The role of green chemistry in biomass processing and conversion

THE ROLE OF GREEN CHEMISTRY IN BIOMASS PROCESSING AND CONVERSION THE ROLE OF GREEN CHEMISTRY IN BIOMASS PROCESSING AND CONVERSION Edited by Haibo Xie Nicholas Gathergood Copyright # 2013 by John Wiley & Sons, Inc All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 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Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002.Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com Wiley also publishes its books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit our web site at www.wiley.com Library of Congress Cataloging-in-Publication Data: The role of green chemistry in biomass processing and conversion / edited by Haibo Xie, Nicholas Gathergood p cm Includes index ISBN 978-0-470-64410-2 (cloth) Environmental chemistry–Industrial applications Biomass energy I Xie, Haibo, 1978- II Gathergood, Nicholas, 1972TP155.2.E58R65 2013 333.950 39–dc23 2012017190 Printed in the United States of America ISBN: 9780470644102 10 CONTENTS Foreword vii Preface xi Contributors xiii About the Editors xvii Introduction of Biomass and Biorefineries Birgit Kamm Recent Advances in Green Chemistry 27 Nicholas Gathergood Biorefinery with Ionic Liquids 75 Haibo Xie, Wujun Liu, Ian Beadham, and Nicholas Gathergood Biorefinery with Water 135 X Philip Ye, Leming Cheng, Haile Ma, Biljana Bujanovic, Mangesh J Goundalkar, and Thomas E Amidon Supercritical CO2 as an Environmentally Benign Medium for Biorefinery 181 Ray Marriott and Emily Sin Dissolution and Application of Cellulose in NaOH/Urea Aqueous Solution 205 Xiaopeng Xiong and Jiangjiang Duan Organosolv Biorefining Platform for Producing Chemicals, Fuels, and Materials from Lignocellulose 241 Xuejun Pan v vi CONTENTS Pyrolysis Oils from Biomass and Their Upgrading 263 Qirong Fu, Haibo Xie, and Dimitris S Argyropoulos Microwave Technology for Lignocellulosic Biorefinery 281 Takashi Watanabe and Tomohiko Mitani 10 Biorefinery with Microbes 293 Cuimin Hu and Zongbao K Zhao 11 Heterogeneous Catalysts for Biomass Conversion 313 Aiqin Wang, Changzhi Li, Mingyuan Zheng, and Tao Zhang 12 Catalytic Conversion of Glycerol 349 Jie Xu, Weiqiang Yu, Hong Ma, Feng Wang, Fang Lu, Mukund Ghavre, and Nicholas Gathergood 13 Ultrasonics for Enhanced Fluid Biofuel Production 375 David Grewell and Melissa Montalbo-Lomboy 14 Advanced Membrane Technology for Products Separation in Biorefinery 407 Shenghai Li, Suobo Zhang, and Weihui Bi 15 Assessment of the Ecotoxicological and Environmental Effects of Biorefineries 435 Kerstin Bluhm, Sebastian Heger, Matthew T Agler, Sibylle Maletz, Andreas Sch€affer, Thomas-Benjamin Seiler, Largus T Angenent, and Henner Hollert Index 469 FOREWORD Many predictions have been made as to when global oil production will reach its maximum, most predicting it to occur in the early 21st century with the demand for oil continuing to rise while production is reducing When combined with the now very clear fact that remaining oil is difficult to obtain and comes at a very high environmental as well as economic cost, it is inevitable that oil prices will rise probably at a more dramatic rate than we have seen before leading to market and political instabilities While public and most political attention has focused on the impact of this on energy costs, there is an equally inevitable effect on chemicals derived from petroleum Indeed, it could be argued that the prospects for chemicals are worse as with energy there are noncarbon alternatives Clearly, we must quickly seek economically and environmentally sound sustainable alternative feedstocks for the manufacture of key commodity chemicals The economics and availability of oil feedstocks is a key factor in the drive to get more sustainable alternatives, but it is not the only driver Protection of the natural environment is also widely recognized as a key aspect in building a sustainable future Global warming as a result of CO2, CH4, and other emissions; the accumulation of plastics in landfill sites and in the ocean; acid rain; smog in highly industrialized areas; and many other forms of pollution, can all be attributed to the use of oil and other fossil fuels as feedstocks The challenge for scientists to support a sustainable economy is to produce material products for society which are based on green and sustainable supply chains We cannot sustainably use resources more quickly than they are produced and we cannot sustainably produce waste more quickly than the planet can process it back into useful resources We need short-cycle renewable resources Biomass offers the only sustainable and practical source of carbon for our chemical and material needs It is also available for a cycle time measured in years rather than hundreds of millions of years for fossil resources The concept of a biorefinery is the key to unlocking biomass as a feedstock for the chemical industry Biorefineries of the future will incorporate the production of fuels, energy, and chemicals, via the processing of biomass The move from petroleum to biomass as the carbon feedstock for the chemical industry provides only half the answer We need to use efficient technologies in the biorefineries and protect the environment: to this, the concepts outlined by green chemistry must be applied Green chemistry was originally developed to eliminate the use, or generation, of environmentally harmful and hazardous chemicals as well as reduce waste Green chemistry today takes a more life cycle point of view and vii viii FOREWORD seeks to use clean manufacturing to convert renewable resources into safe products, products that ideally can be recycled at the end of life thus maintaining the principle of “closed loop manufacturing.” It offers a tool kit of techniques and underlying principles that any researcher could, and should, apply when developing green and sustainable chemical-product supply chains This book addresses this challenge by studying in depth how different green chemical technologies can help turn biomass into green and sustainable chemicals The chapters cover the use of benign solvents, alternative energy technologies, catalytic methods and separation techniques, as well as the basics of biomass, biorefineries, and green chemistry After introductory chapters on biorefineries and green chemistry, there are three chapters focusing on how the three most studied alternative reaction media in green chemistry, can be applied to biorefineries Ionic liquids represent one of the most fascinating of the green chemical technologies – getting around the volatile solvent problem by using nonvolatile liquids that can also be incredibly powerful solvents and even combined catalyst–solvent systems Ionic liquids are one of the more likely solutions to the problem of often highly intractable biomass There can be no better solvent from an environmental point of view and in terms of convenience in a biorefinery than water – biomass is inevitably wet anyway and the more we can processing in water the simpler, safer, and cheaper the biorefinery products are likely to be Biorefineries will produce a lot of CO2 and making use of that CO2 will be an especially important goal; supercritical CO2 is a rather useful solvent for extractions from biomass and for some downstream chemistry These “alternative media” chapters are followed by chapters tackling the critical issue of cellulose dissolution for processing – NaOH/urea/water being a very simple and effective medium for dissolving cellulose and then using those solutions, while the organosolv method and especially the organosolv-ethanol process can also be used to help process lignocellulosics more generally and even help tackle the problematic issue of lignin valorization One of the most popular product types from biomass have been pyrolysis oils that are being seriously considered as partial replacements for petroleum fuels Chapter addresses this area and includes the vital issue of upgrading since most as-produced pyrolysis oils are not of the required chemical quality for example, they are too acidic, for direct mixing with petroleum Microwave processing is an alternative to conventional heating as a way to turn biomass into pyrolysis oils as well as for biomass pretreatment and saccrification – some of the topics covered in Chapter Catalysis is the most important green chemical technology, tackling the fundamental green-chemistry challenges of improved efficiency, better selectivity, and lower energy consumption Three chapters look at different ways that different catalysts can help make the most out of biomass as a feedstock Chapter 10 looks at biotransformations and how they can be used to turn biomass into different fuels and chemicals Heterogeneous catalysts including solid acids and bases and supported metals are often considered to be preferable to homogeneous equivalents as they enable simpler and less wasteful separations at the end of the process and it is appropriate that their use in some biomass conversions are considered here A particularly interesting and current challenge in biomass conversion is the utilization FOREWORD ix of glycerol produced in very large quantities as a by-product in the manufacture of biodiesel, one of the most successful biofuels The use of the glycerol would greatly support biodiesel manufacture and Chapter 12 looks at catalytic ways to help this Green chemistry offers alternatives to conventional reactors and energy sources Apart from microwaves discussed in Chapter 9, ultrasonics have also proven popular and their use in biorefineries and especially in assisting biofuel production is discussed in Chapter 13 Separations are often the biggest source of waste in a chemical manufacturing process and clever ways to separate complex products in biorefinery processes are essential In Chapter 14, advanced membrane technologies including the important pervaporation method and different membrane materials including polymers and zeolites are discussed In the final chapter, the critical issues of ecotoxicity and environmental impact from using biorefineries are addressed including biofuel production and biofuel emissions Biomass utilization alone is not the answer to the sustainable production of liquid fuels and organic chemicals but when combined with the best of green chemistry we have the real opportunity to help create a truly sustainable society JAMES CLARK PREFACE Our high quality of living standards in many parts of the world is largely due to and dependent on the development of fossil-based energy and chemical industries While the products from these industries have enriched our life, they have also directly or indirectly placed our environment under immense stress One of most noticeable issues is global warming, caused by the accumulation of “Green House” gases, due to over dependence on nonrenewable fossil-based resources To counteract this, the concept of green-chemistry was proposed towards the design of products and processes that minimize the use and generation of hazardous substances The aim is to avoid problems before they occur Fossil fuels are considered nonrenewable resources because they take millions of years to form It is estimated that they will be depleted by the end of this century Furthermore, the production and use of fossil fuels raises considerable environmental concerns A global movement toward the generation of energy and chemicals from renewable sources is therefore under way This will help meet increased energy and chemical-feedstock needs Biomass has an estimated global production of around 1.0 Â 1011 tons per year, through natural photosynthesis using CO2 as the carbon source Therefore, the carbon in biomass is regarded as a “carbon neutral” carbon source for the construction of chemicals and materials through biological and chemical approaches It is estimated that by 2025, up to 30% of raw materials for the chemical industry will be produced from renewable sources To achieve this goal it will require a major readjustment of the overall techno-economic approach From a sustainability point of view, and learning from decades of petroleum-refinery process, the introduction and integration of green-chemistry concept into biomass processes and conversion is one of the key issues towards a concept of avoiding problems before they happen Biomass can refer to species biomass, which is the mass of one or more species, or to community biomass, which is the mass of all species in the community It can include microorganisms, plants, or animals In this book, we focus on lignocellulosic biomass, because they represent the most abundant of biomass resources They are mainly composed of cellulose, hemicellulose, and lignin To differentiate the research of petroleum refinery, a new biorefinery process has been proposed according to biomass-based research activities Current knowledge of lignocelluose-based biomass and the biorefinery process have been introduced in the first chapter in this book, which presents the basic and whole ideas to convert the biomass into valuable chemicals and materials xi xii PREFACE Since the concept of green chemistry was proposed, significant accomplishments have been achieved according to the widely recognized “twelve principles,” and recent advances have been introduced in the second chapter in this book This gives a more in-depth understanding of green chemistry and potential green technologies; those that could be used for biomass processing and conversion With a better understanding of challenges during biomass processing and conversion, the introduction and exploration of suitable green-chemistry technologies is important to meet the tailored-processing and conversion of biomass The contributors from different specific research areas provide us with the latest progress and insight in the biomass processing and conversion using green-chemistry technologies For example, the introduction of green solvents (e.g., ionic liquids, supercritical CO2, water); sustainable energy sources (e.g., microwave irradiation, sonification); green catalytic technologies; advanced membrane separation technology; etc We believe that all of these will be strong bases for the foundation and exploration of a cost-competitive and sustainable bioeconomy in the near future Traditionally, a focus on the economic assessments of technologies was exercised while social and environmental assessments were often neglected, which is one of the reasons for the ultimate environmental deterioration The balance of economic assessments, social assessments, and environmental assessments is one of most important issues for any emerging technologies towards a sustainable biorefinery The last chapter of the book gives us in-depth understanding of environmental assessments of the conversion and use of fuels, chemicals, and materials from biomass Research into biomass processing and conversion is a wide-ranging interdisciplinary research field, and the book presents an up-to-date multidisciplinary treatise for the utilization of biomass from a sustainable chemistry point of view We thank all the people who made valuable contributions and suggestions, from the esteemed contributors to the diligent reviewers, which laid the foundations for a successful project and publication of this book DR HAIBO XIE and DR NICHOLAS GATHERGOOD 460 ASSESSMENT OF THE ECOTOXICOLOGICAL AND ENVIRONMENTAL EFFECTS cells of vertebrates, have only a cell membrane Toxicity is likely to be influenced by structural differences as well as by different cellular responses, such as apoptosis or detoxification mechanisms Overall, the results obtained from the YES-assay are ambiguous Although an increased endocrine activity was indicated by the assay for two samples, the concentrations applied for substrate and effluent samples are not comparable Whereas the endocrine activity of sample R1-S was investigated starting at 62.5%, the highest concentration of the complementary effluent sample R1-E was 0.4% The lack of estrogenic activity, especially regarding the effluent sample R1-E, was unexpected as discussed above However, a higher estrogenic potential for this sample might still be conceivable but not detectable in the YES-assay due to high sample dilution Thus, the YES assay might not be an appropriate test for this kind of samples Consequently, the investigation of the endocrine activity of these samples should be continued using more sensitive assays, such as the ER CALUX1 assay [119] Additionally, effect-directed analysis could be applied for the investigated samples In earlier studies, for example [88], masking toxicity of crude sediment extracts was reduced using fractionation techniques to evaluate the mechanismspecific toxicity of a given strong toxic sample With respect to the results presented and other available data, it seems to be appropriate to select certain endpoints separately for each biomass pretreatment method An overview of the bioassays discussed, their applicability as well as preliminary estimations regarding their relevance for the testing of differently pretreated samples are presented in Table 15.4 We recommend assays for the investigation of cytotoxic potentials for samples from biomass pretreatment in general due to their utilization as a screening assay for further sublethal ecotoxicological endpoints, such as EROD induction Taking into account the results presented by Tame et al [111] and Zhao et al [120], the EROD assay should be at least considered for investigations of ionic liquids and samples from pyrolysis With regard to the dilute acid and the alkaline pretreatment, the implementation of the TABLE 15.4 Applicability and Preliminary Estimation of the Relevance of Bioassays with Regard to Biomass Pretreatment Methods Pretreatment Cytotoxicity EROD Activity Embryotoxicity Mutagenicity Endocrine Activity Dilute acid Alkaline Ionic liquidsb Pyrolysisc ỵ ỵ ỵ ỵ ỵ/ ỵ/ ỵ ỵ ỵ n.a n.a n.a ỵa n.a n.a n.a ỵa ỵ n.a n.a ỵ ẳ investigations highly recommended ỵ/ ẳ applicable but appeared to be of less relevance with regard to the initial results a applicable but, with regard to the extracts used in this study, other test systems than the Ames fluctuation assay and the YES assay, respectively, might be more suitable; n.a ¼ no data available b Ref [120] c Ref [111] RESULTS AND DISCUSSION 461 EROD assay is generally possible but, based on our results, seems to be of little relevance Other assays, such as the embryotoxicity and the mutagenicity assay investigations, were only performed with dilute acid pretreated samples, and we are aware of no available literature on their application to other pretreatments Concerning the results of the dilute acid pretreatment, the mutagenic and embryotoxic effects demonstrate a great importance for corresponding samples to be investigated in assays revealing effects on the embryotoxicity and mutagenicity To make recommendations for the application of embryotoxicity and mutagenicity assays regarding samples from alkaline pretreatment, ionic liquids or pyrolysis, initial investigations are needed (these have to be assayed as well) This also holds true with regard to endocrine activity However, with respect to samples from alkaline pretreatment, endocrine activities were indicated by first results (unpublished data), and thus tests regarding this endpoint should be considered It has to be emphasized that all of these suggestions represent only a small fraction of all known (eco)toxicologically relevant endpoints Nevertheless, they illustrate the need for more investigations of these biofuel-related samples In summary, ecotoxicological investigations of biomass samples after dilute acid pretreatment revealed cytotoxic and embryotoxic effects, no significant effects in the YES assay but indications for endocrine as well as mutagenic potentials Dioxin-like activities were not detected The dilute acid pretreatment of the substrates CS and R1-S were found to increase the cytotoxic potential for RTLW1 cells and to decrease the survival rate of D rerio embryos, compared to the effluent sample R1-E and the untreated substrate sample R4-S This indicates a positive correlation with intensified pretreatments In contrast, higher mutagenic potentials were revealed for the samples R1-S and R1-E than for CS, but the substances that caused these effects still remain unknown Thus, there is a strong need for further investigations of the mutagenic potential With respect to endocrine activity, however, no significant effects could be recorded, albeit indications for a low increase of endocrine potentials were found However, further studies are highly recommended to decide whether the YES assay is the best-suited test system for this (eco)toxicological endpoint and to allow a better estimation of a reproduction toxicological potential risk for the environment and human health Induction of the phase-I metabolism of xenobiotics, on the contrary, was not detected for any sample Obviously, EROD-inducing compounds were not formed, neither by means of dilute acid pretreatment nor by the undefined mixed cultures during fermentation; and might not be of high relevance with respect to the samples tested Nevertheless, depending on the pretreatment method the risk of increased dioxin-like activity has to be considered differently The biotest results together with the data available from literature strongly propose further ecotoxicological investigations with regard to biofuel-related samples, in order to identify any possible harm for the environment and human health The respective biotests and endpoints to be studied should be chosen according to the kind of biofuel, the pretreatment method of the substrate, and the production process However, further investigations are indispensable to define such decision criteria 462 ASSESSMENT OF THE ECOTOXICOLOGICAL AND ENVIRONMENTAL EFFECTS 15.3.6 Implications for a Sustainable Production and Use of Biofuels Knowledge on the potential hazards of biofuel-related samples is important to minimize adverse effects on the environment and/or human health Ecotoxicological investigations provide important information regarding such effects and can therefore serve as an important tool for a sustainable development of biofuels Beside biofuels themselves, relevant samples are also biofuel combustion products and their waste or by-products from the production processes, including biomass pretreatments and the conversion process At first, samples that induce certain adverse effects and, thus, permit conclusions regarding disadvantageous steps in the production process need to be identified using a multifaceted biotest battery By chemical analyses of the samples the hazardous compounds causing adverse effects could subsequently be identified Based on the test results, adaptations of a pretreatment method or changes in the production processes would then be carried out with the aim to minimize the hazard potential of a biofuel A successful implementation of changes in the production process or the need for further improvement could be revealed through verification with further biotesting of samples from the adapted process Ecotoxicological investigations of biofuels and associated processes should be initiated early already accompanying the biofuel development process This would allow to identify those biofuels and related production processes that are as environmentally compatible as possible and therefore avoid unintended release of a fuel with high hazard potentials Changes in the production process as a result of ecotoxicological testing may, therefore, improve the ecological profile of biofuels 15.4 CONCLUSIONS Information on ecotoxicological effects of biofuels and biofuel emissions are limited but potential adverse effects to the environment cannot be ruled out Furthermore, waste or by-products formed during pretreatment or fermentation may be sources of problematic substances, but even less data is available on this topic Recently conducted investigations on the (eco)toxicological effectiveness of dilute-acid pretreated biofuel substrates and an effluent sample by means of a biotest battery address this topic Test results revealed no dioxin-like activities but cytotoxic and embryotoxic effects, as well as indications for mutagenic effects and an increase of endocrine activities Cytotoxic and embryotoxic effects varied depending on the pretreatment method Samples pretreated with dilute acid (CS, R1-S) increased the cytotoxic potential and adverse effects on the survival rate of D rerio embryos The fermentation process, on the other hand, revealed a potential to remove cytotoxicity-inducing compounds Mutagenic potentials were found for the samples CS, R1-S, and R1-E by using the Ames fluctuation assay and were discussed in the view of possible impacts due to the composition of the samples; but the substances behind these effect potentials still need to be identified Nevertheless, the findings demonstrate that pretreatment can lead to adverse effects on organisms As a REFERENCES 463 consequence, the ecotoxicological impacts of biofuels, biofuel combustion products, and their waste or by-products from the production processes, including biomass pretreatments and the conversion process, have to be evaluated before a biofuel is deployed Early identification of toxic intermediates, by-products, or wastes should be taken into consideration to allow production-process optimization regarding an improved ecological profile of biofuels Further knowledge on adverse effects would help optimize the production process and could serve as an early warning system to prevent the formation of toxic by-products or restrain the release of dangerous substances to the environment ACKNOWLEDGMENTS This work was partly performed as part of 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and Z D Zhang, Clean-Soil Air Water 2007, 35, 42 INDEX (ỵ)-Ambiguine 46 (ỵ)-Ambiguine H 46 (ỵ)-Welwitindolinone 46 (ỵ)-Welwitindolinone A 46, 47 ()-Fischerindole 46 (À)-Fischerindole I 46, 47 (À)-Hapalindole 46 (À)-Hapalindole U 46 (À)-Oseltamivir 62, 63 (extraction) co-solvents 189 1,2-Propylene glycol 353 1,3-Propylene glycol 356 5-(Chloromethyl)furfural 59, 61 5-Hydroxylmethylfurfural (HMF) 5, 92–9, 122, 152, 160, 161, 165, 245–6, 248, 250, 258–60, 297, 301, 304–6, 315, 318–9, 321–8, 342, 407, 426, Anaerobic digestion 158, 395–6 Anselme Payen Award 206 Antibacterial toxicity 40, 46, 223 Antifungal toxicity 39, 46, 328 Anti-HIV compounds 51 Antimicrobial toxicity 38, 52, 54, 107–11, 118, 121, 233 Antioxidant 144, 248, 256–8, 273 Aquatic eukaryote 111 Aqueous phase reforming 163, 278, 367–8 Acrylic acid 13, 170, 361–2, 365–6 Atom economy 28, 30, 33–35, 58, 351 Attenuation 378, 379 Autohydrolysis (AH) 141–3, 147–8 Autoxidation 3, 256 Autothermal reforming 367–8 Auxiliaries 28, 41 ABT-341 63, 64 Acetol 152, 277, 353–364 Acetone–butanol–ethanol fermentation 300 Acidic hydrolysis 84, 87, 142, 146, 296, 441, 442, 248 Acidity 267 Acoustic streaming (microstreaming) 382 Acrolein 170, 172, 353, 361–6 Agaricus bisporus crude extract 49 Alcohol recovery 417 Alcohol-water separation 421 Alcoholysis 122 Algae 102, 112–4, 118–9, 154, 159, 169–73, 389, 398, 436 Aminium lactate 19–20, 24 Amplitude 376–8, 381 Bacteria 23, 46–7, 54, 108–11, 118–9, 121, 144, 299–300, 304–5, 440, 448–9, 458–9 Bimetallic catalyst 322, 331–4 Biobased products 2, 3, 21–2 Biobutanol 300 Biocatalysis 86 Biocatalysis (in scCO2) 199 Biocompatibility 86 Bioconversion 23, 242, 247–8, 250, 259, 294–303 Bio-crude 150–3, 172, 272–3 Biodegradation 38, 54, 106–7, 110, 120–3 Biodiesel 2, 46, 75, 92, 102–4, 106, 122, 169, 185, 189, 273, 288, 300–1, 315, 319, 322, 335–42, 349, 351, 357, 366, 370, 388–9, 396–8, 401, 437–9 The Role of Green Chemistry in Biomass Processing and Conversion, First Edition Edited by Haibo Xie and Nicholas Gathergood Ó 2013 John Wiley & Sons, Inc Published 2013 by John Wiley & Sons, Inc 469 470 INDEX Bioenergy 2, 21–2, 92, 435–6 Bioethanol 2, 6, 92, 181, 184–5, 194, 235, 248, 282, 284, 288, 298–301, 306, 407–8 Biofuel 2, 3, 10, 15, 22, 49, 75, 80, 84, 95, 123, 138, 145, 150–2, 59, 169, 171–3, 181, 185, 187, 281, 288, 294–302, 304, 322, 375–404, 407, 418, 421, 428, 435–446, 454, 461–3 Biogas 1, 2, 10, 15–9, 295, 395, 412 Biomass 1–468 Biomass conversion 10, 29, 41, 75, 79, 95, 155, 159–62, 172–3, 295, 313–5, 318–4, 326–8, 330, 332, 334, 336, 338–9, 341–2, 407, 413, 440, Biomass densification 197 Biomass utilization 3, 26, 75, 77, 79, 91, 297 Biomethanol Biopolymer 55, 77, 81–2, 84, 99, 140, 171, 174, 205, 226, 230, 413 Biorefinery 1–26, 29, 62, 75–123, 135–173, 181–200, 242–3, 247, 281–290, 293–308, 407–428, 440, 442, 444, 445, Biorefining 1, 15, 18–9, 241–2, 246, 254 Biorenewable resource 79, 122 Biotests (battery of) 444–7, 461 Biotransformation 293, 307–8, 445–8 Bisphenol-A (BPA) 57–8, 66 Blend 81, 148, 219, 223, 230, 242, 254, 273, 423–4, 437–8 Carbohydrate 5, 7, 10–1, 16–7, 20, 44, 77–9, 84, 89, 92, 94–5, 97, 100, 122–3, 139–40, 143, 145, 147, 163–4, 182, 248, 253, 276, 288, 293, 296, 301, 305, 313, 322, 327–8, 402, 407, 444, 454, Carbon fiber 248, 253–6 Catalysis 21, 28, 39, 48, 73, 76–7, 94, 138, 159, 170, 198, 200, 243, 313–4, 318, 320, 324–6, 329, 336, 338, 342, 354, 356, 364, 367 Catalyst 2, 30, 34, 37–9, 41–7, 48–53, 57, 59, 69, 75, 79, 82–4, 86, 90–5, 97–104, 122, 141, 149, 152–3, 155, 157–60, 162–5, 168, 170, 172–3, 182, 184, 198–200, 241, 246, 259, 269–72, 274–8, 281, 285, 287–8, 290, 293–4, 300, 313–22, 324–44, 353–69, 396–7 Catalytic conversion 45, 75, 79, 85, 99, 100–1, 103, 122–3, 327, 329, 331, 333, 349–73 Catalytic cracking 263, 269, 271, 276 Cavitation 382–4, 399 Cellulase 86–7, 159, 246, 248, 251–2, 287, 296, 413, 442–3 Cellulose 4–8, 10, 15, 21, 44–5, 49, 59–60, 75–92, 94–5, 97–9, 101, 106, 122, 138–41, 145, 152, 158–61, 172, 184–5, 205–36, 241–2, 245–6, 248–52, 256, 258–9, 269–70, 276–7, 281, 284, 288, 295–8, 315–9, 321–2, 325, 328–35, 341–3, 393–5, 407, 413, 422, 440–3 Cellulose composites 10, 15, 80–81 Cellulose derivatives 83, 140, 205, 211, 216, 230–2, 236 Cellulose fiber 78, 81–2, 85, 91, 122, 138, 160, 205–206, 208, 216–220, 235, 248, 440 Cellulose gel 225–6 Cereal straw waxes 191–3 Chitin 81, 230, 235, 338 Choline hexanoate 55 Chromium (VI) 40 Chromium(II) chloride 92, 94, 99 Closed Bottle test 38, 54, 69, 120–1 CO2 27, 139, 150–2, 155, 157, 166, 172, 206, 271, 275, 305, 307, 320, 327, 341, 355–6, 368, 369, 395 CO2 Headspace test 54, 120–1 CO2 capture 185, 370 CO2 density 188 CO2 extraction 188 CO2 polarity 183–4 Cold pressed oil 190 Composite 82–3, 222, 253–4, 281, 320 Composite fibers 219–20 Composite films 222–5 Composite membrane 410–1, 419, 421–5 Consolidated bioprocessing 298 Continuous-flow-type 284–5, 290 Converters 380–1 Crop fractionation 10, 15, 17 Cryptococcus curvatus 301 Cumene hydroperoxide (CHP) 57 Cuticle waxes 185, 187, 194 Cytotoxicity 115–6, 233, 446–7, 452–3, 456, 458–62 INDEX Defoaming 398–9 Dehydration 18, 84, 92, 94–6, 99–100, 122–3, 144, 148, 161–4, 168, 170, 172, 245–6, 269, 278, 314, 321, 324–6, 328, 351–58, 361–66, 370, 407, 409, 418–25 Dehydrositagliptin 30, 32–3 Delignification 138–140, 143, 145, 148, 245, 252, 259, 288 Depolymerization 75, 91, 94, 99–101, 122, 143, 149, 152, 172, 248, 256, 258, 314, 390 Designable solvent 76 Dielectric heating 282–3 Dielectric loss 281, 288 Diethylcarbonate 36 Diffraction 209–10, 217, 378–9 Dihydroxyacetone 160–2, 359–60 Dilute acid pretreatment 296, 441–3, 453, 457–8, 461 Diketones-(beta) 191–2 Dimethylether 2–3 Dissolution 76–7, 80–2, 84, 86, 90, 100, 106, 118, 120, 122, 205–235, 249, 319–20, 394–5, 441 Direct reforming 272 Domino reaction 48 Dry fractionation Ecotoxicity 106–122 Ecotoxicological potential 435–468 Embryotoxicity 446, 450, 452, 460–1 Emulsification 265, 269, 272, 396 Emulsions 272, 382, 397, 399, 401 Endocrine activity 437, 439, 446, 450–1, 457–62 Energy balance 155, 173, 288, 375, 385, 399–400, 436 Energy efficiency 28, 43, 58, 136, 163, 248, 290, 385, 388, 393, 395–6, 428 Enzymatic digestibility 242, 246, 248, 251–2 Enzymatic hydrolysis 78, 84–6, 235, 248, 251, 296–7, 392–4, 442 Enzymatic saccharification 284, 286–7, 290 Enzyme catalyzed 49, 94, 102–3 Enzyme inhibition 112, 116 EROD activity 446–7, 460 Esomeprazole 60 471 Esterification 7, 40, 70, 102, 106, 200, 254, 270, 274–5, 315, 335–40, 368 Ethanol 2–3, 5, 7, 10, 13–5, 19, 22–3, 36, 49, 85, 88, 101, 136, 140–1, 145, 147–8, 151, 160, 163, 183–5, 189–90, 193–4, 221, 241–3, 246–59, 270–1, 274, 285–6, 293, 295, 298–301, 338, 357, 366, 387–90, 392–4, 396, 400, 407–9, 412, 418–28, 443–5 Etherification 7, 198, 254, 351, 366–7 Ethylene carbonate 39, 49, 66, 369 Ethylene glycol (EG) 7, 44–5, 50, 66, 278, 283–5, 290, 321, 331–4, 342, 351–2, 358 Extraction economics (CO2) 195–7 Extractives 138–9, 143–5, 147–8, 190, 194, 288, 295 Fast pyrolysis 152–3, 159, 263–8, 273, 276–7 Fermentable sugar 16, 84, 86, 250, 390, 393–4 Fermentation 6–7, 10, 14, 16–18, 20, 24–5, 46, 92, 110, 139, 145–6, 159, 172, 181, 242, 259, 286–7, 290, 293, 297–306, 389–96, 407, 409, 411–18, 423, 428, 440–6, 453–4, 459, 461–2 Formic acid 141, 145, 242, 244–5, 250, 258–9, 276, 297, 326 Fractionation 7, 10, 14–7, 138, 139, 144, 159, 172, 187, 191, 306, 460 Free phenolic hydroxyl groups (PhOH) 146, 149, 243, 257 Free radical generation 379–80, 382, 387 Functionalized ionic liquids 101–2, 106 Furfural 12, 61–2, 95, 98, 139, 141–5, 148, 160–2, 242, 245–6, 248, 250, 258–9, 275–7, 297, 301–6, 319, 321, 407, 426, 442 Furfural derivatives 92, 94, 100, 143, 145, 152 Gas assisted mechanical extraction (GAME) 190 Gasification 10, 11, 136, 150–1, 154–9, 173, 265, 272, 290 Gasification-electrochemical catalytic reforming (G-ECR) 272 Gel 81, 215, 226–7, 233 472 INDEX Gel permeation chromatography (GPC) 91 Gel retardation assay (GRA) 233 Glucose 5–7, 13–4, 20, 45, 59, 78–9, 85–6, 88, 90–2, 94–9, 101, 140, 144, 155, 159–63, 232, 248–53, 293, 296, 298–305, 315–8, 322, 325, 327–9, 334, 393, 407–8, 411 Glyceric acid 359–60 Glycerol 12, 45, 52, 100, 102, 104–5, 159, 168–72, 285, 288–90, 294, 335, 349–70 Glycerol carbonates 369 Glycerol tert-butyl ether 366 Green biomass 1, 3, 9–10, 14–5, 17–19, 154 Green chemistry 27–74, 107, 120, 158, 294, 297–8, 304, 306, 315, 334, 349, 351 Green technology 206, 219, 235 Guaiacyl (G-) ethers 80, 99, 100, 164, 244, 253, 268 Guaiacylglycerol-guaiacyl ether 100 Heating value 136, 139, 150–2, 267–8, 274 Heck reaction 50, 51 Hemicellulose 4–6, 86, 90, 141, 152, 159, 184, 241–2, 245–6, 248–50, 252, 258–9, 269, 282, 284, 295–6, 319, 335, 343, 393, 407, 440–3 Heterogeneous catalysis 138, 198, 313, 324–6, 356 Hexafluoroisopropanol (HFIP) 43–4, 66 High & low power ultrasonics 375 High pressure thermal treatment 277 Hock process 57 Homogeneous catalysis 101, 138, 182, 269, 313–4, 318, 324, 331, 335–42, 356, 363, 367 Homogeneous cellulose solution 82, 208, 215, 230 Homogeneous membrane 410, 422–3 Homogeneous nucleation 384 Homogeneous reactions 77, 79, 82, 84, 91, 138, 160, 161, 166, 168, 216 Hot-water extraction (HWE) 135, 139, 144–5 Hybrid poplar 248–50 Hydrogen 2–3, 6–7, 11, 13, 29, 44, 51–2, 77, 101, 151, 154–7, 163, 171, 182–3, 270–4, 277–8, 331, 351, 353, 357, 362, 367–8 Hydrogen bonding 77–8, 86, 94, 169, 205, 209–10, 212–3, 230, 235, 257, 424 Hydrogen transfer 331, 369 Hydrogenation 30, 33, 44–5, 51–2, 95, 100–1, 153, 163–4, 168, 172, 182–4, 198, 263, 269–74, 277–8, 304, 314, 319–22, 329–34, 353–4, 358, 360, 365, 407 Hydrogenolysis 84, 122, 255, 272, 314, 351–9, 370, 404 Hydrolysis 5, 16, 79, 84–5, 87–8, 90–2, 94–5, 101, 107, 113, 122, 138–42, 145–8, 151, 153, 154, 159, 160–1, 165–6, 168–9, 171–2, 200, 243–6, 251–2, 269, 275, 296, 298, 300, 302–3, 314–6, 318, 321, 327–30, 333–5, 341, 351, 357, 388, 394, 402, 407, 411–3, 426, 440–2, 456 Hydroxypropyl cellulose 232 Imino-sugars 47, 61–2 Immobilized enzymes 200 IMPROVEMENTS 65 Inclusion complex 209, 212–3 Industrial production 205, 207, 235 Insol fraction 145–9 Ionic liquids 36–7, 50, 52–4, 66, 69, 78, 80, 83–4, 86, 90–2, 99–104, 106–7, 110–112, 114, 117–8, 120, 123, 206, 270, 274–7, 331, 367, 394–5, 441, 443 Jet cooking 391–2, 396, 400 Jetting 382, 384–5, 387 Ketonization 274–5 Lactic acid 1, 10, 12, 14–20, 45–6, 110, 140, 147, 163, 170–172, 289, 303–4, 351, 354 Levulinic acid 10, 12, 15, 84, 92, 95, 98, 101, 122, 160, 198, 245, 248, 258–9, 322, 326, 407, 426 Lignin 4–6, 11, 79–81, 86, 90, 99–100, 122–3, 139–40, 142–3, 145–50, 152, 158–9, 164–8, 172, 175, 184, 198, 241–6, 248–60, 269–70, 276, 281, 284, 287–9, 295–6, 313, 335, 343, 388–90, 393, 407, 440, 442–4, 446, 453–4, 458 Lignin model compound 99–100 INDEX Lignocellulose 4, 10, 13, 79–81, 83–6, 88, 91, 241–2, 259, 295, 302, 306, 313–4, 321, 325, 342–3, 413, 440–3 Lignocellulosic biomass 86, 135, 138, 157–9, 172, 241, 246, 248, 250, 259, 271, 281–2, 286, 288, 295, 298–301, 303–4, 321, 393–4, 413, 440, 442–3 Lignocellulosic feedstock (LCF) 4–6, 15, 19 LiOH/urea 211–2, 231–2 Lipid extraction 189 Lipomyces starkeyi 297, 301 Liquid CO2 182–4, 187–8 Liquid crystal display (LCD) 29, 30, 66 L-lysine-L-lactate 20 Lodgepole pine 248–50, 299 Long-chain alkyl glycoside 84, 100–1 Low temperature 50, 76, 155, 157, 161, 206–7, 212–5, 276–7, 282, 416, 421, 425 LY518674 55 Lyocell fibers 216 Lyocell process 206 L-Lysine 1, 13, 15–20 L-Lysine L-Lactate 20 Mammalian cell 114–5 Mass balance 17, 248–50 Membrane distillation 427 Membrane fouling 413–7, 428 Membrane materials 81, 415, 417, 419, 423, 428 Membrane-separation technology 409, 411, 427–8 Metabolites 37, 53–4, 107, 115, 120, 181, 184–5, 190, 193, 195, 197, 445 Metathesis 44–5 Methanol 2–3, 6, 13, 78, 88, 102, 104, 106, 111, 113, 115–6, 145–6, 153, 166, 168, 241, 267, 269, 276, 319, 321, 336–40, 349, 396–7, 418 Methyl isobutyl ketone (MIBK) 41, 66, 98, 325 Methylcellulose 231–2 Microbial oxidation 360 Microbial biodiesel 92 Microbial lipid 301–2 Microorganism 6, 111, 140, 293, 296–301, 304–7, 390, 393, 398, 413, 417, 425, 438, 453 473 Microwave irradiation 92, 94, 98, 281–291, 317, 342 Monosugar 84, 87–8, 91–2, 159 Multilayer membrane 424 Mutagenicity 110–1, 437, 439, 446–9, 454–6, 460–1 NaOH/thiourea 211–213, 217, 223, 235 NaOH/urea 205–36 Nanocomposites 91, 225, 423 Natural glycerol 349 Near and far field 378–9 NMMO 206, 211, 215, 217 Oil extraction 35, 196, 389, 398 Oleaginous yeast 102, 301–2 Omeprazole 60 One-pot cascade reaction 62, 64 One-pot strategy 60 One-pot process 101, 168, 327, 334, 341 Organism 107–15, 117–8, 121, 123, 300, 445, 448 Organocatalysts 48–49, 59, 62 Organosolv lignin 99, 166, 242, 248–50, 252–6, 258–60 Organosolv process 146, 241–4, 246, 248, 259 Organosolvolysis 281, 286, 288–9 Oxidation 29–30, 39–41, 46, 49, 57, 95, 99–100, 146–49, 153–4, 163, 171, 173, 183, 198, 257, 273, 286, 297, 314, 320, 332, 334, 342, 351, 359–62, 365, 368–70, 407 Oxidation with oxygen/air 40–1 Paal–Knorr procedure 43 Pellets 10, 15–6, 140, 196–8 Pelleting plant 196 Pelletization 197–8 Permittivity 137, 282–4, 290 Pervaporation process 410, 417–8, 423–6 P-factor 141, 145 Photoacylation 42 Pichia stipitis 140, 299 Plant (Biomass) 2, 9–10, 19, 79–81, 114, 118, 121, 143–4, 159, 187, 190–5, 284, 295, 389, 393, 396, 446, 458 Plant (Industrial) 5–6, 10–1, 14–9, 114, 118, 136–7, 139, 156–7, 159, 185, 190, 195–7, 242–3, 378, 393, 400, 408–9 474 INDEX Plant waxes 191, 194 Platform chemicals 1, 3, 12–13, 15, 21, 75, 101, 144, 246, 258, 303–4, 342, 407, 436 Platform molecules 59–2, 100, 198 Polycosanols 195 Polymer gel 228 Polymeric membrane 417, 421 Polyols 45, 164, 277–8, 315, 321–2, 328–9, 331–4, 349 Polyurethane foam 248, 254–5 Polyvinylacetate Polyvinyl-alcohol (PVA) 29 Polyvinylsulfate (PVS) 424 Power and energy density 377–8, 380 Power level 376–7, 382, 401 Power supply 377, 380–1, 399 Precipitation gel method 335 Precooling 207–8, 210, 214–6, 218, 235 Prehydrolysis 139, 246, 252 Pressurized hot-water extraction (PHWE) 139, 144 Pretreatment 78–80, 84, 86, 90, 122, 138– 41, 159, 189, 194, 200, 235, 241, 246, 248–50, 252, 259, 270, 281–2, 284–90, 296–8, 300, 304, 307, 330, 342–3, 388–91, 393–6, 400, 413, 426, 440–7, 453–4, 457–8, 460–3, Primary process Primary processing Primary products 8, 150, 272 Primary refinery 10, 15 PRODUCTIVELY 65 Propylene carbonate 49, 369 Protecting group free synthesis 46–8, 59 Pyrolysis 3, 6, 10, 136–7, 150–5, 157, 159, 165, 167–9, 173, 263–8, 270–8, 280, 387, 396, 440–4, 454, 460–1 Pyrolysis oil 273, 277–8 Ranitidine 59–2 Rayleigh distance 378–9 Rayleigh streaming 385 ReactIR 56, 59, 73 Rectified diffusion 384 Reforming 351, 367–8, 407 Regenerate cellulose beads 230 Regenerate cellulose fiber 81–2, 205–6, 216–7, 235 Regenerate cellulose film 206–7, 216, 220–6, 236 Regenerate cellulose microspheres 228–9 Rhodosporidium toruloides 297, 301 S/G ratio 146, 149 Saccharomyces cerevisiae 109, 297, 450 Selective heating 282 Semiochemicals 195 Separation technologies 77, 122–3, 408–9, 427–8 Sequential fractionation 139, 144 Simultaneous saccharification and fermentation (SSF) 297–9, 303–5, 396 Sitagliptin 30–3 Slow pyrolysis 264 Sol gel 215, 226, 424 Sol fraction 146–8, 150 Solid catalyst 91, 163, 272, 314–5, 322, 329–30, 343 Solution properties 214–5 Soybean oil 35, 104–6, 189–90, 271, 295, 337–8, 396, 398, 439 Speed 376 Speed of sound 376, 378, 384 Speed of light 283 Speed (stirring) 230, 251, 417 Standing wave 376–7 Starch gelatinization 138, 391–2 Steam reforming 153, 162, 263, 269, 271–2, 367 Sterols 185, 187, 191, 193–5, 200 Stop-and-go 60 Subcritical water 135–6, 138–9, 151–2, 159, 168, 325 Succinic acid 6, 23, 303–5 Sugar alcohol 100–1, 258, 333 Supercritical CO2 181–200, 228, 369 Supercritical water 135–6, 150, 154, 161–3, 166, 168–9, 171–3 Sustainable material 75, 77, 79, 81, 122 Swern oxidation 39 Switchable-hydrophilicity solvents 36, 41, 150 Synthetic glycerol 349 Syringyl (S-) 80, 164, 245, 253 INDEX Tandem conversion 94–5, 123 Tensile strength 217–8, 221–2, 225, 256, 422 Total reducing sugar (TRS) 88–91, 94, 97–98 Toxicity 28, 35, 37–8, 41, 49, 53–6, 101, 106–23, 268, 306, 438, 444, 446–7, 450, 456–7, 460 Transesterification 106, 169, 301, 315, 319, 335–42, 349, 368, 389, 396–7 Trichosporon cutaneum 301 Tungsten carbide 44–5, 321, 331–4, 342 Twelve Principles of Green Chemistry 27–8, 58, 64, 294, 315 Twelve Principles of Green Engineering 64 Ultrasonic frequency 144, 376, 379 Upgrading 151–2, 156, 168, 172, 263–4, 269–78, 321 Urea-hydrogen peroxide (UHP) 56 475 Valuable compound 8, 10, 15, 17, 75, 77, 79, 84, 92, 95, 99–100, 123, 148, 170, 181, 200, 242, 258, 276, 278, 306, 328, 331, 349, 351, 359, 361, 366, 368, 370, 407 Vapor barrier effects/coupling 387–8 Viscose 215–7, 219, 221 Viscose process 205–6 Viscosity 76, 86–7, 137, 151, 183–4, 198–9, 214–5, 263, 266–7, 269–70, 272, 274–5, 288, 377, 396 Wacker oxidation 40 Wavelength 282–3, 376, 378, 382, 385 Wax esters 187, 191 Wet fractionation 10, 14–15 Wood chemistry 76, 79–80, 122 Woody biomass 90, 139, 248, 284–9, 443 Zantac 60 Zeolite membrane 417, 419–20 ... His main research interests focus on the use of green solvents and green chemistry technologies in the processing and conversion of biomass into biofuels, value-added chemicals and sustainable... energy flows of the biorefining of green biomass 1.3.4 Mass and Energy Flows for Green Biorefining Green biorefining is described as an example of a type of agricultural factory in greenland-rich... environmental point of view and in terms of convenience in a biorefinery than water – biomass is inevitably wet anyway and the more we can processing in water the simpler, safer, and cheaper the biorefinery