Hydrodeoxygenation xúc tác guaiacol & ứng dụng nâng cấp dầu sinh học (UTP)

STATUS OF THESIS Catalytic hydrodeoxygenation of guaiacol and its application in bio-oil Title of thesis upgrading TRAN THI TO NGA I _________________________________________________________________________ hereby allow my thesis to be placed at the Information Resource Center (IRC) of Universiti Teknologi PETRONAS (UTP) with the following conditions: 1. The thesis becomes the property of UTP 2. The IRC of UTP may make copies of the thesis for academic purposes only. This thesis is classified as Confidential  Non-confidential If this thesis is confidential, please state the reason: ___________________________________________________________________________ ___________________________________________________________________________ ___________________________________________________________________________ The contents of the thesis will remain confidential for ___________ years.

Remarks on disclosure: ___________________________________________________________________________ ___________________________________________________________________________ ___________________________________________________________________________ Endorsed by ________________________________ __________________________ Signature of Author Signature of Supervisor 22 Chau Hiep Permanent address:________________ Name of Supervisor town, Nam Phuoc ward, Duy Xuyen ________________________________ Prof. Yoshimitsu Uemura __________________________ district, Quang Nam province, ________________________________ Vietnam ________________________________ Date : _____________________ Date : __________________ UNIVERSITI TEKNOLOGI PETRONAS CATALYTIC HYDRODEOXYGENATION OF GUAIACOL AND ITS APPLICATION IN BIO-OIL UPGRADING by TRAN THI TO NGA The undersigned certify that they have read, and recommend to the Postgraduate Studies Programme for acceptance this thesis for the fulfillment of the requirements for the degree stated. Signature: ______________________________________ Main Supervisor: Prof. Yoshimitsu Uemura ______________________________________ Signature: ______________________________________ Co-Supervisor: Assoc.

Anita Bt Ramli ______________________________________ Signature: ______________________________________ Head of Department: Assoc. Suriati Bt Sufian ______________________________________ Date: ______________________________________ CATALYTIC HYDRODEOXYGENATION OF GUAIACOL AND ITS APPLICATION IN BIO-OIL UPGRADING by TRAN THI TO NGA A Thesis Submitted to the Postgraduate Studies Programme as a Requirement for the Degree of DOCTOR OF PHILOSOPHY CHEMICAL ENGINEERING UNIVERSITI TEKNOLOGI PETRONAS BANDAR SERI ISKANDAR, PERAK OCTOBER 2018 DECLARATION OF THESIS Catalytic hydrodeoxygenation of guaiacol and its application in bio-oil Title of thesis upgrading TRAN THI TO NGA I _________________________________________________________________________ hereby declare that the thesis is based on my original work except for quotations and citations which have been duly acknowledged. I also declare that it has not been previously or concurrently submitted for any other degree at UTP or other institutions. Witnessed by ________________________________ __________________________ Signature of Author Signature of Supervisor 22 Chau Hiep Permanent address:________________ Name of Supervisor town, Nam Phuoc ward, Duy Xuyen ________________________________ Prof.

Yoshimitsu Uemura __________________________ district, Quang Nam province, ________________________________ Vietnam ________________________________ Date : _____________________ Date : __________________ DEDICATION To my family for their unconditional love, encouragement and support. To my supervisor who always be the inspiration for this thesis. v ACKNOWLEDGEMENTS I would like to express my deepest gratitude and appreciation to my supervisor, Prof. Yoshimitsu Uemura, for his excellent and constant guidance, patience, generous support, and encouragement.

I am also very thankful to my co-supervisors, AP. Anita Binti Ramli and Dr. Sujan Chowdhury, for tremendous support and valuable discussion. Moreover, I would like to offer my most profound gratitude to Centre for Biofuel and Biochemical Research, and Chemical Engineering department, Universiti Teknologi PETRONAS, Malaysia for providing a congenial work environment and state-of-the-art research facilities.

I gratefully acknowledge Prof. Masaharu Komiyama and Prof. Taufiq Yap Yun Hin for their valuable supports, comments and suggestions. I would like to acknowledge the financial support from Mitsubishi Corporation Educational Trust Fund and Universiti Teknologi PETRONAS, Malaysia.

Last but not least, I would like to thank to my parents for raising, loving and supporting me all my life; to my brother for his guideline in my childhood; to my husband, Trinh Hoai Thanh, for being on my side, supporting, inspiration and encouraging me to achieve my goals; and to my daughter for what she means to my life. vi ABSTRACT Fast pyrolysis of lignocellulosic biomass is an attractive thermochemical conversion process to produce bio-oil as an alternative liquid fuel source. Upgrading of bio-oil via hydrodeoxygenation (HDO) is an important route to accomplish this renewable energy production process. However, there are still some challenges such as high hydrogen consumption, carbon loss, catalyst deactivation, complex reaction network, and limitation in upgrading of real bio-oil.

In this study, Al-MCM-41 supported monometallic (Ni, Co and Fe) and bimetallic (Pd-Co and Pd-Fe) catalysts were prepared, characterized and evaluated for HDO of guaiacol at atmospheric pressure in a fixed-bed continuous flow reactor. A detail kinetic model has been established for HDO of guaiacol over Pd-Co and Pd-Fe catalysts. Furthermore, Pd-Fe and Pd-Co catalysts were screened for successive pyrolysis and catalytic upgrading of lignin to produce bio-oil. In vapor-phase HDO of guaiacol, Ni was found as an active metal for methanization activity while Co favored the deoxygenation activity.

The Co/Al-MCM-41 catalyzed not only HDO to remove oxygen but also transalkylation to prevent the carbon loss via methanization. Furthermore, increasing reaction temperature improved the HDO and suppressed the hydrogenation but promoted the methanization activities. In comparison with Co catalyst, Fe catalyst had higher HDO yield and lower gas-phase yield in HDO of guaiacol. Moreover, bimetallic Pd-Co and Pd-Fe shown higher stability and HDO yield than monometallic Co and Fe.

The addition of Pd enhanced significantly the stability of both Co and Fe catalysts since it might prevent the coke formation during the HDO reaction. Pd-Fe had higher stability, regeneration ability and lower gasification activity than Pd-Co catalyst. From the kinetic model, guaiacol was converted to phenol through demethoxylation over Pd-Fe catalyst while it was transformed to catechol and further to phenol over Pd-Co catalyst. The lignin-derived bio-oil mainly contained phenolic compounds which have one to three oxygen atoms.

The catalytic upgrading could eliminate significantly the oxygen vii in phenolic molecular to produce the lower oxygen content bio-oil. In summary, Pd-Fe/Al-MCM-41 present as a suitable catalyst for upgrading of lignin-derived bio- oil since it produced not only more monooxygenated phenolic but also less dioxygenated, trioxygenated and gas-phase products than Pd-Co catalyst. viii ABSTRAK Pirolisis pantas dengan menggunakan biomas lignoselulosa merupakan proses penukaran termokimia yang berkesan untuk menghasilkan bio-minyak yang memainkan peranan sebagai sumber alternatif bahan api cecair. Penaikkan taraf bio- minyak melalui hidrodeoksigenasi (HDO) merupakan laluan proses yang penting untuk memastikan pengeluaran tenaga yang boleh diperbaharui lancar.

Walau bagaimanapun, masih terdapat banyak cabaran seperti penggunaan hidrogen yang tinggi, kehilangan karbon, penyahaktifan pemangkin, rangkaian reaksi yang kompleks, dan had dalam peningkatan bio-minyak tulen. Dalam kajian ini, Al-MCM-41 menyokong mono-logam (Ni, Co dan Fe) dan bi-logam (Pd-Co dan Pd-Fe) pemangkin dikategorasikan dan dinilai untuk HDO guaikol yang beroperasi pada tekanan atmosfera dalam reaktor tetap. Model kinetik yang terperinci iaitu HDO guaikol melalui pemangkin Pd-Co dan Pd-Fe telah dihasilkan. Selain daripada itu, pemangkin Pd-Fe dan Pd-Co telah dikaji melalui pirolisis berturutan dan peningkatan lignin untuk menghasilkan bio-minyak.

Tambahan pula, bi-logam Pd-Fe dan Pd-Co pemangkin disaring untuk. Dalam fasa wap HDO, Ni telah dijumpai sebagai logam aktif untuk aktiviti pembukaan cincin manakala Co lebih sesuai untuk aktiviti deoksigenasi. Co/Al-MCM-41 pemangkin bukan sahaja HDO untuk mengeluarkan oksigen tetapi transaklisasi untuk mengelakkan kehilangan karbon melalui aktiviti metanisasi. Selainitu, meringgikai suhu reaksi telah bertanbah baik HDO dan merirdas hidrogerasi, tetapi merggalakkar aktiviti metarisasi.

Dalam membandingkan dengan pemangkin Co, pemangkin Fe mempunyai HDO hasil yang lebih tinggi dan hasil fasa gas yang kurang dalam HDO guaikol. Selain itu, bi-logam Pd-Co dan Pd-Fe menunjukkan kestabilan yang lebih tinggi dan hasil HDO daripada mono-logam Co dan Fe. Penambahan Pd meningkatkan dengan ketara kestabilan pemangkin Co dan Fe sebab pemangkin yang dinyatakan mungkin dapat mengelakkan pembentukan kok semasa reaksi HDO. Pd-Fe mempunyai kestabilan yang lebih tinggi, keupayaan penjanaan semula dan aktiviti gasifikasi yang lebih rendah daripada ix pemangkin Pd-Co.

Daripada model kinetik, guaiacol telah ditukar kepada fenol melalui demethoxylation dengan pemangkin Pd-Fe manakala ia telah berubah kepada catechol dan seterusnya kepada fenol dengan pemangkin Pd-Co. Lignin yang diperolehi daripada bio-minyak terutamanya mengandungi sebatian fenolik yang mempunyai satu hingga tiga atom oksigen. Penaik taraf pemangkin dapat menghapuskan oksigen dalam molekul fenolik untuk menghasilkan bio-minyak dengan kandungan oksigen yang rendah. Ringkasnya, Pd-Fe/Al-MCM-41 hadir sebagai pemangkin yang sesuai untuk menaik taraf bio-minyak lignin kerana ia menghasilkan bukan sahaja menghasillar lebih bayak mono-oksigen fenol, tetapi juga kurang diokseganisi, tri-oksigenasi dan fasa gas produk berbanding pemangkin Pd-Co.

x In compliance with the terms of the Copyright Act 1987 and the IP Policy of the university, the copyright of this thesis has been reassigned by the author to the legal entity of the university, Institute of Technology PETRONAS Sdn Bhd. Due acknowledgement shall always be made of the use of any material contained in, or derived from, this thesis. © Tran Thi To Nga, 2018 Institute of Technology PETRONAS Sdn Bhd All rights reserved. xi TABLE OF CONTENT ABSTRACT.

ix LIST OF FIGURES. xv LIST OF TABLES. xx LIST OF ABBREVIATION. xxi LIST OF SYMBOLS.

xxiii CHAPTER 1 INTRODUCTION .1 Back ground of study .4 Scope of Research. 7 CHAPTER 2 LITERATURE REVIEW .1 Bio-oil production .2 Bio-oil properties .3 Upgrading of bio-oil .1 Catalyst in HDO .3 HDO of actual oil in batch reactor .4 HDO of actual bio-oil in continuous flow reactor .5 HDO of guaiacol in continuous flow reactor .4 Catalyst deactivation and regeneration .5 HDO reactions pathway and mechanism .1 Overall Research Project’s Methodology .1 Monometallic Ni and Co catalysts .2 Bimetallic Pd-Me catalysts (Me = Co or Fe) .4 Characterization of catalyst .6 Catalytic HDO of model compound .1 Fixed-bed reactor .2 Catalytic HDO on Al-MCM-41 supported Ni and Co catalysts .3 Catalytic HDO on Al-MCM-41 supported Pd, Fe and Co catalysts .1 Reaction rate equations .2 MATLAB modeling and optimization .8 Catalytic upgrading of lignin-derived bio-oil. 54 CHAPTER 4 RESULTS AND DISCUSSION .1 Al-MCM-41 supported Ni and Co catalysts .2 Al-MCM-41 supported Pd-Co and Pd-Fe catalysts .2 Catalytic HDO of guaiacol .1 GC-FID calibration .2 Blank test for hydrotreatment of guaiacol .3 HDO of guaiacol over Ni and Co catalysts .1 Effect of metal sites .2 Effect of reaction conditions .3 Reaction pathway of HDO of guaiacol on Al-MCM-41 supported Ni and Co .4 Catalyst deactivation and regeneration .4 HDO of guaiacol over bimetallic Pd-Co and Pd-Fe catalysts .1 The synergistic effect of bimetallic in catalytic HDO .3 Kinetic and reaction pathway of catalytic HDO of guaiacol .1 Study on HDO of different feedstock.2 Kinetic study of HDO of guaiacol .2 Kinetic model for bimetallic catalysts .4 Catalytic upgrading of lignin-derived bio-oil .1 Successive of pyrolysis and upgrading process .2 Bio-oil composition. 121 APPENDIX A LIST OF SUPPORTING FIGURES AND TABLES.

139 APPENDIX B SAMPLE CALCULATIONS. 166 APPENDIX C OPTIMIZATION CODE FOR KINETIC USING MATLAB. 168 xiv LIST OF FIGURES Figure 2.1: Products from thermal biomass conversion .2: Pyrolysis for biomass conversion [59].3: Phase behavior of aged bio-oil. LP-raw and LP-310T form gum phase at 9 or 12 months storage while LP-280T and LP-330T keep one phase after 12 months storage [21] (LP-T are pyrolysis oil from torrified biomass).4: Relative peak area percentage distribution of major component of EFB (#75) and pine wood (#85) bio-oil samples [58].5: Reaction pathways for pyrolysis of lignocellulosic biomass [83].6: Number of HDO related publications according to Web of Science (Data retrieved on January 13, 2018 ) [51] .7: Reaction pathway of furfural on Cu catalyst at 1 atm H2 pressure, 290C [128].8: Two reaction possibility of hydrogen with furfural on catalyst surface [128].9: Proposed reaction pathway for the HDO of phenol at 40 bar initial H2 and 473K [129].10: Proposed model for hydrotreating of pine pyrolysis oil [130].1: Flow chart of overall research project.2: Flow chart of catalyst preparation of monometallic catalyst .3: Flow chart of catalyst preparation of bimetallic catalyst .4: A schematic diagram of continuous fixed-bed tubular reactor for catalytic HDO of model compound.5: Flow chart of catalytic HDO of guaiacol on Ni and Co catalysts.6: Flow chart of catalytic HDO of guaiacol on Pd, Fe and Co catalysts.7: A schematic diagram of continuous fixed-bed tubular reactor for catalytic upgrading of lignin-derived bio-oil .1: N2 adsorption (solid line)/desorption (dashdot line) isotherms (A) and BJH pore size distribution (from adsorption branch) (B) of fresh Al-MCM-41 supported Ni and Co catalysts.2: TEM images of fresh catalysts (A) Ni/Al-MCM-41, (B) Co/Al-MCM-41, (C) Ni-Co/Al-MCM-41.3: SEM images combined with EDX spectra of fresh Al-MCM-41 supported Ni and Co catalysts.

A) 10Co/Al-MCM-41, B) 10Ni/Al-MCM-41 .4: XRD patterns of support and fresh metal modified catalysts. A) Fresh and B) reduced catalysts.