], using promoters [33, 35], utilizing active support materials and the optimization of the operating conditions for higher hydrogen yield and improved catalyst stability [36, 37]. Table 1.1
