1. 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

2. 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

3. 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 √

4. 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

5. 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

6. 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.

7. 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

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

9. 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)

10. 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:

11. 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)

12. 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.

13. RESULTS AND DISCUSION
11.39 – nm nm
11.98 – 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).

14. 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.

15. Spectra into visible region 400-600 nm (Fe)
RESULTS AND DISCUSION
Spectra into visible region
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.

16. 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

17. THANK YOU