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Héctor A. Ruiz
Mette Hedegaard Thomsen
Heather L. Trajano Editors
Hydrothermal
Processing in
Biorefineries
Production of Bioethanol and High
Added-Value Compounds of Second and
Third Generation Biomass
Hydrothermal Processing in Bioreﬁneries
Héctor A. Ruiz • Mette Hedegaard Thomsen
Heather L. Trajano
Editors
Hydrothermal Processing
in Biorefineries
Production of Bioethanol and High
Added-Value Compounds of Second
and Third Generation Biomass
Editors
Héctor A. Ruiz Mette Hedegaard Thomsen
Autonomous University of Coahuila, Department of Energy Technology
School of Chemistry, Aalborg University
Food Research Department, Esbjerg, Denmark
Biorefinery Group
Saltillo, Coahuila, Mexico
Cluster of Bioalcohols,
Mexican Centre for Innovation
in Bioenergy (Cemie-Bio)
Mexico City, Mexico
Heather L. Trajano
Department of Chemical
and Biological Engineering
University of British Columbia
Vancouver, BC, Canada
ISBN 978-3-319-56456-2 ISBN 978-3-319-56457-9 (eBook)

DOI 10.1007/978-3-319-56457-9
Library of Congress Control Number: 2017941184
© Springer International Publishing AG 2017

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Preface and Editorial
Biomass from lignocellulosic and aquatic material is seen as an interesting source

of raw material for conversion into biofuels, biochemicals, and biomaterials that are
coproduced via biomass upgrading. The main reason is that biofuels such as
bioethanol and new bio/co-products with high added value can contribute to
sustainable development. Subsequently, both are attractive in industry and the
bioeconomy in terms of an integrated biorefinery for second and third generation.
The integrated biorefinery concept is centered on environmental and economic
aspects. Therefore, the pretreatment process plays an important role in an integrated
biorefinery, since this stage allows the fractionation of the main components of the
lignocellulosic and aquatic biomass. Hydrothermal processing is easy to operate
and is the first step allowing the solubilization and depolymerization of the hemi-
cellulose fraction while increasing the accessibility of cellulose to enzymes pro-
ducing sugars for bioethanol production. Thus, hydrothermal processing is a
potential technology to convert raw materials such as lignocellulosic and aquatic
biomass into bioenergy and high added value compounds. In the near future,
second- and third-generation biofuel facilities are expected to develop toward the
biorefinery concept. The biorefinery economy is a vision for a future in which
renewable energy from biomass replaces fossil fuels.
This book aims to show fundamental concepts and key technological develop-
ments that enabled industrial application of hydrothermal processing on lignocellu-
losic and aquatic biomass in terms of biorefineries. This book brings together experts
in the application of hydrothermal processes on lignocellulosic and aquatic biomass.
This book is dedicated to Prof. Esteban Chornet and Dr. Ralph P. Overend in
recognition of the role that they have played in the development and application of
severity parameter as a variable to measure the hydrothermal processing, and also
we want to dedicate to the Memory of Professor Ortwin Bobleter (Institute of
Radiochemistry, University of Innsbruck, Austria), who passed away in September
2014; he was one of pioneers of the hydrothermolysis process.
In addition, the editors want to dedicate this book to those who have established
the process for using hydrothermal processing with water or steam (also called
v
vi Preface and Editorial
autohydrolysis, hydrothermal pretreatment, hot compressed water, hydro-

thermolysis, liquid hot water, aquasolve process, aqueous pretreatment pressure
cooking in water, and hot water flow-through pretreatment) and severity parameter:
William H. Mason{ (pioneer in steam explosion process), Prof. Morris Wayman{
(University of Toronto, Canada), Dr. Jairo H. Lora (Lora Consulting LLC), Prof.
Robert F. H. Dekker (Biorefining Research Institute, Lakehead University, Canada),
Prof. Charles (Charlie) E. Wyman (University of California, USA), Prof. Jack (John)
Saddler (University of British Columbia, Canada), Prof. Lee R. Lynd (Dartmouth
College, USA), Prof. Michael R. Ladisch (Purdue University, USA), Prof. Juan C.
Parajó (University of Vigo, Spain), and Guido Zacchi (Professor emeritus, Lund
University, Sweden), Dr. Helena Chum (National Renewable Energy Laboratory
(NREL), USA), Prof. Nicolas Abatzoglou (Université de Sherbrooke, Canada) and
Prof. Khaled Belkacemi (Université Laval, Canada).
We are, therefore, pleased to introduce this book on Hydrothermal Processing in
Biorefineries. This book contains 21 chapters about various aspects of the use of
hydrothermal processing including liquid hot water, steam explosion, raw mate-
rials, and severity parameter application.
In Chap. 1, Dr. Chornet and Dr. Overend provide a retrospective on the develop-
ment of the severity factor as well as a perspective on the importance of biorefining.
In Chap. 2, the effects of hydrothermal pretreatment on lignin are reviewed. This
review includes a discussion of how pretreatment conditions affect the extent of
lignin removal as well as the types of products that are produced. A brief introduc-
tion to analytical techniques for lignin is also provided. As the phenols produced by
pretreatment are potential antioxidants, the authors review the categorization of
antioxidants, the mechanisms of antioxidant behavior, and methodologies for
measuring antioxidant capacity and report the antioxidant behavior of extracts
produced by hydrothermal pretreatment of biomass.
Chapter 3 examines the effects of hydrothermal pretreatment on hemicellulose.
The chapter begins with a brief description of hemicellulose reactions during
hydrothermal pretreatment. This is followed by a discussion of hemicellulose
structure by type of biomass. Liquid hot water pretreatment and steam explosion
are discussed. The reaction mechanism of hemicellulose hydrolysis is presented and
relevant kinetic models are summarized. This is followed by a discussion of
analytical techniques for measuring concentration and molecular size of hemicel-
lulose-derived oligomers and monomers. Techniques for examining the structure of
hemicellulose in biomass solids are also presented.
Chapter 4 presents the effects of hydrothermal pretreatment by biomass type:
wood, bamboo, agricultural residues, and agave bagasse. The structure and com-
position of each biomass type is summarized. The chapter reviews acidic and alkali
hydrothermal pretreatment conditions by summarizing the changes in hemicellu-
lose, cellulose, lignin, ash, extractives, and ultrastructure. The effect of tempera-
ture, time, particle size, and reactor type on the outcomes of hydrothermal
pretreatment is also presented.
Chapter 5 provides a review of hemicellulose hydrolysis operating conditions
and reactor design. The chapter summarizes kinetic models of hemicellulose
Preface and Editorial vii
hydrolysis. Finally, the chapter describes a wide range of applications for hemicel-
lulose derivatives including pulp additives, films, nutraceuticals, and furfural and
organic acid production.
Chapter 6 describes the development of the severity parameter in greater detail.
The chapter begins with an introduction on dilute acid hydrolysis and a derivation
of kinetic rate expressions for hemicellulose hydrolysis. Against this background,
the derivation of the severity factor and the combined severity factor is presented.
Xylose yields from pretreatment, glucose yields from enzymatic hydrolysis, and
total glucose plus xylose yields from a range of biomass are presented as a function
of severity factor in order to identify overarching trends. Finally, the use of the
combined severity factor for dilute acid hydrolysis of xylo-oligomers is examined.
Chapter 7 begins with an introduction to the effects of pretreatment on biomass
as well as the need for pretreatment as a step in the production of lignocellulosic
ethanol. The authors then review the families of enzymes utilized during enzymatic
hydrolysis. Steam explosion, liquid hot water pretreatments, and the severity factor
are discussed, particularly in relation to subsequent enzymatic hydrolysis. Building
on this foundation, the authors present methods to reduce enzyme loading. This is
followed by a review of inhibitor production during pretreatment and methods to
reduce inhibition. Finally, the use of pretreated biomass for on-site production of
enzymes is presented.
Chapter 8 examines the current state of process modeling and economic assess-
ment of hydrothermal pretreatment and identifies opportunities for advancement and
improvement. The chapter begins with a description of the pretreatment process as
well as a description of auxiliary operations such as size reduction and solid–liquid
separations. The chapter reviews available process simulation software and methods
of modeling pretreatment reactions within the software. Techniques for calculating
capital and operating costs and evaluating plant economics are also presented.
Chapter 9 summarizes the effects of pretreatment on herbaceous energy crops such
as prairie cordgrass and switchgrass, the agricultural residue date palm tree fronds, and
halophytic species, Salicornia bigelovii. The chapter also examines the performance
of the same pretreated materials during enzymatic hydrolysis and fermentation.
Chapter 10 begins with a review of hemicellulose hydrolysis conditions, reactor
configurations, and reaction modeling through the perspective of oligomer produc-
tion. The chapter then summarizes techniques for recovering high-purity xylo-
oligomers from biomass hydrolysates, emphasizing the need for multistage
processing. Chromatographic and spectroscopic techniques for analyzing oligosac-
charides are presented. The chapter concludes with a description of oligomer
applications in functional foods, hydrogels, and films.
Chapter 11 provides a brief introduction to the structure of hemicellulose, its
processing, and potential applications for the production of enzymes, xylitol, and
furans. The chapter discusses in detail the activities of hemicellulases. This is
followed by a review of industrial applications and world market for hemicellulases
as well as the production of hemicellulases using hydrolysates produced by hydro-
thermal pretreatment. The applications for and production of xylitol and furans are
presented. For each end product, the authors present current and emerging produc-
tion processes.
viii Preface and Editorial
In Chap. 12, Hongzhang Chen and Wenjie Sui describe the basic principles of
steam explosion and integration of this process in biorefinery systems.
In Chap. 13, Nicolas Jacquet and Aurore Richel describe the adaptation of the
severity factor model to fit the complex dynamics and varying operating conditions
in steam explosion processes.
In Chap. 14, Ana Rita C. Morais and Rafal M. Lukasik provide the state of the art
of hydrothermal processing using supercritical CO2 as catalyst and its implemen-
tation in biorefineries.
In Chap. 15, Viviane Marcos Nascimento, Carlos Eduardo Vaz Rossell, and
George Jackson de Moraes Rocha compare hydrothermal pretreatment of sugarcane
bagasse in laboratory and pilot for second-generation ethanol production.
In Chap. 16, Alfred Rossner and Carolina Parra present pilot plant experiences
with hydrothermal pretreatment of hardwood (eucalyptus wood) to obtain ethanol, as
part of a Chilean consortium for utilization of woody biomasses called BioEnercel.
In Chap. 17 Michael Persson, Borbála Erdei, Mats Galbe, and Ola Wallberg
describe techno-economic evaluation as a tool in developing more economically
and environmentally sustainable second-generation biorefineries.
In Chap. 18, Adriaan van Heiningen, Yusuke Yasukawa, Kefyalew Dido, and
Raymond Francis describe the use of formic acid in hot water hydrolysis as a means
of minimizing precipitated lignin formation while maximizing monomeric sugar
yield.
In Chap. 19, Shuntaro Tsubaki, Ayumu Onda, Tadaharu Ueda, Masanori
Hiraoka, Satoshi Fujii, and Yuji Wada describe the fundamentals of hydrothermal
microwave-assisted biomass processing and demonstrate this pretreatment method
on seaweed biomass.
In Chap. 20, Daniela E. Cervantes-Cisneros, Dulce Arguello-Esparza, Alejandra
Caebello-Galindo, Brian Picazo, Cristóbal N. Aguilar, Hector A. Ruiz, and Rosa M.
Rodriguez-Jasso describe and discuss the most relevant hydrothermal processes for
extraction and fractionation of seaweed molecules while keeping the properties of
the active components intact.
In Chap. 21, Cristina González-Fernández, Lara Méndez, Mercedes Ballesteros,
and Elia Tomás-Pejó describe hydrothermal processing of microalgae biomass as a
means to disrupt the microalgae cells and hydrolyze biomass components prior to
biofuels production.
The editors would like to thank all of the authors for their compelling contribu-
tions to this book and the reviewers for their willingness to assess the submitted
chapters.
The text should be of interest to students, academics scientists, engineers from
industry, and potential investors in the biorefinery field. We hope you will enjoy
reading the chapters presented in the book as much as we enjoyed writing and
editing it.
Saltillo, Coahuila, Mexico Héctor A. Ruiz

Esbjerg, Denmark Mette Hedegaard Thomsen
Vancouver, BC, Canada Heather L. Trajano
Acknowledgments
We, the editors, would like to thank our families who supported us throughout this
endeavor. We also thank the editorial staff of Springer Publishers in the production
of this book.
Héctor A. Ruiz would like to thank the financial support from the Energy
Sustainability Fund 2014-05 (CONACYT-SENER), Mexican Centre for Innova-
tion in Bioenergy (Cemie-Bio), and Cluster of Bioalcohols (Ref. 249564). Also,
support to the Mexican Science and Technology Council (CONACYT, Mexico) for
the infrastructure project—INFR201601 (Ref. 269461), CB-2015-01 (Ref. 254808)
and the Mexican Thematic Network in Mexico (http://rtbioenergia.org.mx)—is
gratefully acknowledged. Finally, thanks are also due to the Autonomous Univer-
sity of Coahuila, Mexico, for the support given to the development of this book.
ix
About This Book
The concept of a biorefinery that integrates processes and technologies for biomass
conversion demands efficient utilization of all components. Hydrothermal
processing is a potential clean technology to convert raw materials such as ligno-
cellulosic materials and aquatic biomass into bioenergy and high added-value
compounds. This book aims to show scientific and technological concepts that
lead to developments in the industry of biorefineries applying this technology:
hydrothermal processing. Also, the scope of this book is primarily for scientists
working in this area of biorefineries, engineers from the industry, and potential
investors in biofuels. Therefore, the information in this book will provide an
overview of this technology applied to lignocellulosic materials and aquatic bio-
mass and especially new knowledge. It is very important to note that this book
brings together experts in the application of hydrothermal processes on lignocellu-
losic and aquatic biomass.
xi
Contents
1 How the Severity Factor in Biomass Hydrolysis Came About . . . . 1

Esteban Chornet and Ralph P. Overend
2 Effect of Hydrothermal Pretreatment on Lignin
and Antioxidant Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Andrés Moure, Gil Garrote, and Herminia Domı́nguez
3 Effect of Hydrothermal Processing on Hemicellulose
Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Ling-Ping Xiao, Guo-Yong Song, and Run-Cang Sun
4 Response of Biomass Species to Hydrothermal
Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
Jingqian Chen, Zhaoyang Yuan, Elisa Zanuso,
and Heather L. Trajano
5 Kinetic Modeling, Operational Conditions,
and Biorefinery Products from Hemicellulose:
Depolymerization and Solubilization During
Hydrothermal Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
Elisa Zanuso, Anely A. Lara-Flores, Daniela L. Aguilar,
Jesús Velazquez-Lucio, Cristóbal N. Aguilar,
Rosa M. Rodrı́guez-Jasso, and Héctor A. Ruiz
6 Combined Severity Factor for Predicting Sugar Recovery
in Acid-Catalyzed Pretreatment Followed by Enzymatic
Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Charles E. Wyman and Bin Yang
7 Hydrothermal Pretreatment of Lignocellulosic Biomass
for Bioethanol Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
Eduardo Ximenes, Cristiane S. Farinas, Youngmi Kim,
and Michael R. Ladisch
xiii
xiv Contents
8 Hydrothermal Pretreatment: Process Modeling

and Economic Assessment Within the Framework
of Biorefinery Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
Ana I. Torres, Muhammad T. Ashraf, Tanmay Chaturvedi,
Jens Ejbye Schmidt, and George Stephanopoulos
9 Bioethanol Production from Pretreated Solids Using
Hydrothermal Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
Iwona Cybulska and Mette Hedegaard Thomsen
10 Production and Emerging Applications of Bioactive
Oligosaccharides from Biomass Hemicelluloses
by Hydrothermal Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Beatriz Gullón, Izaskun Dávila, Marı́a Garcı́a-Torreiro,
Remedios Yá~nez, Jalel Labidi, and Patricia Gullón
11 Production of Hemicellulases, Xylitol, and Furan
from Hemicellulosic Hydrolysates Using
Hydrothermal Pretreatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Michele Michelin, Aloia Romanı́, José Manuel Salgado,
Lucı́lia Domingues, and José A. Teixeira
12 Steam Explosion as a Hydrothermal Pretreatment
in the Biorefinery Concept . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
Hongzhang Chen and Wenjie Sui
13 Adaptation of Severity Factor Model According
to the Operating Parameter Variations Which Occur
During Steam Explosion Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
Nicolas Jacquet and Aurore Richel
14 Hydrothermal Pretreatment Using Supercritical CO2
in the Biorefinery Context . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
Ana Rita C. Morais and Rafal M. Lukasik
15 Scale-Up Hydrothermal Pretreatment of Sugarcane
Bagasse and Straw for Second-Generation
Ethanol Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
Viviane Marcos Nascimento, Carlos Eduardo Vaz Rossell,
and George Jackson de Moraes Rocha
16 Pilot Plant Design and Operation Using a Hydrothermal
Pretreatment: Bioenercel Experience . . . . . . . . . . . . . . . . . . . . . . . 389
Alfred Rossner and Carolina Parra
17 Techno-Economic Aspects in the Evaluation of Biorefineries
for Production of Second-Generation Bioethanol . . . . . . . . . . . . . . 401
Michael Persson, Borbála Erdei, Mats Galbe, and Ola Wallberg
Contents xv
18 Minimizing Precipitated Lignin Formation and Maximizing

Monosugar Concentration by Formic Acid Reinforced
Hydrolysis of Hardwood Chips . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
Adriaan van Heiningen, Yusuke Yasukawa, Kefyalew Dido,
and Raymond Francis
19 Microwave-Assisted Hydrothermal Processing
of Seaweed Biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
Shuntaro Tsubaki, Ayumu Onda, Tadaharu Ueda,
Masanori Hiraoka, Satoshi Fujii, and Yuji Wada
20 Hydrothermal Processes for Extraction of Macroalgae
High Value Added Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . 461
Daniela E. Cervantes-Cisneros, Dulce Arguello-Esparza,
Alejandra Cabello-Galindo, Brian Picazo, Cristóbal N. Aguilar,
Héctor A. Ruiz and Rosa M. Rodŕıguez-Jasso
21 Hydrothermal Processing of Microalgae . . . . . . . . . . . . . . . . . . . . . 483
Cristina González-Fernández, Lara Méndez,
Mercedes Ballesteros, and Elia Tomás-Pejó
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
Contributors
Cristóbal N. Aguilar Biorefinery Group, Food Research Department, School of

Chemistry, Autonomous University of Coahuila, Saltillo, Coahuila, Mexico
Daniela L. Aguilar Biorefinery Group, Food Research Department, School of
Cluster of Bioalcohols, Mexican Centre for Innovation in Bioenergy (Cemie-Bio),
Mexico City, Mexico
Dulce Arguello-Esparza Biorefinery Group, Food Research Department, School
of Chemistry, Autonomous University of Coahuila, Saltillo, Coahuila, Mexico
Muhammad T. Ashraf Department of Chemical and Environmental Engineering,
Masdar Institute of Science and Technology, Abu Dhabi, UAE
Mercedes Ballesteros Biotechnological Processes Unit, IMDEA Energy Institute,
Móstoles, Spain
Renewable Energy Division, Biofuels Unit, CIEMAT, Madrid, Spain
Alejandra Cabello-Galindo Biorefinery Group, Food Research Department,
School of Chemistry, Autonomous University of Coahuila, Saltillo, Coahuila,
Mexico
Daniela E. Cervantes-Cisneros Biorefinery Group, Food Research Department,
School of Chemistry, Autonomous University of Coahuila, Saltillo, Coahuila,
Mexico
Tanmay Chaturvedi Department of Chemical and Environmental Engineering,
Hongzhang Chen State Key Laboratory of Biochemical Engineering, Institute of
Process Engineering, Chinese Academy of Sciences, Beijing, China
xvii
xviii Contributors
Jingqian Chen Department of Chemical and Biological Engineering, University

of British Columbia, Vancouver, BC, Canada
Esteban Chornet Enerkem, Sherbrooke, QC, Canada
CRB Innovations, Sherbrooke, QC, Canada
Iwona Cybulska Faculty of Bioscience Engineering, Earth and Life Institute,
Université Catholique de Louvain, Louvain-la-Neuve, Belgium
Izaskun Dávila Chemical and Environmental Engineering Department,
University of the Basque Country, San Sebastián, Spain
Kefyalew Dido Department of Chemical and Biological Engineering, University
of Maine, Orono, ME, USA
Lucı́lia Domingues CEB—Centre of Biological Engineering, University of
Minho, Braga, Portugal
Herminia Domı́nguez Departamento de Enxe~nerı́a Quı́mica, Universidade de
Vigo (Campus Ourense), Ourense, Spain
Borbála Erdei Department of Chemical Engineering, Lund University, Lund,
Sweden
Cristiane Farinas Graduate Program of Chemical Engineering, Federal Univer-
sity of S~ao Carlos, S~ao Carlos, SP, Brazil
Embrapa Instrumentaç~ao, S~ao Carlos, SP, Brazil
Raymond Francis State University of New York, College of Environmental
Science and Forestry, Syracuse, NY, USA
Satoshi Fujii Department of Chemical Science and Engineering, School of Mate-
rials and Chemical Technology, Tokyo Institute of Technology, Tokyo, Japan
Department of Information and Communication Systems Engineering, Okinawa
National College of Technology, Okinawa, Japan
Mats Galbe Department of Chemical Engineering, Lund University, Lund,
Sweden
Marı́a Garcı́a-Torreiro Department of Chemical Engineering, Institute of Tech-
nology, University of Santiago de Compostela, Santiago de Compostela, Spain
Gil Garrote Departamento de Enxe~nerı́a Quı́mica, Universidade de Vigo (Cam-
pus Ourense), Ourense, Spain
Cristina González-Fernández Biotechnological Processes Unit, IMDEA Energy
Institute, Móstoles, Spain
Beatriz Gullón Department of Chemical Engineering, Institute of Technology,
University of Santiago de Compostela, Santiago de Compostela, Spain
Contributors xix
Patricia Gullón Chemical and Environmental Engineering Department,

University of the Basque Country, San Sebastián, Spain
Masanori Hiraoka Usa Marine Biological Institute, Kochi University, Kochi,
Japan
Nicolas Jacquet University of Liège – Gembloux AgroBio Tech, Gembloux,
Belgium
Youngmi Kim Laboratory of Renewable Resources Engineering, Purdue Univer-
sity, West Lafayette, IN, USA
Department of Agricultural and Biological Engineering, Purdue University, West
Lafayette, IN, USA
Jalel Labidi Chemical and Environmental Engineering Department, University of
the Basque Country, San Sebastián, Spain
Michael R. Ladisch Laboratory of Renewable Resources Engineering, Purdue
University, West Lafayette, IN, USA
Lafayette, IN, USA
Anely A. Lara-Flores Biorefinery Group, Food Research Department, School of
Mexico City, Mexico
Rafal M. Lukasik Laboratório Nacional de Energia e Geologia, I.P., Unidade de
Bioenergia, Lisboa, Portugal
Lara Méndez Biotechnological Processes Unit, IMDEA Energy Institute,
Móstoles, Spain
Michele Michelin CEB—Centre of Biological Engineering, University of Minho,
Braga, Portugal
George Jackson de Moraes Rocha Laboratório Nacional de Ciência e
Tecnologia do Bioetanol, S~ao Paulo, Brazil
Ana Rita C. Morais Laboratório Nacional de Energia e Geologia, I.P., Unidade de
Bioenergia, Lisboa, Portugal
LAQV-REQUIMTE, Departamento de Quı́mica, Faculdade de Ciências e
Tecnologia, Universidade NOVA de Lisboa, Caparica, Portugal
Andrés Moure Departamento de Enxe~nerı́a Quı́mica, Universidade de Vigo
(Campus Ourense), Ourense, Spain
Viviane Marcos Nascimento Laboratório Nacional de Ciência e Tecnologia do
Bioetanol, S~ao Paulo, Brazil
xx Contributors
Ayumu Onda Research Laboratory of Hydrothermal Chemistry, Faculty of

Science, Kochi University, Kochi, Japan
Ralph P. Overend Biomass & Bioenergy Journal, Elsevier, United Kingdom
Carolina Parra Laboratorio de Recursos Renovables – Centro de Biotecnologı́a,
Universidad de Concepción – Barrio Universitario, Concepción, Chile
Michael Persson Department of Chemical Engineering, Lund University, Lund,
Sweden
Brian Picazo Biorefinery Group, Food Research Department, School of Chemis-
try, Autonomous University of Coahuila, Saltillo, Coahuila, Mexico
Aurore Richel University of Liège – Gembloux AgroBio Tech, Gembloux,
Belgium
Rosa M. Rodrı́guez-Jasso Biorefinery Group, Food Research Department, School
of Chemistry, Autonomous University of Coahuila, Saltillo, Coahuila, Mexico
Mexico City, Mexico
Aloia Romanı́ CEB—Centre of Biological Engineering, University of Minho,
Braga, Portugal
Carlos Eduardo Vaz Rossell Laboratório Nacional de Ciência e Tecnologia do
Bioetanol, S~ao Paulo, Brazil
Alfred Rossner Laboratorio de Recursos Renovables – Centro de Biotecnologı́a,
Universidad de Concepción – Barrio Universitario, Concepción, Chile
Héctor A. Ruiz Biorefinery Group, Food Research Department, School of Chem-
istry, Autonomous University of Coahuila, Saltillo, Coahuila, Mexico
Mexico City, Mexico
José Manuel Salgado CEB—Centre of Biological Engineering, University of
Minho, Braga, Portugal
Jens Ejbye Schmidt Department of Chemical and Environmental Engineering,
Guo-Yong Song Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing
Forestry University, Beijing, China
George Stephanopoulos Department of Chemical Engineering, Massachusetts
Institute of Technology, Cambridge, MA, USA
Wenjie Sui State Key Laboratory of Biochemical Engineering, Institute of
Process Engineering, Chinese Academy of Sciences, Beijing, China
Contributors xxi
College of Food Engineering and Biotechnology, Tianjin University of Science and

Technology, Tianjin, China
Run-Cang Sun Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing
State Key Laboratory of Pulp and Paper Engineering, South China University of
Technology, Guangzhou, China
José A. Teixeira CEB—Centre of Biological Engineering, University of Minho,
Braga, Portugal
Mette Hedegaard Thomsen Department of Energy Technology, Aalborg
University, Esbjerg, Denmark
Elia Tomás-Pejó Biotechnological Processes Unit, IMDEA Energy Institute,
Móstoles, Spain
Ana I. Torres Facultad de Ingenierı́a, Instituto de Ingenierı́a Quı́mica,
Universidad de la República, Montevideo, Uruguay
Heather L. Trajano Department of Chemical and Biological Engineering,
University of British Columbia, Vancouver, BC, Canada
Shuntaro Tsubaki Department of Chemical Science and Engineering, School of
Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo, Japan
Tadaharu Ueda Department of Marine Resource Science, Faculty of Agriculture
and Marine Science, Kochi University, Kochi, Japan
Adriaan van Heiningen Department of Chemical and Biological Engineering,
University of Maine, Orono, ME, USA
Jesús Velazquez-Lucio Biorefinery Group, Food Research Department, School of
Mexico City, Mexico
Yuji Wada Department of Chemical Science and Engineering, School of
Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo, Japan
Ola Wallberg Department of Chemical Engineering, Lund University, Lund,
Sweden
Charles E. Wyman Chemical and Environmental Engineering Department,
Center for Environmental Research and Technology, University of California
Riverside, Riverside, CA, USA
Ling-Ping Xiao Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing
xxii Contributors
State Key Laboratory of Pulp and Paper Engineering, South China University of
Technology, Guangzhou, China
Eduardo Ximenes Laboratory of Renewable Resources Engineering, Purdue
University, West Lafayette, IN, USA
Lafayette, IN, USA
Remedios Yán ~ez Faculty of Science, Department of Chemical Engineering,
University of Vigo, Ourense, Spain
Bin Yang Bioproduct Sciences and Engineering Laboratory, Department of
Biological Systems Engineering, Washington State University, Richland, WA,
USA
Yusuke Yasukawa Nippon Paper Industries Co. Ltd., Tokyo, Japan
Zhaoyang Yuan Department of Chemical and Biological Engineering, University
of British Columbia, Vancouver, BC, Canada
Elisa Zanuso Biorefinery Group, Food Research Department, School of
Mexico City, Mexico
About the Authors
Héctor A. Ruiz obtained his Ph.D. in chemical

and biological engineering from the Centre of
Biological Engineering at the University of
Minho, Portugal, in 2011. Then, 1 year later, he
worked as postdoctoral researcher at the Univer-
sity of Minho (Portugal) and University of Vigo
(Spain) under the supervision of Prof. José
A. Teixeira and Prof. Juan C. Parajó (2012). He
is currently full professor in the School of Chem-
istry at the Autonomous University of Coahuila
and founder of the biorefinery group in the Food
Research Department, Saltillo, Coahuila, Mexico,
and leader of the pretreatment step in the Cluster of Bioalcohols in the Mexican
Centre for Innovation in Bioenergy (Cemie-Bio), Mexico. Dr. Ruiz is currently the
leader of the biorefinery group that is actively working on the development of
biorefinery strategies for the production of high added-value compounds and
bioethanol from lignocellulosic and macroalgal biomass. His research has been
specifically on hydrothermal processing (autohydrolysis) and biorefinery strategies
for the production of high added-value compounds and bioethanol from lignocel-
lulosic, micro-macroalgal biomass. Dr. Ruiz has conducted several research stays
and technical visits: at the Federal University of Sergipe (Brazil); Brazilian
Bioethanol Science and Technology Laboratory (CTBE, Brazil); Chemical and
Biological Engineering Department at the University of British Columbia
(Canada); CIEMAT, Renewable Energy Division, Biofuels Unit (Spain); Univer-
sity of Jaén (Spain); Sardar Swaran Singh National Institute of Bio-Energy (India);
and Tokyo Institute of Technology (Japan).
He has authored or co-authored several research publications with an H factor of
14 (Google Scholar Citations). Currently, Dr. Ruiz is editor in chief of the
Bioethanol journal (De Gruyter Open, since 2014) and associate editor of the
BioEnergy Research journal (Springer, since 2015) and participates in the editorial
xxiii
xxiv About the Authors
advisory board of Industrial Crops and Products (Elsevier, since 2013) and the
Biofuel Research Journal. Dr. Ruiz was awarded with the prize “Dr. Carlos Casas
Campillo” of the Mexican Society of Biotechnology and Bioengineering in 2016.
This award aims to encourage young researchers and give recognition to their
contributions to the development of biotechnology and bioengineering in Mexico.
Dr. Mette Hedegaard Thomsen is a Assistant

Professor in the Department of Energy Technology
at the Aalborg University in Esbjerg, Denmark, she
has worked on the utilization of waste products and
aquatic biomass for biofuels and green chemicals
for more than 10 years. MHT has worked closely
with European, American, and Middle Eastern
industries to develop and scale up biorefinery pro-
cesses and has PI experience from several national
and international research projects. MHT is author
and co-author of more than 60 scientific papers
including 38 ISI journal papers, five book chapters,
and several conference contributions in areas
related mainly to bioenergy and biochemical pro-
duction. Major contributions in the field of
biorefineries include application of amylolytic lactic acid bacteria in the production
of biopolymers, being part of the team that developed the acidification process for
grass juice as substrate to produce l-lysine, being part of the team that developed the
demonstration-scale hydrothermal treatment of wheat straw, chemical characteri-
zation and development of conversion processes for many different biomasses,
progress in biomass-to-ethanol fermentation technology, and isolation and appli-
cation of natural antibiotics.
About the Authors xxv
Heather L. Trajano is an assistant professor in the

Department of Chemical and Biological Engineering at
the University of British Columbia in Vancouver,
Canada. She obtained her Ph.D. in chemical engineer-
ing at the University of California Riverside.
Dr. Trajano’s focus is on exploring and harnessing
fundamental knowledge of biomass fractionation and
conversion for maximum economic and environmental
benefit. Specific research interests include (1) funda-
mentals of biomass deconstruction to separate carbohy-
drates from lignin, (2) recovery and purification of
extractives, and (3) heterogeneous catalysis for chemical production. Dr. Trajano
searches for biorefining opportunities that complement existing forestry operations
by utilizing waste streams and by-products.
Dr. Trajano has published numerous articles on biomass pretreatment and
enzymatic hydrolysis in leading biorefining journals including Biotechnology and
Bioengineering, Biotechnology for Biofuels, Bioresource Technology, and Biofuels,
Bioproducts and Biorefining.
Chapter 1
How the Severity Factor in Biomass Hydrolysis
Came About
Esteban Chornet and Ralph P. Overend
The search for a useful index that could provide a simple descriptor of pretreatment
operations motivated us, in the 1970s, to explore the concept of severity in chemical
reactions. The literature showed that industrially there had been numerous efforts to
define such indices. For example, pre-hydrolysis in kraft pulping is an operation
which includes steam and aqueous pretreatment methods similar to those that we
were pursuing in our labs at the time. This
R had been modeled by Brasch and Free via
the P-factor, as well as the H factor ¼ (k(T )/k(373)dt, between times 0 and t, with
the temperature in K, with k being the rate constant which traditionally has been
considered to follow the Arrhenius temperature dependency. Delignification rates
are proportional to the H factor, hence its usefulness in controlling the final pulp
consistency. Outside of wood processing, the high temperature cracking of petro-
leum fractions resulted in similar indexes which had been developed and
implemented in plant operations. With increasing analytical insight into petroleum
chemistry and processing, the cracking indices have gradually been replaced by a
chemical kinetic-based “lumping” approach used for each of the petroleum frac-
tions in a given crude oil.
We felt that a severity index, to be useful, had to be simple and workable using
the rapid computational technologies available to us in 1975 (no personal com-
puters, internet, or smart phones then). Our goals were that an operator with
moderate skills would be able to use such indices to control processes and that
research scientists would have a better tool for experimental design and scale-up.
E. Chornet (*)
Enerkem, Sherbrooke, QC, Canada
CRB Innovations, Sherbrooke, QC, Canada
e-mail: echornet@enerkem.com
R.P. Overend (*)
Biomass & Bioenergy Journal, Elsevier, United Kingdom
e-mail: ROverend12@gmail.com
© Springer International Publishing AG 2017 1

H.A. Ruiz et al. (eds.), Hydrothermal Processing in Biorefineries,
DOI 10.1007/978-3-319-56457-9_1
2 E. Chornet and R.P. Overend
From the P-factor, we migrated to a “severity factor” that used two variables
(temperature and time) and, later, three variables, with the addition of a function
related to acid catalyst activity in hydrothermal treatments of lignocellulosics. This
was important as steam treatments, including “steam explosion,” had become
routine pretreatment methods to release the carbohydrates from wood and straw
to allow their fermentation to ethanol. Data from labs could thus be scaled up to
industrial applications with a certain degree of confidence.
The adoption of the severity factor has become universal in the hydrothermal
processing of biomass. It provides an understandable mapping of the biomass
ultrastructure changes through the sequence of dehydration, alteration of
H-bonding, rupture of C–O–C bonds, as well as of C–C bonds and condensation
reactions as severity is increased. Attempts have been made to introduce the effects
of other variables to account for phenomena such as shear rates, intensity of fluid
dynamic fields, and ultrasound in the deconstruction of biomass. However, the
defining variables to account for such phenomena and their effect in the chemical
processes are not simple and have been incorporated mostly in design configura-
tions that claim enhancements in yields of desired intermediates or products.
The “energy crisis” of the early 1970s triggered the development of alternative
energy sources. Biomass has always been understood as the only “biogenic C”
source that could, progressively, make its place not only in the energy landscape but
also in the bio-economy at large. The societal move toward energy efficiency, clean
energy, and bio-products incorporating an increasing fraction of biogenic C is a
major achievement, which is still in the making. Growing and harvesting biomass in
a sustainable manner, and converting it into useful intermediates from which
marketable bio-products can be made, is the job our generation started and that a
new generation is pursuing from the lab all the way to commercial business
implementation via corporate or entrepreneurial companies. The establishment
(i.e., the fossil C sector) will accept us insofar we are able to create an emerging
biogenic C sector whose products and costs rival those of the fossil sector. Tech-
nology and biogenic C incentives (such a fossil C tax) are key components of the
new societal drive toward sustainability.
Technology pathways are well defined by the spectrum of bio-products required
by society: bio-power, biofuels, biochemicals, biopolymers, etc. The pathways may
involve biological or thermochemical processes or a combination of the two. Other
than the direct use of biomass in bio-power and heat production, all the other
approaches aim at de-structuring the native biomass producing homogenous inter-
mediates to be converted into marketable products by biocatalytic or thermo-
catalytic routes and their combinations.
Hydrothermal treatments are low-severity treatments whose main purpose is to
de-structure the biomass to facilitate its deconstruction into constitutive fractions
(hence the word “fractionation” often used). Such fractions become homogeneous
intermediates (e.g., fermentable sugars). The significance of hydrothermal methods
such as those discussed in this book is their potential to produce the homogenous
intermediates at low cost. However, to accomplish such a goal, the “water” costs
1 How the Severity Factor in Biomass Hydrolysis Came About 3
must be appropriately addressed since the process water will have to be recovered,
treated, and recycled to secure an operational permit.
Alternatives to hydrothermal processes exist and compete with them. These
processes require drying the biomass to 15–20% moisture mass fraction. Once
dried two options are possible: fast pyrolysis and gasification. Pyrolysis converts
the biomass into a bio-oil (directly used in boilers or as feed to fluid catalytic
crackers in petroleum refineries), a water phase (from moisture and dehydration),
and a solid charcoal (known as “char”). Gasification using O2 and steam produces a
rather uniform synthetic gas that can be conditioned to serve as intermediate for
either bio- or thermo-catalytic syntheses. Water is recovered, treated, and recycled.
The difference between the alternatives and hydrothermal treatment is that the
amount of external water used in gasification is much less than that used in
hydrothermal processes.
We have enjoyed the collaboration of many students, colleagues, and yes critics
of the severity concept, yet its utility has been demonstrated over time as this
volume attests. Among the many collaborators, we wish to single out a wonderful
professor whose life was tragically ended in an attack on his Mosque in Quebec
City on January 29, 2017. Khaled Belkacemi was our student during the 1980s as
we tried to get more deeply into understanding why the severity concept works (see:
http://pubs.acs.org/doi/abs/10.1021/ie00059a009), and we wish to dedicate this
introduction to his memory.
Chapter 2
Effect of Hydrothermal Pretreatment
on Lignin and Antioxidant Activity
Andrés Moure, Gil Garrote, and Herminia Domı́nguez
2.1 Introduction
Lignin accounts for up to 30% of the weight of biomass and consists of three basic
structural units, p-coumaryl alcohol, coniferyl alcohol and sinapyl alcohol. Based
on its renewable character, it can be considered a source of phenolics with different
functionalities and properties, offering possibilities for a sustainable production of
higher value-added compounds.
The lignin structure is highly influenced by extraction and separation processes
(Zakzeski et al. 2010). The initial fractionation stage for the separation of lignin is
an important step in biorefinery, and compared with other lignin degradation
methods, the hydrothermal treatment has some advantages (Kang et al. 2013).
During autohydrolysis water is in subcritical state (temperature in the range
100–374.2 C and pressure <22.1 MPa) and behaves as a good solvent for solutes
insoluble at ambient pressure and temperature. Near the critical temperature, the
dissociation constant is three orders of magnitude greater than at ambient temper-
ature, and hot pressurized water has a high reactivity (Brunner 2009). In
autohydrolysis, the cleavage of carbohydrate-lignin bonds increases the lignin
extractability with aqueous alkali or with organic solvents, and decomposition of
lignin would be accelerated and reinforced (Kang et al. 2013). Lignin depolymer-
ization and repolymerization reactions may occur simultaneously during
autohydrolysis (Lora and Wayman 1980; Garrote et al. 2004; Leschinsky et al.
2009). Under harsh conditions, condensation of dissolved lignin, sugar degradation
products and phenolic extractives lead to lignin repolymerization, which has neg-
ative effects on lignin properties and reactivity.
A. Moure • G. Garrote • H. Domı́nguez (*)

Departamento de Enxe~ nerı́a Quı́mica, Universidade de Vigo (Campus Ourense),
Edificio Politécnico, As Lagoas, 32004 Ourense, Spain
e-mail: herminia@uvigo.es
© Springer International Publishing AG 2017 5

H.A. Ruiz et al. (eds.), Hydrothermal Processing in Biorefineries,
DOI 10.1007/978-3-319-56457-9_2
6 A. Moure et al.
During the hydrothermal processing of lignocellulosic materials (LCM), frac-

tionation of biomass takes place, and the liquors obtained may contain sugar
oligomers and/or monomers, sugar degradation products, organic acids, extractives
and phenolics. The saccharidic fraction in the hydrolysates (sugar oligomers and
sugars) has commercial applications as prebiotics (Alonso et al. 2011) or as a
carbon source during fermentation into food additives (Rivas et al. 2002), biofuels
(Garrote et al. 2001a, b) or chemicals (Rivas et al. 2013). Non-saccharide com-
pounds in hydrolysates, decreasing the purity of xylooligosaccharides or inhibiting
the microbial metabolism of sugars in bioconversion processes, should be removed
by physical and/or chemical means (Parajó et al. 1996, 1997; Soto et al. 2011).
Solvent extraction has been successfully addressed, and the ethyl acetate-soluble
fraction of hydrothermal hydrolysates from LCM typically contains phenolic com-
pounds as well as sugar-derived compounds, aliphatic fatty acids and other struc-
tures (Garrote et al. 2007; Castro et al. 2008; Conde et al. 2008). The valorization of
the phenolic fraction, which may be considered a by-product with possible appli-
cation as antioxidant, was proposed for the development of an integrated,
multiproduct process (Cruz et al. 2004, 2005; Garrote et al. 2003, 2004, 2008;
Moure et al. 2005; Rodrı́guez et al. 2008; Alonso et al. 2011). Phenolic compounds
of natural origin showed antioxidant activity and exhibit great potential in replacing
synthetic compounds (Cruz et al. 2001; Garrote et al. 2004; González et al. 2004).
Lignins from steam explosion processes are efficient antioxidants and safe ingre-
dients that can be proposed for use in cosmetic and topical formulations (Vinardell
et al. 2008).
Oxidation decreases consumer acceptability of food and cosmetic products by
destroying nutrients, producing toxic compounds and also changing the sensorial
properties. The controversial toxicological data on the effects of synthetic food
antioxidants and the increasing demand for natural ingredients have favoured the
interest in manufacturing natural antioxidants from various sources (Thorat et al.
2013). Phenolic compounds present in the extractives of waste fractions from
agroindustrial, food and forest activities (Domı́nguez et al. 2001; Moure et al.
2001), and also those in the lignin-soluble fraction recovered in the ethyl acetate
extracts from autohydrolysis liquors of LCM (Cruz et al. 2001; Garrote et al. 2004),
are abundant, renewable and promising sources of antioxidant phenolic compounds.
2.2 Effect of Treatment Conditions in Lignin Solubilization
In hydrothermal processes there are several independent variables that can be

influential in the results:
– Temperature (normal range: 150–220 C)
– Time (normal range: 0–5 h)
– Particle size (normally in a range from some mm to 1–5 cm)
2 Effect of Hydrothermal Pretreatment on Lignin and Antioxidant Activity 7
– Lignocellulosic material concentration (normally measured as liquid to solid

ratio or as consistency)
The main effect of hydrothermal processes, but not the only, is the solubilization
of the hemicellulosic fraction. In order to study the behaviour of the water-
lignocellulosic material system under hydrothermal processing, it is possible to
develop kinetic models to explain the hemicellulose solubilization, including sev-
eral fractions, oligomers, monomers, furfural and others (Garrote et al. 1999,
2001c). These models can be generalized to explain the behaviour of all the
polysaccharide fractions in lignocellulosic material during hydrothermal process
(Yá~nez et al. 2009), facilitating both understanding and prediction of the concen-
tration of many species with time and temperature. These models lead to complex
equations, often impractical, since many kinetic parameters are necessary.
The severity factor or reaction ordinate, R0, was defined by Overend and Chornet
(1987) for the solubilization of hemicelluloses in isothermal hydrothermal treat-
ments as

T 100
R0 ¼ exp t ð2:1Þ
14:75
where R0 is the reaction ordinate (min), T is the temperature of hydrothermal

process ( C) and t is the reaction time (min). This parameter is similar to others
used in pulp and paper industry, as P or H factor in kraft pulping processes. The
simplicity of R0 is useful for an industrial use.
If the hydrothermal process is carried out under non-isothermal conditions,
Eq. (2.1) can be modified as
ð tF
T ðtÞ 100
R0 ¼ exp dt ð2:2Þ
0 14:75
where T(t) is the temperature versus time profile in the considered experiment (with
duration from t ¼ 0 min to t ¼ tF min). Several years later, the same researchers
proposed a relationship between R0 and the kinetic modelling of the hemicellulose
solubilization in an irreversible, pseudohomogeneous, first-order reaction
(Abatzoglou et al. 1992), by means of the following equations:
ðt
T T ref
R0 ¼ exp dt ð2:3Þ
0 ω
C ¼ C0 exp ðkref R0 Þ ð2:4Þ
where C represents the concentration of the hemicellulose remaining in lignocel-

lulosic material, C0 is the initial hemicellulose content, kref is the kinetic coefficient
calculated in “reference” conditions and Tref is the reference temperature, and the
parameter ω is
8 A. Moure et al.
R T ref 2
ω¼ ð2:5Þ
Ea
where R ¼ 8.314 J mol/K and Ea is the activation energy of hemicellulose

solubilization reaction. Although Tref and ω can be varied to obtain a better adjust
of the experimental data (Garrote et al. 2002), it is common to select Tref ¼ 373.15 K
(100 C, at this temperature no substantial hemicellulose hydrolysis occurs) and
ω ¼ 14.75 K, resulting Eq. (2.2) under non-isothermal conditions, the most
common expression for reaction ordinate.
In the presence of a catalyst (as an externally added acid, during acid hydrolysis
treatments), the severity factor was modified by Chornet and coworkers and
denoted as ROH (Abatzoglou et al. 1992; Montané et al. 1994):
ðt
X Xref T T ref
RoH ¼ exp exp dt ð2:6Þ
0 λ Xref ω0
where X is the catalyst concentration (weight fraction), Xref is the reference con-
centration and ω0 and λ are empirical constants. In the case of acid hydrolysis, it is
usually the expression (Abatzoglou et al. 1992; Gütsch et al. 2012):
log R0 pH ð2:7Þ
Due to the wide range of variation of R0, it is common to use it in logarithmic

form, and Chornet and coworkers defined severity as (Lavoie et al. 2010):
S0 ¼ log R0 ð2:8Þ
The severity factor has been successfully applied to the interpretation of hydro-
thermal hemicellulose solubilization; its generalized form is the most widely used
parameter for the study of hydrothermal treatments, also for lignin solubilization
and phenolics generation (Garrote et al. 2002, 2003). Garrote et al. (2004) have
summarized the literature experimental data on the influence of severity on the
fraction of lignin solubilized under mild acid hydrolysis of LCM. Figure 2.1 shows
the percentage of initial lignin extracted with hydrothermal treatments, reported in
recent studies. As a general trend, the amount of lignin removed increases at higher
severities, but two types of behaviour can be observed. In some cases, as in
hydrothermal processes carried out with olive tree pruning (Requejo et al. 2011),
corn stover (Buruiana et al. 2014) or coconut fibre (Gonçalves et al. 2015), the
extraction of lignin is limited (about 10%), and values of S0 > 3.5 do not lead to
higher lignin extraction. In most scientific works, the amount of extracted lignin
continuously increases with severity, reaching values close to 50% of lignin
removal (at severities of S0 ¼ 4.5–5.0). It is remarkable that the type of hydrother-
mal process seems not be very influential in lignin extraction; autohydrolysis
(Gütsch et al. 2012; Martin-Sampedro et al. 2014) or steam explosion (Romanı́
et al. 2013) of E. globulus wood showed similar amounts of extracted lignin at
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to about two hundred young priests and theological students on “The
Personal Qualifications for a Minister of Religion.” The address was
in no important respect different from that which would be suitable on
the same subject for an audience of theological students in England
or the United States; nor did its reception and appropriation seem
any less thorough and sincere.
After inspecting the work in drawing and water-colours of which—so
the posted notice read—“An Exhibition is given in honour of ——,”
Mrs. Ladd returned to Tokyo; but I remained to carry out my purpose
of spending a full day and night among my priestly Buddhist friends.
In our many confidential talks while we were in the relations of
teacher and pupil, the latter had avowed his life-work to be the moral
reform and improved mental culture of the priesthood of his sect. It
had then seemed to me a bold, even an audacious undertaking. But
seeming audacity was quite characteristic of the youth of all those
very men who now, in middle life and old-age, are holding the posts
of leadership in Japan in a way to conserve the best results of the
earlier period of more rapid change. Besides, I knew well that my
pupil had the necessary courage and devotion; for he was not only a
priest but also a soldier, and had been decorated for his bravery in
the Chino-Japanese war. And again, toward the close of the Russo-
Japanese war, when he had been called out with the reserves, he
had once more left the position of priestly student and teacher to
take his place at arms in the defence of his country.
How wholesome and thoroughly educative of their whole manhood
was the training which was being given to these young temple boys,
I had abundant reason to know before leaving the Nichiren College
at Osaki. After tea and welcome-addresses by one of the teachers
and two of the pupils, followed by a response by the guest, an
exhibition of one side of this training was given in the large dining-
hall of the school. For as it was in ancient Greece, so it is now in
Japan; arms and music must not be neglected in the preparation to
serve his country of the modern Buddhist priest. Sword-dancing—
one of the chants which accompanied the action being Saigo’s
celebrated “death song”—and a duet performed upon a flute and a
harp constructed by the performer out of split bamboo and strings of
silk, followed by banzais for their guest, concluded the
entertainment.
Of the nine who sat down to dinner that evening in a private room
belonging to another building of the school, four besides the host
were priests of the Nichiren sect. They constituted the body of the
more strictly religious or theological instructors; the courses in
literature and the sciences being taught for the most part by
professors from the Imperial University or from the private university
founded by Japan’s great teacher of youth, the late Mr. Fukuzawa.
Of the priests the most conspicuous and communicative was proud
to inform me that he had been the chaplain of General Noghi at the
siege of Port Arthur. With reference to the criticisms passed at the
time upon that great military leader he said with evident emotion that
General Noghi was “as wise as he was undoubtedly brave.” This
same priest had also interesting stories to tell of his experiences in
China. In speaking of the ignorance of the teachers of religion in that
country he declared, that of the hundreds of Tâoist priests he had
met, the vast majority could not even read the Chinese ideographs
when he wrote them; and none of the numbers he had known could
make any pretence to scholarship. They were quite universally
ignorant, superstitious, and physically and morally filthy. Among the
Buddhist priests in China, however, the case was somewhat better;
for perhaps three or four in every ten could make some pretence of
education; and there were even a very few who were real scholars.
But neither Tâoists nor Buddhists had much influence for good over
the people; and “priest, priest,” was a cry of insult with which to
follow one. As to their sincerity, at one of the Tâoist temples he had
asked for meat and wine, but had been told that none could be had,
because they abstained religiously from both. But when he replied
that he had no scruples against either, but needed them for his
health and wished to pay well for them, both were so quickly
produced he knew they could not have come from far away. (I may
remark in this connection that if the experiences and habits of the
Chinese in Manchuria resemble at all closely the experiences and
customs of the Koreans in their own country, the unwillingness to
furnish accommodations to travelling strangers is caused rather by
the fear of having them requisitioned without pay than to any
scruples, religious or otherwise, as to what they themselves eat and
drink or furnish to others for such purposes).
The same subject which had been introduced at the priests-house,
on occasion of the all-night festival at Ikegami, was now brought
forward again. What had been my impressions received from the
spectacle witnessed at that time? When to the inquiry I made a
similar answer,—namely, that only a portion of the vast crowd
seemed to be sincere worshippers, but that with the exception of a
few rude young men in the procession, who appeared to have had
too much saké, I saw no immoral or grossly objectional features—all
the priests expressed agreement with my views. Where the
superstitions connected with the celebration were not positively
harmful, it was the policy of the reforming and progressive party of
the sect to leave them to die away of themselves as the people at
large became more enlightened.
After a night of sound sleep, Japanese fashion, on the floor of the
study in my pupil’s pretty new home, we rose at six and hastened
across the fields to attend the morning religious services in the
chapel of the school. Here for a full half-hour, or more, what had
every appearance of serious and devout religious worship was held
by the assembled teachers and pupils. All were neatly dressed in
black gowns; no evidences of having shuffled into unbrushed
garments, with toilets only half-done or wholly neglected, were
anywhere to be seen, nor was there the vacant stare, the loud
whisper, the stolen glance at newspaper or text-book; but all
responded to the sutras and intoned the appointed prayers and
portions of the Scriptures, while the time was accented by the not too
loud beating of a musical gong. Certainly, the orderliness and
apparent devotion quite exceeded that of any similar service at
“morning prayers” in the average American college or university.
A brief exhibition of judo, (a modified form of jiujitsu), and of
Japanese fencing, which was carried on in the dining-room while the
head-master was exchanging his priestly for his military dress, in
order to take part in a memorial service to deceased soldiers, at
which General Noghi was expected to be present, terminated my
entertainment at this Buddhist school for the training of temple boys.
As we left the crowd of them who had accompanied us thus far on
the way, and stood shouting banzais on the platform of the station,
there was no room for doubting the heartiness of their friendly feeling
toward the teacher of their teacher; although the two, while sharing
many of the most important religious views, were called by names
belonging to religions so different as Christianity and Buddhism.
The impressions from these two visits to Ikegami regarding the
changes going on in Buddhistic circles in Japan, and in the attitude
of Buddhism toward Christianity, were amply confirmed by
subsequent experiences. At Kyoto, the ancient capital and religious
centre of the empire, I was invited by the Dean of the Theological
Seminary connected with the Nishi Honwangi to address some six
hundred young priests of various sects on the same topic as that on
which the address was given at the Nichiren College near Ikegami. It
should be explained that this temple is under the control of the Shin-
shu, the most numerous and probably the most wealthy sect in the
Empire. The high priest of this sect is an hereditary count and
therefore a member of the House of Peers. He is also a man of
intelligence and of a wide-spreading interest in religion. At the time of
my visit, indeed, the Count was absent on a missionary tour in
China. This address also was listened to with the same respectful
attention by the several hundred Buddhist priests who had gathered
at the temple of Nishi Honwangi. Here again Mrs. Ladd and I were
made the recipients of the same courteous and unique hospitality.
Before the lecture began, we were entertained in the room which
had been distinguished for all time in the estimate of the nation by
the fact that His Majesty the Emperor held within its walls the first
public reception ever granted to his subjects by the Mikado; and after
the lecture we were further honoured by being the first outsiders ever
invited to a meal with the temple officers within one of the temple
apartments.
Later on at Nagoya, further evidence was afforded of the important
fact that the old-time religious barriers are broken down or are being
overridden, wherever the enlightenment and moral welfare of the
people seem likely to be best served in this way. Now Nagoya has
hitherto been considered one of the most conservative and even
bigoted Buddhist centres in all Japan. Yet a committee composed of
Buddhists and of members of the Young Men’s Christian Association
united in arrangements for a course of lectures on education and
ethics. This was remarked upon as the first instance of anything of
the sort in the history of the city.
When we seek for the causes which have operated to bring about
these important and hopeful changes in the temper and practises of
the Buddhism which is fast gaining currency and favour in Japan, we
are impressed with the belief that the greatest of them is the
introduction of Christianity itself. This influence is obvious in the
following three essential ways. Christian conceptions and doctrines
are modifying the tenets of the leading Buddhistic thinkers in Japan.
As I listened for several hours to his exposition of his conception of
the Divine Being, the divine manner of self-revelation, and of his
thoughts about the relations of God and man, by one of the most
notable theologians of the Shin Shu (the sect which I have already
spoken of as the most popular in Japan), I could easily imagine that
the exponent was one of the Alexandrine Church-Fathers, Origen or
Clement, discoursing of God the Unrevealed and of the Logos who
was with God and yet who became man. But Buddhism is also giving
much more attention than formerly to raising the moral standards of
both priests and people. It is sharing in the spirit of ethical quickening
and revival which is so important an element of the work of Christian
missions abroad, but which is alas! so woefully neglected in the so-
called Christian nations at home. Japanese Buddhism is feeling now
much more than formerly the obligation of any religion which asks
the adherence and support of the people, to help the people, in a
genuine and forceful way, to a nobler and better way of living.
Hitherto in Japan it has been that peculiar development of Confucian
ethics called Bushidō, which has embodied and cultivated the nobler
moral ideals. Religion, at least in the form which Buddhism has taken
in Japan, has had little to do with inspiring and guiding men in the life
which is better and best, here and now. But as its superstitions with
regard to the future are falling away and are ceasing practically to
influence the body of the people, there are some gratifying signs that
its influence upon the spiritual interests of the present is becoming
purer and stronger.
That Buddhism is improving its means of educating its followers, and
is feeling powerfully the quickening of the national pulse, due to the
advancing strides in educational development, is obvious enough to
any one able to compare its condition to-day with its condition not
more than a score of years ago. There are, of course, in the ranks of
all the Buddhist sects leaders who are ready to cry out against
heresies and the mischief of changes concealed under the guise of
reforms. The multitudes of believers are still far below the desirable
standard of either intelligence in religious matters, or of morals as
controlled by religious motives. But the old days of stagnation and
decay seem to be passing away; and the outlook now is that the
foreign religion, instead of speedily destroying the older native
religion, will have helped it to assume a new and more vigorous and
better form of life.
As the period of more bitter conflict and mutual denunciation gives
way to a period of more respectful and friendly, and even co-
operative attitude in advancing the welfare of the nation, the future of
both Buddhism and Christianity in Japan affords a problem of more
complicated and doubtful character. The nation is awakening to its
need of morals and religion,—in addition to a modern army and
navy, and to an equipment for teaching and putting to practical uses,
the physical sciences,—as never before. The awakening is
accompanied there, as elsewhere in the modern world, by a thirst for
reality. Whatever can satisfy this thirst, however named, will find
acceptance and claim the allegiance of both the thoughtful and the
multitudes of the common people; for in Japan, as elsewhere in the
modern world, men are not easily satisfied or permanently satisfied
with mere names.
CHAPTER X
HIKONÉ AND ITS PATRIOT MARTYR
Among the feudal towns of Japan which can boast of a fine castle
still standing, and of an illustrious lord as its former occupant, there
are few that can rival Hikoné. Picturesquely seated on a wooded hill
close to the shores of Lake Biwa, with the blue waters and almost
equally blue surrounding mountains in full sight, the castle enjoys the
advantages of strength combined with beauty; while the lords of the
castle are descended from a very ancient family, which was awarded
its territory by the great Iyéyasu, the founder of the Tokugawa
Shōgunate, in return for the faithful services of their ancestor,
Naomasa, in bringing the whole land under the Tokugawa rule. They
therefore belonged to the rank of the Fudai Daimio, or Retainer
Barons, from whom alone the Roju, or Senators, and other officers of
the first class could be appointed. Of these lords of Hikoné much the
most distinguished was Naosuké, who signed the treaty with the
United States negotiated in 1857 and 1858. And yet, so strange are
the vicissitudes of history, and so influential the merely incidental
occurrences in human affairs, that only a chance visit of the Mikado
saved this fine feudal castle from the “general ruin of such buildings
which accompanied the mania for all things European and the
contempt of their national antiquities, whereby the Japanese were
actuated during the past two decades of the present régime.” Nor
was it until recent years that Baron Ii Naosuké’s memory has been
rescued from the charge of being a traitor to his country and a
disobedient subject of its Emperor, and elevated to a place of
distinction and reverence, almost amounting to worship, as a clear-
sighted and far-seeing statesman and patriot.
“PICTURESQUELY SEATED ON A WOODED HILL”
However we may regard the unreasonableness of either of these two
extreme views of Naosuké’s character, one thing seems clear. In
respect to the laying of foundations for friendly relations between the
United States and Japan, we owe more to this man than to any other
single Japanese. No one can tell what further delays and resulting
irritation, and even accession of blood-shed, might have taken place
in his time had it not been for his courageous and firm position
toward the difficult problem of admitting foreigners to trade and to
reside within selected treaty-ports of Japan. This position cost him
his life. For a generation, or more, it also cost him what every true
Japanese values far more highly than life; it cost the reputation of
being loyal to his sovereign and faithful to his country’s cause. Yet
not five Americans in a million, it is likely, ever heard the name of
Baron Ii Kamon-no-Kami, who as Tairō, or military dictator, shared
the responsibility and should share the fame of our now celebrated
citizen, then Consul General at Shimoda, Townsend Harris. My
purpose, therefore, is two-fold: I would gladly “have the honour to
introduce” Ii Naosuké to a larger audience of my own countrymen;
and by telling the story of an exceedingly interesting visit to Hikoné, I
would equally gladly introduce to the same audience certain ones of
the great multitude of Japanese who still retain the knightly courtesy,
intelligence and high standards of living—though in their own way—
which characterised the feudal towns of the “Old Japan,” now so
rapidly passing away.
Baron Ii Naosuké, better known in foreign annals as Ii Kamon-no-
Kami, was his father’s fourteenth son. He was born November 30,
1815. The father was the thirteenth feudal lord from that Naomasa
who received his fief from the great Iyéyasu. Since the law of
primogeniture—the only exceptions being cases of insanity or bodily
defect—was enforced throughout the Empire, the early chances that
Naosuké would ever become the head of the family and lord of
Hikoné, seemed small indeed. But according to the usage of the Ii
clan, all the sons except the eldest were either given as adopted
sons to other barons, or were made pensioned retainers of their
older brother. All his brothers, except the eldest, had by adoption
become the lords of their respective clans. But from the age of
seventeen onward, Naosuké was given a modest pension and
placed in a private residence. He thus enjoyed years of opportunity
for training in arms, literature, and reflective study, apart from the
corrupting influences of court life and the misleading temptations to
the exercise of unrestricted authority—both of which are so injurious
to the character of youth. Moreover, he became acquainted with the
common people. That was also true of him, which has been true of
so many of the great men of Japan down to the present time. He
made his friend and counsellor of a man proficient in the military and
literary education of the day. And, indeed, it has been the great
teachers who, more than any other class, through the shaping of
character in their pupils, have influenced mankind to their good. It
was Nakagawa Rokurō who showed to Naosuké, when a young
man, the impossibility of the further exclusion of Japan from foreign
intercourse. It was he also who “influenced the future Tairō to make a
bold departure from the old traditions” of the country.
On the death, without male issue, of his oldest brother, Naosuké was
declared heir-apparent of the Hikoné Baronetcy. And on Christmas
day of 1850 he was publicly authorised by the Shōgunate to assume
the lordly title of Kamon-no-Kami. It is chiefly through the conduct of
the man when, less than a decade later, he came to the position
which was at the same time the most responsible, difficult and
honourable but dangerous of all possible appointments in “Old
Japan,” that the character of Baron Ii must be judged. On the side of
sentiment—and only when approached from this side can one
properly appreciate the typical knightly character of Japanese
feudalism—we may judge his patriotism by this poem from his own
hand:
Omi no mi kishi utsu nami no iku tabimo,

Miyo ni kokoro wo kudaki nuru kana;
or as freely translated by Dr. Griffis:—
“As beats the ceaseless wave on Omi’s strand

So breaks my heart for our beloved land.”
(Omi is the poetical appellation of Lake Biwa, on which the feudal

castle of the lords of Hikoné has already been said to be situated.)
How the sincerity of this sentiment may be reconciled with the act
which for an entire generation caused the baron to be stigmatised a
traitor is made clear through the following story told by the great
Ōkubo. In the troubled year of 1858, the Viscount, just before
starting on an official errand to the Imperial Court at Kyoto, called on
Baron Ii, who was then chief in command under the Shōgun, to
inform him of his expected departure on the morrow. He had
embodied his own views regarding the vexed question of foreign
affairs, on his “pocket paper,” in the form of a poem. This paper the
Viscount handed to the Baron and asked him whether his views
were the same as those of the poem. Having carefully read it Ii
approved and instructed Ōkubo to act up to the spirit of the poem,
which reads:
“However numerous and diversified the nations of the earth may be,
the God who binds them together can never be more than one.”
Whatever differences of view prevailed, between his political
supporters and his political enemies, as to the purity of Naosuké’s
patriotic sentiments, there was little opportunity for difference as to
certain other important elements of his character. He had
conspicuously the qualities needed for taking a position of dictatorial
command in times of turbulence and extreme emergency. Serious in
purpose, but slow in making up his mind, he had undaunted firmness
in carrying out his plans, such that “no amount of difficulties would
make him falter or find him irresolute.”
The burning question of foreign intercourse which the coming of
Commodore Perry had forced upon the Shōgunate in 1853, had
afterward been referred to the barons of the land. They favoured
exclusion by a large majority; and some of them were ready to
enforce it at the expense of a foreign war. But the recent experience
of China at the hands of the allied forces was beginning to teach the
Far East that lesson of preparedness by foreign and modern
education which Japan has since so thoroughly learned; and to the
fuller magnitude of which China herself is just awakening. To take
the extreme position of complete and final resistance to the demands
of the foreign forces seemed obviously to court speedy and
inevitable ruin for the country at large. Yet none of the barons,
except the Baron of Hikoné, had a plan to propose by which to
exclude alike the peaceful foreigner come to trade and the armed
foreigner come to enforce his country’s demand for peaceful
intercourse by the use of warlike means.
It is interesting to notice that Naosuké answered the question of the
Shōgunate in a manner to indicate the consistent policy of his
country from 1853 down to the present time. He did not, it is
probable, love or admire the personality of the foreign invader more
than did his brother barons; or more than does the average Chinese
official at the present time. On consulting with his own retainers, he
found the “learned Nakagawa” the sole supporter of his views. All the
clan, with the exception of this teacher and scholar, favoured
exclusion at any cost. “The frog in the well knows not the great
ocean,” says the Japanese proverb. And as to the Japanese people,
who at that time were kept “in utter ignorance of things outside of
their own country,” Count (now Prince) Yamagata said in 1887, with
reference to the superior foresight of Baron Ii: “Their condition was
like that of a frog in a well.”
In spite of the almost complete loneliness of his position among the
barons of the first rank, Naosuké advised the Shōgunate that the
tendencies of the times made it impossible longer to enforce the
traditional exclusiveness of Japan. But he also—and this is most
significant of his far-sighted views—advised the repeal of the law,
issued early in the seventeenth century, which prohibited the building
of vessels large enough for foreign trade; and this advice he coupled
with the proposal that Japan should build navies for the protection, in
future, of her own coasts. “Thus prepared,” he writes, “the country
will be free from the menaces and threatenings of foreign powers,
and will be able to uphold the national principle and polity at any
time.”
The division of opinion, and the bloody strifes of political parties, in
Japan, over the question of exclusion were not settled by the
Convention for the relief of foreign ships and sailors which followed
upon the return of the war-ships of the United States, and of other
foreign countries, in 1854. Quite the contrary was the truth. When
Mr. Townsend Harris arrived as Consul General in 1856, and began
to press the question of foreign trade and residence in a more
definite form, the party favouring exclusion was stronger, more bitter,
and more extreme than before. In their complete ignorance of the
very nature of a commercial treaty, the rulers of Japan quite
generally mistook the American demand to open Kanagawa, Yedo,
Osaka, Hiogo, and Niigata for an extensive scheme of territorial
aggression. This they were, of course, ready to resist to their own
death and to the ruin of the country. When the senators prepared a
memorial to the Imperial Cabinet, stating their difficulty and the
necessity of conforming to the foreign demand, and sent it to the
Imperial Capital by the hand of their president, Baron Hotta, they
were therefore instructed to delay, and to consult further with the
Tokugawa Family and with the Barons of the land, before again even
venturing to refer the matter to the Government at Kyoto. These
instructions were, under the circumstances, equivalent to a flat and
most dangerous refusal to allow the opening of the country at all.
It has not been generally recognised in his own country, how
extremely important and yet how difficult was the position of Mr.
Townsend Harris during the years, 1857-1858. Nor has he, in my
judgment, been awarded his full relative share of credit for laying in
friendly foundations the subsequent commercial and other forms of
intercourse between the United States and Japan. Mr. Harris’ task
was in truth larger and more complicated than that of Commodore
Perry. The factors of Japanese politics opposed to its
accomplishment were more manifold and vehement. Moreover, the
question of foreign intercourse was then complicated by two other
questions of the most portentous magnitude for the internal politics
and political development of Japan. These were, the question of who
should be the heir-apparent to the then ruling Shōgun; and the yet
more important, and even supremely important question of how the
Shōgunate should in the future stand related to the virtual—and not
merely nominal—supremacy of the Imperial House. The opposition
on both these questions was substantially the same as the
opposition to permitting foreign trade and residence in the land. If
then Commodore Perry deserves the gratitude of all for making the
first approaches, in a way without serious disruption and lasting
hatred, to begin the difficult task of opening Japan, Townsend Harris
certainly deserves no less gratitude for enlarging and shaping into
more permanent form the same “opening,” while quite as skilfully
and effectively avoiding the exasperation of similar and even greater
political evils.
His many embarrassments forced upon the somewhat too timid and
hesitating Shōgun the necessity of selecting some one man upon
whom the responsibility and the authority for decisive action could be
confidently reposed. Seeing this man in the person only of Ii Kamon-
no-Kami, Lord of Hikoné, he appointed him to the position of Tairō.
Now, this position of Tairō, or “Great Elder,” which may be
paraphrased by “President-Senator,” was one of virtual dictatorship.
Only the Shōgun, who appointed him, could remove the Tairō or
legally resist his demands. Naosuké was the last to hold this office;
for fortunately for Japan the Shōgunate itself soon came to an end;
but he will be known in history as Go-Tairō,—the dictator especially
to be honoured, because he was bold, clear-sighted, and ready to
die in his country’s behalf. On June 5, 1858, Baron Ii was installed in
the position which gave him the power to conclude the treaty, and
which at the same time made him responsible for its consequences
of weal or woe, to individuals and to the entire nation,—even to the
world at large. In this important negotiation the Japanese Baron
Naosuké, and the American gentleman, Harris, were henceforth the
chief actors.
It is not my intention to recite in detail the history of the negotiations
of 1858, or of the difficulties and risks which the Tairō had to face in
his conduct of them. While the Mikado’s sanction for concluding the
treaty with Mr. Harris was still anxiously awaited, two American men-
of-war arrived at Shimoda; and a few days later these were followed
by Russian war-ships and by the English and French squadrons
which had so recently been victorious in their war with China. It was
by such arguments that America and Europe clinched the consent of
reluctant Japan to admit them to trade and to reside within her
boundaries!
It seemed plain enough now that the Yedo Government could not
longer wait for permission from the Imperial Government to abandon
its policy of exclusion. Two of its members, Inouyé and Iwasé, were
forthwith sent to confer with the Consul General at Shimoda. When
Mr. Harris had pointed out the impossibility of continuing the policy of
exclusion, the dangers of adhering obstinately to the traditions of the
past, and had assured them of America’s friendly intervention to
secure favourable terms with the other powers of the West, the
commissioners returned to Yedo to report. But still the opposing
party grew; and still the Imperial Government delayed its consent.
Meantime the bitterness against Baron Ii was increased by the
failure of his enemies to secure the succession to the Shōgunate for
their favoured candidate. None the less, the Tairō took upon himself
the responsibility of despatching the same men with authority to sign
that Convention between the United States and Japan which, in spite
of the fact that it bore the name of the “Temporary Kanagawa Treaty”
and was subject to revision after a specified term of years, remained
unchanged until as late as 1895. This important event bore date of a
little more than a half-century ago—namely, July 29, 1858.
It is foreign to my purpose to examine the charges, urged against Ii
Kamon-no-Kami, of disobedience to the Imperial Government and of
traitorous conduct toward his country. The latter charge has long
since been withdrawn; and for this has been substituted the praise
and homage due to the patriot who is able to oppose public opinion,
to stand alone, to be “hated even by his relatives,” and to sacrifice
his life in his country’s behalf. That the Tairō did not obey the
Imperial command to submit again the question of exclusion to a
council of the Tokugawa princes and the Barons of the land is indeed
true. On the other hand, it is to be said that the Imperial Government,
by not forbidding the Treaty, had thrown back upon the Shōgunate
the responsibility for deciding this grave question; and that the
appearance of the foreign war-ships gave no further opportunity, in
wisdom, for continuing the policy of procrastination and delay. The
hour demanded a man of audacity, of clear vision into the future, and
of willingness to bear the full weight of a responsible decision. The
hour found such a man in the Japanese Naosuké, hereditary feudal
lord of Hikoné, but by providence in the position of Tairō, or military
dictator. It was fortunate, indeed, for the future relations of the United
States and Japan, and for the entire development of the Far East
under European influences, that an American of such patience,
kindliness, tactful simplicity, and sincere moral and religious
principle, met at the very critical point of time a Japanese of such
knightly qualities of honour, fearlessness, and self-centred force of
character. This point of turning for two political hemispheres, this
pivot on which swung the character of the intercourse between Far
East and Occident, owes more, I venture to think, to Townsend
Harris and to Ii Kamon-no-Kami than to any other two men.
The concluding of the Treaty did not allay the excitement of the
country over the intrusion of foreigners, or discourage the party of
the majority which favoured the policy of either risking all in an
immediate appeal to arms, or of continuing the effort to put off the
evil day by a policy of prevarication and temporising. Less than a
fortnight after its signing, the Shōgun became suddenly ill, and four
days later he died. Two days before his death, the three English
ships had anchored at Shinagawa, a suburb of the capital of the
Shōgunate; while the Russians had invaded the city of Yedo itself
and established themselves in one of its Buddhist temples.
Everything was now in confusion. The influence of the party for
exclusion—forceful, if necessary—was now greatly strengthened
among the Imperial Councillors at Kyoto; and intrigues for the
deposition of the Tairō and even for his assassination went on
apace. A serious and wide-spreading rebellion was threatened. The
resort of the Baron of Hikoné to force in order to crush or restrain his
enemies served, as a natural and inevitable result, to combine them
all in the determination to effect his overthrow—a result which his
opponents suggested he should forestall by committing harakiri, after
acknowledging his mistakes; and which his friends urged him to
prevent by resigning his office at Tairō.
Since Ii Kamon-no-Kami was not the man to retreat in either of these
two cowardly ways, he was destined to perish by assassination. On
March 25, 1860, one of the five annual festivals at which the princes
and barons of the land were in duty bound to present themselves at
the Shōgun’s Castle to offer congratulations, the procession of the
Tairō left his mansion at “half-past the fifth watch,” or 9 o’clock a. m.
Near the “Cherry-Field” gate of the castle, they were attacked by
eighteen armed men, who were all, except one, former retainers of
the Mito Clan, whose princes had been the most powerful enemy of
Baron Ii, but who had resigned from the clan, and become ronin, or
“wave-men,” in order not to involve in their crime the lord of the clan.
The suddenness of the attack, and the fact that the defenders were
impeded by the covered swords and flowing rain-coats which the
weather had made necessary, gave the attacking party a temporary
advantage. Baron Ii was stabbed several times through the sides of
his palanquin, so that when dragged out for further wounding and
decapitation, he was already dead. Thus perished the man who
signed the treaty with Townsend Harris, fifty years ago, in the forty-
sixth year of his age.
The motives of the two parties—that of the majority who favoured
exclusion and that of the minority who saw the opening of the
country to be inevitable—can best be made clear by stating them in
the language of each, as they were proclaimed officially to the
Japanese of that day. Fortunately, we are able to do this. So bitter
was the feeling against their feudal lord, even after his death, that it
seemed necessary, in order to prevent complete ruin from falling
upon the whole Clan of Hikoné, that all his official papers and
records should be burned. But Viscount Ōkubo, at no inconsiderable
danger to himself, managed “to save the precious documents”; for,
said he, “There will be nothing to prove the sincerity and unmixed
fidelity of Lord Naosuké, if the papers be destroyed. Whatever may
come I dare not destroy them.”
From one of these papers we quote the following sentences which
show why Baron Ii as Tairō signed, on his own responsibility, this
detested treaty with the hated and dreaded foreigners. “The question
of foreign intercourse,” it says, “is pregnant with serious
consequences. The reason why the treaty was concluded with the
United States was because of the case requiring an immediate
answer. The English and French Squadrons, after their victory over
China, were very soon expected to our coasts; and the necessity of
holding conferences with different nations at the same time might
cause confusion from which little else than war could be expected.
These foreigners are no longer to be despised. The art of navigation,
their steam-vessels and their military and naval preparations have
found full development in their hands. A war with them might result in
temporary victories on our part; but when our country should come to
be surrounded by their combined navies, the whole land would be
involved in consequences which are clearly visible in China’s
experience.... Trying this policy for ten or twelve years, and making
full preparation for protection of the country during that period, we
can then determine whether to close up or open the country to
foreign trade and residence.... If it were only one nation with which
we had to deal, it would be much easier; but several nations, coming
at this time with their advanced arts, it is entirely impossible to refuse
their requests to open intercourse with our country. The tendency of
the times makes exclusion an entire impossibility.”
But the assassins, on their part, before entering on their bloody
deed, had drawn up a paper which, as signed by seventeen, or all
except one of their number, they wished to have go down to posterity
in justification of their course. They, too, all met death either on the
spot, or subsequently by public execution, for their crime of
assassination. “While fully aware,” says this manifesto, “of the
necessity of some change in policy since the coming of the
Americans to Uraga, it is entirely against the interest of the country
and a shame to the sacred dignity of the land, to open commercial
relations, to admit foreigners into the castle, to conclude a treaty, to
abolish the established custom of trampling on the picture of Christ,
to permit foreigners to build places of worship of their evil religion,
Christianity, and to allow three Foreign Ministers to reside in the
land. Under the excuse of keeping the peace, too much compromise
has been made at the sacrifice of national honour. Too much fear
has been shown in regard to the foreigners’ threatening.”
This remarkable paper then goes on to charge the Tairō, Baron Ii,
with being responsible for so dishonourable an act of compromise.
He has assumed “unbridled power”; he has proved himself “an
unpardonable enemy of his nation,” a “wicked rebel.” “Therefore we
have consecrated ourselves to be the instruments of Heaven to
punish this wicked man; we have assumed on ourselves the duty of
putting an end to a serious evil by killing this atrocious autocrat.” The
assassins then go on to swear before Heaven and earth, gods and
men, that their act was motived by loyalty to the Emperor, and by the
hope to see the national glory manifested in the expulsion of
foreigners from the land.
At this distance of half a century, and considering the spirit of the
former age, we need not judge between Naosuké and his murderers
as regards the sincerity of their patriotism. But as to which of the two
parties followed the path of wisdom, there can be no manner of
doubt. Both Japan and its foreign invaders still owe a great debt of
gratitude and a tribute of wisdom, to Baron Ii Kamon-no-Kami. While
over all our clouded judgment hangs serene the truth of the
autograph of four Chinese characters with which, years afterwards,
the Imperial Prince Kitashirakawa honoured the book written to
vindicate the Tairō: “Heaven’s ordination baffles the human.”
How the memory of its former feudal lord is cherished in Hikoné, and
how his spirit still survives and in some sort dominates its citizens, I
had occasion to know during two days of early February, 1907. The
little city, headed by Mr. Tanaka, the steward of the present Count Ii,
by letter and then by a personal visit from the Christian pastor, Mr.
Sonoda, had urgently invited us to visit them, with the promise that
we should see the castle and other reminders of its former feudal
lord. I, on my part, was to speak to them on education and morality,
the two subjects about which the serious people of Japan are just
now most eager to hear. The same gentleman who had been the
medium of the invitation, was to be our escort from Kyoto to Hikoné.
But on the way, although the wind was piercing and light snow was
falling, we saw again the familiar objects of interest about the lower
end of Lake Biwa;—Miidera Temple, with its relics of the legendary
giant Benkei, such as the bell which he carried part way up the hill
and then dropped and cracked, and the huge kettle out of which he
ate his rice; then the wonderful pine-tree at Karasaki, the sail down
the lake and under the bridge of Seta; and, finally, the sights of
Ishiyama.
At a tea-house near the station here we were met by Mr. Tanaka,
who had come by train to extend the welcome of the city and who
emphasised this welcome by referring to the interest which we, as
Americans, in common with all our countrymen, must feel in the
place that had been the residence of the great Tairō. For had not he
“influenced the Shōgunate to open the country to the United States,
and lost his life for his advanced views?”
As the train conveyed us into the uplands, the snow began to fall
more heavily until it lay nearly a foot deep upon the plain and
wooded hill, crowned with its castle, of the ancient feudal town. Just
as the setting sun was making the mountains and the clouds aglow
with a rose colour, as warm and rich as anything to be seen in
Switzerland, we reached the station of Hikoné, and were at once
taken into its waiting-room to receive and return greetings of some
thirty of the principal citizens who had come out to welcome the city’s
guests. On account of the deep snow it was a jinrikisha ride of nearly
half an hour to the place where we were to be lodged—the Raku-
raku-tei, just beside the castle-moat, under its hill, and almost in the
lake itself. Here a beautiful but purely Japanese house, which was
built by the lord of the castle as a villa, stands in one of the finest
gardens of all Japan.
The fear that their foreign guests would not be entirely comfortable,
even if entertained in the best Japanese style, made it difficult for us
at first to discard or neglect the accessories especially provided, and
disport ourselves as though we were really cherishing, and not
feigning, the wish to be treated by them as their feudal lord would
have treated his friends at the beginning of the half century now
gone by. In the end, however, we succeeded fairly well in the effort to
merge ourselves, and our modern Western habits and feelings, in
the thoughts, ways and emotions of the so-called “Old Japan.”
Flags were hung over the quaint Japanese doorway of the villa; and
the manager, the landlord, and all the servants, were in proper array
to greet the long line of jinrikishas which were escorting the guests.
Our shoes removed, we were ushered through numerous rooms and
corridors, made attractive with the quiet beauty of choice screens
and the finest of mats, into the best apartment of the house. Here
bright red felt had been spread over the mats; a tall lacquer hibachi,
daimyo style, stood in the middle of the chamber; and large lacquer
or brass candlesticks, with fat Hikoné candles and wicks nearly a
half-inch thick, stood on either side of the hibachi and in each of the
corners of the room.
Thus far, the surroundings were well fitted to carry our imaginations
back to the time of Ii Kamon-no-Kami himself. But there were two
articles of the furnishing sure to cause a disillusionment. These were
a pair of large arm-chairs, arranged throne fashion behind the
hibachi, and covered with green silk cushions (or zabuton) which
were expected to contribute both to our comfort and to our sense of
personal dignity, while we were “officially receiving”—so to say.
Without offending our kind hosts, I trust, and certainly to the increase
of our own satisfaction, we begged permission to slip off from our
elevated position, so calculated to produce the feelings of social

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Textbook Hydrothermal Processing in Biorefineries Production of Bioethanol and High Added Value Compounds of Second and Third Generation Biomass 1St Edition Hector A Ruiz Ebook All Chapter PDF

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Hydrothermal Processing in

Biorefineries Production of Bioethanol

Theoretical and Applied Aspects of Biomass Torrefaction

New polymers for encapsulation of nutraceutical

Advances of Basic Science for Second Generation

Climate Change Photosynthesis and Advanced Biofuels The

Biomass as Renewable Raw Material to Obtain Bioproducts

Thermochemical conversion of biomass for the production

Biotechnological Production of Bioactive Compounds 1st

Production of Materials from Sustainable Biomass

ISBN 978-3-319-56456-2 ISBN 978-3-319-56457-9 (eBook)

Library of Congress Control Number: 2017941184

© Springer International Publishing AG 2017

Printed on acid-free paper

This Springer imprint is published by Springer Nature

Biomass from lignocellulosic and aquatic material is seen as an interesting source

autohydrolysis, hydrothermal pretreatment, hot compressed water, hydro-

Saltillo, Coahuila, Mexico Héctor A. Ruiz

1 How the Severity Factor in Biomass Hydrolysis Came About . . . . 1

8 Hydrothermal Pretreatment: Process Modeling

18 Minimizing Precipitated Lignin Formation and Maximizing

Cristóbal N. Aguilar Biorefinery Group, Food Research Department, School of

Jingqian Chen Department of Chemical and Biological Engineering, University

Patricia Gullón Chemical and Environmental Engineering Department,

Ayumu Onda Research Laboratory of Hydrothermal Chemistry, Faculty of

College of Food Engineering and Biotechnology, Tianjin University of Science and

Héctor A. Ruiz obtained his Ph.D. in chemical

Dr. Mette Hedegaard Thomsen is a Assistant

Heather L. Trajano is an assistant professor in the

Esteban Chornet and Ralph P. Overend

© Springer International Publishing AG 2017 1

Andrés Moure, Gil Garrote, and Herminia Domı́nguez

A. Moure • G. Garrote • H. Domı́nguez (*)

© Springer International Publishing AG 2017 5

During the hydrothermal processing of lignocellulosic materials (LCM), frac-

2.2 Effect of Treatment Conditions in Lignin Solubilization

In hydrothermal processes there are several independent variables that can be

– Lignocellulosic material concentration (normally measured as liquid to solid

where R0 is the reaction ordinate (min), T is the temperature of hydrothermal

where C represents the concentration of the hemicellulose remaining in lignocel-

where R ¼ 8.314 J mol/K and Ea is the activation energy of hemicellulose

Due to the wide range of variation of R0, it is common to use it in logarithmic

Omi no mi kishi utsu nami no iku tabimo,

or as freely translated by Dr. Griffis:—

“As beats the ceaseless wave on Omi’s strand

(Omi is the poetical appellation of Lake Biwa, on which the feudal

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