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Luận án tiến sĩ Kỹ thuật hóa học: Catalytic hydrodeoxygenation of guaiacol and its application in bio-oil upgrading

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Tiêu đề Catalytic hydrodeoxygenation of guaiacol and its application in bio-oil upgrading
Tác giả Tran Thi To Nga
Người hướng dẫn Prof. Dr. Yoshimitsu Uemura, Assoc. Prof. Dr. Anita Bt Ramli
Trường học Universiti Teknologi Petronas
Chuyên ngành Chemical Engineering
Thể loại Thesis
Năm xuất bản 2018
Thành phố Bandar Seri Iskandar
Định dạng
Số trang 197
Dung lượng 4,89 MB

Cấu trúc

  • CHAPTER 1 INTRODUCTION (26)
    • 1.1 Back ground of study (26)
    • 1.2 Problem statement (28)
    • 1.3 Objective (30)
    • 1.4 Scope of Research (30)
    • 1.5 Thesis outline (32)
  • CHAPTER 2 LITERATURE REVIEW (34)
    • 2.1 Overview (34)
    • 2.2 Pyrolysis oil (35)
      • 2.2.1 Bio-oil production (35)
      • 2.2.2 Bio-oil properties (38)
    • 2.3 Upgrading of bio-oil (42)
      • 2.3.1 Zeolite cracking (43)
      • 2.3.2 Catalytic hydrodeoxygenation (HDO) (43)
        • 2.3.2.1 Catalyst in HDO (46)
        • 2.3.2.2 Reaction condition (47)
        • 2.3.2.3 HDO of actual oil in batch reactor (48)
        • 2.3.2.4 HDO of actual bio-oil in continuous flow reactor (49)
        • 2.3.2.5 HDO of guaiacol in continuous flow reactor (50)
    • 2.4 Catalyst deactivation and regeneration (54)
    • 2.5 HDO reactions pathway and mechanism (56)
    • 2.6 Research Gap (60)
  • CHAPTER 3 METHODOLOGY (63)
    • 3.1 Overall Research Project’s Methodology (63)
    • 3.2 Materials (64)
    • 3.3 Catalyst preparation (66)
      • 3.3.1 Monometallic Ni and Co catalysts (66)
      • 3.3.2 Bimetallic Pd-Me catalysts (Me = Co or Fe) (67)
    • 3.4 Characterization of catalyst (67)
    • 3.5 Products analysis (70)
    • 3.6 Catalytic HDO of model compound (71)
      • 3.6.1 Fixed-bed reactor (72)
      • 3.6.2 Catalytic HDO on Al-MCM-41 supported Ni and Co catalysts (73)
      • 3.6.3 Catalytic HDO on Al-MCM-41 supported Pd, Fe and Co catalysts (74)
    • 3.7 Kinetic study (76)
      • 3.7.1 Reaction rate equations (76)
      • 3.7.2 MATLAB modeling and optimization (78)
    • 3.8 Catalytic upgrading of lignin-derived bio-oil (79)
  • CHAPTER 4 RESULTS AND DISCUSSION (82)
    • 4.1 Catalyst characterization (82)
      • 4.1.1 Al-MCM-41 supported Ni and Co catalysts (82)
      • 4.1.2 Al-MCM-41 supported Pd-Co and Pd-Fe catalysts (89)
    • 4.2 Catalytic HDO of guaiacol (95)
      • 4.2.1 GC-FID calibration (95)
      • 4.2.2 Blank test for hydrotreatment of guaiacol (97)
      • 4.2.3 HDO of guaiacol over Ni and Co catalysts (98)
        • 4.2.3.1 Effect of metal sites (98)
        • 4.2.3.2 Effect of reaction conditions (99)
        • 4.2.3.3 Reaction pathway of HDO of guaiacol on Al-MCM-41 (105)
        • 4.2.3.4 Catalyst deactivation and regeneration (106)
      • 4.2.4 HDO of guaiacol over bimetallic Pd-Co and Pd-Fe catalysts (112)
        • 4.2.4.1 The synergistic effect of bimetallic in catalytic HDO (112)
        • 4.2.4.2 Catalyst regeneration (116)
    • 4.3 Kinetic and reaction pathway of catalytic HDO of guaiacol (124)
      • 4.3.1 Study on HDO of different feedstock (124)
      • 4.3.2 Kinetic study of HDO of guaiacol (128)
        • 4.3.2.1 Reaction networks (128)
        • 4.3.2.2 Kinetic model for bimetallic catalysts (130)
    • 4.4 Catalytic upgrading of lignin-derived bio-oil (137)
      • 4.4.1 Successive of pyrolysis and upgrading process (137)
      • 4.4.2 Bio-oil composition (140)
  • CHAPTER 5 CONCLUSION (144)
    • 5.1 Conclusions (144)
    • 5.2 Recommendations (146)
  • or 12 months storage while LP-280T and LP-330T keep one phase after 12 months (0)
    • C) Ni-Co/Al-MCM-41 (84)
      • 3.0 g. Upgrading conditions: T = 400 ºC, P = 1 bar, m Catalyst = 1.5 g, and H 2 flow = 90 mL/min (138)

Nội dung

INTRODUCTION

Back ground of study

Malaysia has tremendous biomass resources from agricultural sector such as oil palm, paddy, sugarcane and rubber trees [1, 2] Among them, biomass from oil palm plantation and mill has the main contribution, and this solid biomass is predicted to reach 85-110 million tons by 2020 [2] Nowadays, the biomass residues are utilized for steam and power generation at mills, fiber material, pellets and fertilizer [3, 4] However, a certain big portion of biomass residues is not fully utilized, raising waste treatment and environmental pollution issues [5, 6]

The lignocellulose biomass resource can be used not only as direct energy in combustion, but also as a more valuable fuel after conversion and upgrading process [7] Thermal conversion of biomass is one of the prominent technologies to produce bio-char, bio-oil and bio-gas [7] In comparison with torrefaction or gasification, pyrolysis is conducted at moderate temperature (400600 ºC) and in the absence of oxygen [8] The pyrolysis oil (bio-oil) product has significant advantages in storage, transport and ability to utilize as useful petrochemical and fuel [9] In Malaysia, pyrolysis oil can be produced from different biomass feedstock such as palm kernel shell (PKS) [10, 11], empty fruit bunch (EFB) [12, 13], rice husk [14, 15] and wood sawdust [16] Interestingly, BTG (the coordinator of the EMPYRO project) has already constructed a 2 t/h pyrolysis plan using EFB as the feedstock [17]

Bio-oil is considered a promising second-generation biofuel and has been used to generate heat and electricity, e.g in combustors or turbines or as a co-feed in heat and power production plants However, it is very difficult to directly utilize the pyrolysis

2 oil because of its higher water (1634 wt%) and oxygen contents (3257 wt%) than heavy fuel oil (0.1 wt% and

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