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CHEMISTRY RESEARCH AND APPLICATIONS A B LCOHOLS AND IOALCOHOLS C , P HARACTERISTICS RODUCTION U AND SES No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in rendering legal, medical or any other professional services. C R A HEMISTRY ESEARCH AND PPLICATIONS Additional books in this series can be found on Nova‘s website under the Series tab. Additional e-books in this series can be found on Nova‘s website under the e-book tab. CHEMISTRY RESEARCH AND APPLICATIONS A B LCOHOLS AND IOALCOHOLS C , P HARACTERISTICS RODUCTION U AND SES ANGELO BASILE AND FRANCESCO DALENA EDITORS New York Copyright © 2015 by Nova Science Publishers, Inc. All rights reserved. No part of this book may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical photocopying, recording or otherwise without the written permission of the Publisher. For permission to use material from this book please contact us: [email protected] NOTICE TO THE READER The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No liability is assumed for incidental or consequential damages in connection with or arising out of information contained in this book. The Publisher shall not be liable for any special, consequential, or exemplary damages resulting, in whole or in part, from the readers‘ use of, or reliance upon, this material. Any parts of this book based on government reports are so indicated and copyright is claimed for those parts to the extent applicable to compilations of such works. Independent verification should be sought for any data, advice or recommendations contained in this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage to persons or property arising from any methods, products, instructions, ideas or otherwise contained in this publication. This publication is designed to provide accurate and authoritative information with regard to the subject matter covered herein. It is sold with the clear understanding that the Publisher is not engaged in rendering legal or any other professional services. If legal or any other expert assistance is required, the services of a competent person should be sought. FROM A DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS. Additional color graphics may be available in the e-book version of this book. Library of Congress Cataloging-in-Publication Data Alcohols and bioalcohols : characteristics, production, and uses / editors, Angelo Basile and Francesco Dalena (Institute on Membrane Technology of the Italian National Research Council, c/o University of Calabria, Italy). pages cm. -- (Chemistry research and applications) Includes index. ISBN: (cid:28)(cid:26)(cid:27)(cid:16)(cid:20)(cid:16)(cid:25)(cid:22)(cid:23)(cid:25)(cid:22)(cid:16)(cid:20)(cid:27)(cid:26)(cid:16)(cid:26) (eBook) 1. Alcohols. 2. Alcohol as fuel. 3. Biomass. 4. Chemistry, Technical. I. Basile, Angelo (Angelo Bruno), editor. II. Dalena, Francesco, editor. TP248.A5A43 2014 661'.82--dc23 2014037737 Published by Nova Science Publishers, Inc. † New York CONTENTS Preface vii Chapter 1 Bioalcohol Production 1 Francesco Dalena and Angelo Basile Chapter 2 Bioethanol Production and Metabolism by Aquatic Photosynthetic Microbes: Algae and Cyanobacteria 23 G. Kenchappa Kumaraswamy Chapter 3 Process Development for Hydrolysate Optimization from Lignocellulosic Biomass Towards Biofuel Production 41 Ankita Mazumder, Sunil Maity, Dwaipayan Sen and Kalyan Gayen Chapter 4 Application of Ultrasonication in the Production of Second-Generation Bioethanol 77 Keat Teong Lee and Cynthia Ofori-Boateng Chapter 5 The Electrocatalytic Oxidation of Small Organic Molecules (Methanol, Formic Acid and Ethanol) 95 Zhiming Cui Chapter 6 Bimetallic Catalysts, Alloy Catalysts, and Bed Reactors for Alcohols and Bio-alcohols Reforming 119 Vincenzo Palma, Antonio Ricca, Marco Martino, Daniela Barba and Paolo Ciambelli Chapter 7 Alcohols and Bio-Alcohols and Bio-Alcohols Derived Hydrogen in Fuel Cells 133 Vincenzo Palma, Antonio Ricca, Marco Martino, Daniela Barba and Paolo Ciambelli Chapter 8 Hydrogen Production by Steam Reforming of Alcohols in Conventional Reactors 167 Francesco Frusteri and Giuseppe Bonura vi Contents Chapter 9 Alcohols and Bio-Alcohols Steam and Autothermal Reforming in a Membrane Reactor 181 Jordi Llorca and Ali Hedayati Chapter 10 Photocatalytic Conversion of Alcohols 205 Riitta L. Keiski, Tanja Kolli, Prem Kumar Seelam, Khawer Shafqat, Anna Valtanen and Mika Huuhtanen Index 223 PREFACE During the most recent decades, the industrial research efforts have become more focused on low-cost processes to satisfy the continuously increasing energy demand. Bioethanol production is both a potential and a feasible method to solve this problem. In fact, especially in the last 10 years, many research projects on ethanol production have been carried out principally because it is a prosperous renewable energy carrier mainly produced from biomass fermentation. Production of ethanol (bioethanol) from biomass is one way to reduce both consumption of crude oil and environmental pollution because it is appropriate for the mixed fuel in the diesel engine for its high octane number that impede self-ignition in the gasoline engine; besides the fuel bioethanol production processes from biomass (such as agricultural residues and urban wastes) is the most promising feedstock considering its great availability and low cost. In addition, methanol and bioethanol are considered as promising candidates for hydrogen production via steam reforming using catalytic processes. In fact, the use of catalysts plays a crucial role in hydrogen production through ethanol reforming. Many works of research have been addressed, in the last years, to the investigation of the influence and the optimization of catalysis activity on alcohol and bioalcohol steam reforming in bed-type and in membrane-type reactors. The aim of this book is to provide an overview of worldwide research in the use of bioalcohols in the energy development. It summarizes the characteristics and methods used to produce bioethanol and the current approaches on lignocellulosic-derived biofuel with its performance and its exhaust emissions; besides, this book also provides an overview of recent research activities in the field of reactor and catalytic reaction by steam reforming of alcohol and bioalcohol for the production of H . 2 This book can be considered split in two main parts: bioethanol production and its use. Going a bit in detail, in particular, Ch. 1 (Dalena and Basile) starts giving a global overview of research and development in the chain of production that from biomass induce the production of bioethanol. The main steps involved, and descripted in detail, are four: pretreatment, hydrolysis, fermentation and purification. Concerning Ch. 2 (Kumaraswamy), it mainly concentrates on Algae and Cyanobacteria. They are the robust photosynthetic microbes with innate potential to produce high levels of carbohydrates, which could be harnessed for bioethanol production. Owing to their minimal growth requirements and ease of genome modification than plants, these can be better and cheaper feedstocks for bioethanol. Ch. 3 (Mazumder, Maity, Sen and Gayen) gives a wide overview on the renewable biofuels viii Angelo Basile and Francesco Dalena derived from lignocellulosic biomass through hydrolysis. The focuses on the amalgamated techniques with both hydrolysis and fermentation, such as separate enzymatic hydrolysis and fermentation, simultaneous saccharification and fermentation, non isothermal simultaneous saccharification and fermentation, simultaneous saccharification and cofermentation. Recent studies demonstrate that ultrasound energy could efficiently break the recalcitrant nature of lignocellulosic biomass for further conversion into cellulosic ethanol. To this argument is dedicated Ch. 4 (Lee and Ofori-Boateng), which main focus is geared towards the application of ultrasound energy in different types of lignocellulosic biomass pretreatment, hydrolysis and fermentation stages in a bioethanol refinery. As it is well known, direct liquid fuel cells (especially methanol, formic acid and ethanol) have attracted growing attention because liquid fuels are easily handled, transported and stored; besides they have high specific energy at low operating temperatures. The main limiting factor for their commercialization is the poor oxidation kinetics of liquid fuels. These interesting aspects are presented and discussed in Ch. 5 (Cui), where a brief review about both the fundamental and technological aspects of direct liquid fuel cells are described. Particular emphasis is dedicated on fundamental research, which specifically includes five typical anode reactions: methanol oxidation in acid, methanol oxidation in alkaline media, formic acid oxidation in acid media, ethanol oxidation in acid and ethanol oxidation alkaline media. Ch. 6 (Palma, Ricca, Martino, Barba and Ciambelli) provides a brief review on the state of art in both a) the use of bimetallic and alloy catalysts and to the bed reactors in alcohols and bio-alcohols reforming; and b) the structured catalysts with particular attention to the structural stability in harsh environment that include vibrations, thermal cycling and continuous start up and shut down. Next one is Ch. 7 (Palma, Ricca, Martino, Barba and Ciambelli), which provides a introduction to the use of alcohols, bio-alcohols and bio- alcohols derivatives in fuel cells technology, for energy production processes. For indirect bio-alcohol fuel cells, the configuration of internal reforming, the direct and indirect internal reforming for both the molten carbonate and the solid oxide fuel cells are described. Some features of direct and indirect internal reforming in both these fuel cells are also shown, with respect to the catalytic aspects and the most important operative parameters that the Authors consider to be optimized in order to maximize the efficiency of the two systems, i.e. the reaction temperature and the steam/carbon feed ratio. In this chapter, a brief introduction to the use of the proton exchange membranes and the anion exchange membranes in direct alcohol fuel cells is also presented. Ch. 8 (Frusteri and Bonura) focus on the catalytic conversion of alcohols to produce hydrogen, which is investigated with the aim to highlight the limits encountered in the development of steam reforming processes. The chapter focus the incipient coke formation promoted by olefins generated from alcohols, which is considered by scientists an obstacle not easy to be overcome. The Authors show that the use of bimetallic systems and the employment of fluid bed reactors fed with trace of oxygen can be considered as solutions for the development of an efficient process for the production of CO-free hydrogen to be fed to fuel cell systems. Ch. 9 (Llorca and Hedayati) addressed their chapter on the catalytic steam reforming, partial oxidation and oxidative steam reforming (autothermal reforming) reactions aimed at hydrogen generation from alcohol-water mixtures (such as methanol, ethanol, glycerol, and the exploitiation of renewable bio-alcohols). The Authors of this chapter suggest the use of

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