PhD in Fundamental and Applied Sciences (Sept 2013/Full time) Candidate: FATIMAH BT MOHD (G02229) PhD in Fundamental and Applied Sciences (Sept 2013/Full time) Supervisor: ASSOC. PROF. DR CHONG FAI KAIT Co-Supervisor: PROF. DR. MOHAMED IBRAHIM ABDUL MUTALIB

BACKGROUND AND PROBLEM STATEMENT Photooxidative Extractive Desulfurization using Cu-Fe/TiO2 and Eutectic-based Ionic for Visible Light Deep Desulfurization PROBLEM STATEMENT - Stringent sulfur regulation - HDS is less effective - Sulfur problems - Alternative methods

To develop Cu-Fe/TiO2 Photocatalysts for visible light activity √ RESEARCH OBJECTIVES To develop Cu-Fe/TiO2 Photocatalysts for visible light activity √ To develop Eutectic-based Ionic Liquids for extraction of sulfur species √ To investigate Cu-Fe/TiO2 as a photooxidative catalysts for sulfur removal from fuel oil under visible light followed by extraction of oxidized sulfur species by Eutectic based ionic liquids √ To propose the photooxidative-extractive desulfurization pathways and determine reaction kinetics √

KEY PROJECT MILESTONES PROJECT ACTIVITIES AND KEY PROJECT MILESTONES Synthesis of TiO2 Preparation of Cu-Fe/TiO2 Pre treatment of Cu-Fe/TiO2 Process optimization Characterization of Cu- Fe/TiO2 Recycling of integrated desulfurization system Performance screening Integrated photooxidative- extractive desulfurization system Synthesis of Eutectic based IL Characterization of Eutectic based IL Sol-Gel/Hydrothermal Wet-impregnation Completed in previous semester Calcination in air DRUV-Vis, FTIR , TPR , TGA, FE-SEM, TEM, BET, XRD Current semester achievement Desulfurization of fuel oil under visible light radiation GC monitoring Future work

GANTT CHART No Activities 2012 2013 2014 2015 1 September October November December January February March April May June July August Feburary 1 Chemicals and Apparatus Purchasing   2 Synthesis of TiO2  3 Synthesis and characterization of Fe-C/TiO2 catalyst 4 Completion of Synthesis and characterization of Fe-C/TiO2 catalyst   ● 5  Synthesis and characterization of Eutectic based ionic liquids 6 Completion of synthesis and characterization of Eutectic based ionic liquids   ●  7 Assesing the integrated photooxidative-extractive desulfurization system of fuel oil under visible light 8 Completion of desulfurization process using the integrated photooxidative-extractive desulfurization system   ●  9 Investigateing the recycling of integrated photooxidative-extractive desulfurization of furl oil 10 Completion of recycling the integrated desulfurization system 11 Thesis and journal writing ● Milestone

To investigate the effect of Cu:Fe mass composition MILESTONE OBJECTIVES To investigate the effect of Cu:Fe mass composition To characterize the developed Cu-Fe/TiO2 Photocatalysts. To use the developed Cu-Fe/TiO2 on the photooxidative conversion of sulfur species.

Untreated Photocatalyst (Metal + TiO2) slurry EXPERIMENTAL Metal salt solution (Cu-Fe)  TiO2 powder   Photocatalysts Untreated Photocatalyst (Metal + TiO2) slurry Preparation of Cu-Fe/TiO2 Photocatalyst by Wet-Impregnation Method

Glycerol + Choline Chloride EXPERIMENTAL Synthesis of Eutectic based Ionic Liquid: Choline Chloride:Glycerol Glycerol + Choline Chloride Ionic liquid solution Stir at 60oC

Integrated Photo-Oxidative Extractive Desulfurization EXPERIMENTAL Integrated Photo-Oxidative Extractive Desulfurization Model oil (100ppm DBT) Photocatalyst Light reaction (6h) Oxidized Model oil is filtered Extraction with IL Dark reaction (30min)

System sulfur conversion efficiency: EXPERIMENTAL Si = initial concentration sulfur in the model oil Sf =final concentration of sulfur in the model oil. System sulfur conversion efficiency: Si = initial concentration sulfur in the model oil Sf =final concentration of sulfur in the model oil. System sulfur removal efficiency:

1st → 11% 2nd → 10% 3rd → 5% Total = 26% 400°C – 600°C RESULTS AND DISCUSION 1st → 11% 2nd → 10% 3rd → 5% Total = 26% 400°C – 600°C 5% (50°C – 400°C) Best system 500°C 1 h Figure 1. TGA thermogram for (a) uncalcined TiO2 and (b) 500oC_TiO2 (TiO2 calcined at 500oC)

Metal loading above 5% display small peaks (reported) RESULTS AND DISCUSION 25.3 (101) Metal loading above 5% display small peaks (reported) Separate oxide phases No Cu or Fe phases were seen Well dispered Confirmed with FESEM No rutile peaks Figure 2. XRD patterns of TiO2, Fe/TiO2, Cu/TiO2 and Cu-Fe/TiO2 photocatalyst.

RESULTS AND DISCUSION 11.39 – 15.79 nm 12.05 - 15.68 nm 11.98 – 23.65 nm 12.08 – 23.47nm Figure 3. FESEM micrograph of (a) TiO2, (b) Fe/TiO2, (c) Cu/TiO2 and (d) Cu-Fe/TiO2 photocatalyst (100 KX magnification).

Figure 4. EDX and Mapping images of Cu-Fe/TiO2 photocatalysts. RESULTS AND DISCUSION Cu and Fe metal dopant are we dispersed Uniform distribution Not detected in XRD Leads to better photocatalytic activity Figure 4. EDX and Mapping images of Cu-Fe/TiO2 photocatalysts.

Spectra into visible region 400-600 nm (Fe) RESULTS AND DISCUSION Spectra into visible region 400-600 nm (Fe) Up to 800 nm (Cu and Cu-Fe) TiO2 = 3.09 Fe/TiO2 = 2.74 Cu/TiO2 = 2.60 Cu-Fe/TiO2 = 2.69 Figure 5. UV-Vis diffuse reflectance absorption spectra of TiO2, Fe/TiO2, Cu/TiO2 and Cu-Fe/TiO2 photocatalyst.

Best photocatalyts Cu-Fe/TiO2 100% oxidation (2h) H2O2:S =4 1 g/L CONCLUSION Best photocatalyts Cu-Fe/TiO2 100% oxidation (2h) H2O2:S =4 1 g/L 100% removal with 2 times extraction

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