Production of monomeric aromatics/phenolics from hydrolysis lignin

282 Pages·2017·5.22 MB·English

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Hooman Paysepar, The University of Western Ontario
Supervisor: Xu, Chunbao (Charles), The University of Western Ontario
A thesis submitted in partial fulfillment of the requirements for the Doctor of Philosophy degree
in Chemical and Biochemical Engineering
© Hooman Paysepar 2018
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Paysepar, Hooman, "Production of monomeric aromatics/phenolics from hydrolysis lignin (HL) by
catalytic fast pyrolysis and hydrothermal liquefaction" (2018). Electronic Thesis and Dissertation
Repository. 5381.
https://ir.lib.uwo.ca/etd/5381
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Abstract
Bio-oil, produced from bio-feedstocks by thermochemical conversion technologies (e.g.,
pyrolysis or direct liquefaction), can be renewable replacement for petroleum for energy and
chemical production. However, bio oil has high oxygen content, low stability, and low heating
value. Thus, upgrading of bio-oil is necessary to remove the oxygen and make it a suitable
substitute for conventional liquid transportation fuels or for value-added bio-based chemicals.
Oxygen in a bio-oil can be removed by catalytic cracking or hydro-de-oxygenation to the form
of H O, CO and CO in the presence of a catalyst.
2 2
The overall objective of this PhD project was to develop novel technical solutions to production
of monomeric aromatics/phenolics from hydrolysis lignin (HL) – a residue from cellulosic
ethanol plants, for potential applications as fuels, fuel additives and chemicals. In this PhD
thesis work, a catalytic fast pyrolysis (CFP) reactor system was in-house designed and
constructed, and some novel zeolite-based solid acid catalysts with tailored strengths of acidity
and improved resistance to carbon/coke deposition, such as acidified ZSM-5 catalysts, were
developed to achieve a high yield (151 mg/g-HL) at a mild pyrolysis temperature (450C). In
addition, hydrothermal liquefaction (HTL) – an emerging technology for biomass conversion
under milder temperature (at 350C for 30 min) was employed to produce biocrude from
hydrolysis lignin (HL) in water-ethanol (50:50, v/v) mixture with hematite ore as the catalyst.
More importantly, the phenolics of the HL-derived biocrude was extracted and the phenolic
extracts were used a bio-substitute to phenol for the synthesis of bio-phenol formaldehyde
(BPF) resoles as wood adhesives. The dry bonding strengths of BPF resoles prepared with the
phenolic extracts are higher than that of the BPF resoles prepared with the whole biocrude oils
and the neat PF resole.
Keywords

Bio-oil, heavy oil (HO), hydrolysis lignin (HL), Xilinguole lignite (XL), fast pyrolysis (FP),
catalytic fast pyrolysis (CFP), hydrothermal liquefaction (HTL), co-liquefaction, zeolite-X,
zeolite-Y, H-ZSM-5, ZSM-5, hematite, iron ore, resin, phenol formaldehyde (PF) resole, bio
oil phenol formaldehyde (BPF) resole, phenol extract (PE).
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Co-Authorship Statement
Chapter 3: Catalytic fast pyrolysis of hydrolysis lignin for the production of
aromatic/phenolic fuels or chemicals
Authors: Paysepar, H., Rao, K.T.V., Yuan, Z., Shui, H., and Xu, C.
The experiment work was conducted by Hooman Paysepar under supervision of Prof. Charles
(Chunbao) Xu and Prof. Hengfu Shui, and the guidance of Dr. Kasanneni Tirumala
Venkateswara Rao and Dr. Zhongshun Yuan. Writing and data analysis of this publication
were conducted by Hooman Paysepar. It was reviewed and revised by Prof. Charles Xu and
Prof. Hengfu Shui. The manuscript is ready for submission to “Fuel”.
Chapter 4: Co-liquefaction of lignin and lignite coal for aromatic liquid fuels and
chemicals in mixed solvent of ethanol-water in the presence of hematite ore
The experiment work was conducted by Hooman Paysepar under the supervision of Prof.
Charles (Chunbao) Xu, Prof. Hengfu Shui, and Prof. Shibiao Ren, and guidance of Dr. Shigang
Kang. Writing and data analysis of this publication were conducted by Hooman Paysepar. It
was reviewed and revised by Prof. Charles Xu and Prof. Shibiao Ren. The manuscript was
submitted to “Analytical and Applied Pyrolysis”.
Chapter 5: Zeolite catalysts screening for production of monomer aromatics/phenolics
from hydrolysis lignin by catalytic fast pyrolysis.
Authors: Paysepar, H., Rao, K.T.V., Yuan, Z., Shui, H., Nazari, L., and Xu, C.
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The experiment work was conducted by Hooman Paysepar under supervision of Prof. Charles
Xu and Prof. Hengfu Shui, and the guidance of Dr. Kasanneni Tirumala Venkateswara Rao
and Dr. Zhongshun Yuan. Writing and data analysis of theis publication were conducted by
Hooman Paysepar. It was reviewed and revised by Prof. Charles Xu and Dr. Hengfu Shui. The
manuscript is ready for submission to a journal for publication.
Chapter 6: Improving activity of ZSM-5 zeolite catalyst for the production of
monomeric aromatics/phenolics from hydrolysis lignin via catalytic fast pyrolysis effect
of acidic.
Authors: Paysepar, H., Rao, K.T.V., Yuan, Z., Shui, H., and Xu, C.
The experiment work was conducted by Hooman Paysepar under supervision of Prof. Charles
Xu and Prof. Hengfu Shui, and the guidance of Dr. Kasanneni Tirumala Venkateswara Rao
and Dr. Zhongshun Yuan. Writing and data analysis of this publication were conducted by
Hooman Paysepar. It was reviewed and revised by Prof. Charles Xu and Prof. Hengfu Shui.
The manuscript is ready for submission to a journal for publication.
Chapter 7: Bio-phenol formaldehyde (BPF) resoles prepared using phenolic extracts
from the biocrude oils derived from hydrothermal liquefaction of hydrolysis lignin.
Authors: Paysepar, H., Shanghuan Feng, Yuan, Z., Shui, H., and Xu, C.
The experiment work was conducted by Hooman Paysepar under supervision of Prof. Charles
Xu and Prof. Hengfu Shui, and the guidance of Dr. Shanghuan Feng and Dr. Zhongshun Yuan.
Writing and data analysis of this publication were conducted by Hooman Paysepar. It was
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reviewed and revised by Prof. Charles Xu and Prof. Hengfu Shui. The manuscript is ready for
submission to a journal for publication.

v
Dedication

To

My beloved wife, Fereshteh,

&

My wonderful parents, Hassan & Farideh,

For their endless love, encouragement, and support.

vi
Acknowledgments
Many people have supported me during the completion of my thesis with insightful criticism,
assistance, and expertise. This thesis would have never been possible without them.
I would like to express my sincere gratitude to my supervisors Professor Charles (Chunbao)
Xu at Western University and Prof. Hengfu Shui at Anhui University of Technology, Anhui
Province, China for their valuable guidance, continuous support, encouragement, advice and
help throughout my PhD study.
My sincere appreciation is extended to Dr. Zhongshun (Sean) Yuan, Dr. Kasanneni Tirumala
Venkateswara Rao, Dr. Shibiao Ren, Dr. Shanghuan Feng for them priceless feedback, advice
and guidance in the transition and completion of this research project.
In addition, I would like to thank my PhD supervision committee members, Dr. Cedric Briens
and Dr. Dominic Pjontek, from the Institute for Chemicals and Fuels from Alternative
Resources (ICFAR), and my thesis examination committee (Dr. Ramin Farnood at U. of T.,
Drs. Yang Song, Sohrab Rohani and Cedric Briens at Western University), for their invaluable
comments and suggestions.
I also gratefully acknowledge the financial support provided by the University of Western
Ontario Graduate Studies, the Department of chemical and Biochemical Engineering at the
University of Western Ontario (Teaching Assistantship, Graduate Research Scholarship),
NSERC/FPInnovations Industrial Research Chair Program in Forest Biorefinery and the
Ontario Research Fund-Research Excellence (ORF-RE) from Ministry of Economic
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Development and Innovation as well as the MITACS Accelerate Program. Support from the
industrial partners including FPInnovations is also acknowledged.
I would also like to thank Fang (Flora) Cao and Thomas Johnston for their contributions and
assistance in analyzing and characterization of my samples.
My deepest appreciation and sincere gratitude goes to my family, without whom I would have
never been able to reach this point. Words cannot express how grateful I am to my parents for
their love and support. At last, I would like to gratefully thank my beloved wife, Fereshteh
Najafi, for her patience, care, unconditional love, encouragement and support during all these
years.

Hooman Paysepar
Western University
April 2018
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Table of Contents
Abstract ................................................................................................................................ i
Co-Authorship Statement................................................................................................... iii
Dedication .......................................................................................................................... vi
Acknowledgments............................................................................................................. vii
Table of Contents ............................................................................................................... ix
List of Tables ................................................................................................................... xvi
List of Figures ................................................................................................................ xviii
List of Abbreviations and Symbols................................................................................. xxii
Chapter 1 ............................................................................................................................. 1
1 General Introduction ...................................................................................................... 1
1.1 Introduction ............................................................................................................. 2
1.2 Background ............................................................................................................. 2
1.3 Research Objectives ................................................................................................ 5
1.4 Thesis Overview ..................................................................................................... 6
1.5 References ............................................................................................................... 7
Chapter 2 ............................................................................................................................. 9
2 Literature Review ........................................................................................................... 9
2.1 Sources of Lignocellulosic Biomass ..................................................................... 10
2.1.1 Cellulose ................................................................................................... 11
2.1.2 Hemicellulose ........................................................................................... 12
2.1.3 Lignin ........................................................................................................ 13
2.2 Thermochemical Conversion ................................................................................ 16
2.2.1 Combustion ............................................................................................... 17
2.2.2 Gasification ............................................................................................... 18
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