Draft Thesis Final

MECHANISM AND KINETIC REACTIONS OF
MALAYSIAN ILMENITE ORE IN

HYDROCHLORIC ACID LEACHING SYSTEM
SITI ASMIDAR BINTI IBRAHIM
UNIVERSITI SAINS MALAYSIA
2022
MECHANISM AND KINETIC REACTIONS OF
MALAYSIAN ILMENITE ORE IN
HYDROCHLORIC ACID LEACHING SYSTEM
by
SITI ASMIDAR BINTI IBRAHIM
Thesis submitted in fulfilment of the requirements

for the degree of
Master of Science
December 2022
ACKNOWLEDGEMENT
I would like to convey my gratitude to Allah SWT for giving this opportunity in
completing my master's studies. This thesis became a considerably more efficient and
thanks to the generous support and assistance of many individuals, for which I am
grateful. A very special appreciation goes out to my mother, Fadzilah Kassim and the
whole De’Abraham family members for the encouragement which insisted me in
completion of this study. Not forgetting to the crucial person in this research which I
am immensely grateful, my supervisor, Dr. Nurul'Ain Jabit, for her undying support,
patience, motivation, enthusiasm, and vast knowledge. Her advice was invaluable to
me throughout the research and writing of this thesis. I could not have imagined
having a better advisor for my master’s project. My sincere appreciation also goes to
my fellow friends who are willingly helped me out with their own potentiality. Finally,
I would like to acknowledge to technical staffs from USM and JMG Terengganu who
helped me during this study.
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TABLE OF CONTENTS
ACKNOWLEDGEMENT ......................................................................................... ii
TABLE OF CONTENTS ........................................................................................... ii
LIST OF TABLES ................................................................................................... vii
LIST OF FIGURES .................................................................................................. ix
LIST OF SYMBOLS .............................................................................................. xiv
LIST OF ABBREVIATIONS ................................................................................. xv
LIST OF APPENDICES ........................................................................................ xvi
ABSTRAK .............................................................................................................. xvii
ABSTRACT ............................................................................................................. xix
CHAPTER 1 INTRODUCTION .......................................................................... 1
1.1 Introduction ...................................................................................................... 1
1.2 Problem statement ............................................................................................ 4
1.3 Objective .......................................................................................................... 6
1.4 Scope of study .................................................................................................. 6
CHAPTER 2 LITERATURE REVIEW .............................................................. 9
2.1 Introduction ...................................................................................................... 9
2.1.1 Titanium mineralogy ...................................................................... 10
2.1.2 Ilmenite mineralogy ....................................................................... 13
2.2 Natural weathering of ilmenite ....................................................................... 14
2.3 Crystal structure of ilmenite ........................................................................... 17
2.4 Diversity of raw materials for titanium production ........................................ 20
2.5 Manufacture of titanium dioxide .................................................................... 21
2.5.1 Sulphate process ............................................................................. 22
2.5.2 Chloride process ............................................................................. 23
2.6 Process of upgrading ilmenite ........................................................................ 24
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2.7 Design of experiment (DOE) ......................................................................... 25
2.7.1 Evaluation of MINITAB data ........................................................ 26
2.8 Factor affecting direct leaching ...................................................................... 27
2.8.1 Particle size .................................................................................... 27
2.8.2 Acid concentration ......................................................................... 29
2.8.3 Temperature ................................................................................... 32
2.8.4 Solid to liquid ratio......................................................................... 33
2.8.5 Reducing agent ............................................................................... 35
2.9 Kinetic study of ilmenite leaching ................................................................. 37
2.9.1 Selection of leaching kinetic models .............................................. 38
2.9.2 Kinetic study of hydrochloric acid leaching .................................. 40
2.10 Research background on prospecting area ..................................................... 43
CHAPTER 3 MATERIALS AND METHODOLOGY .................................... 49
3.1 Study description ............................................................................................ 49
3.2 Site description ............................................................................................... 51
3.3 Materials and reagents .................................................................................... 53
3.4 Characterization analysis................................................................................ 53
3.4.1 Sample preparation ......................................................................... 53
3.4.2 Morphological studies .................................................................... 54
3.4.3 Particle size distribution (PSD) ...................................................... 55
3.4.4 Mineral phase identification using X-Ray Diffraction (XRD) ...... 56
3.4.5 Elemental composition using X-Ray Fluorescence (XRF) ............ 56
3.4.6 Mineral Liberation studies ............................................................. 57
3.5 Batch Leaching experiment ............................................................................ 58
3.6 Batch leaching ................................................................................................ 61
3.6.1 Analytical measurement for leaching analysis ............................... 63
3.6.1(a) Determination of iron and titanium in leaching

solution .......................................................................... 63
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3.6.1(b) Leaching residue ............................................................ 64
CHAPTER 4 RESULT AND DISCUSSIONS ....................................................... 65
4.1 Introduction .................................................................................................... 65
4.2 Mineral Characterization ................................................................................ 67
4.2.1 Mineral phase identification ........................................................... 67
4.2.2 Chemical composition discovery through XRF analysis ............... 69
4.2.3 Particle size distribution (PSD) ...................................................... 70
4.2.4 Ore morphological studies ............................................................. 73
4.2.4(a) Optical light microscope ................................................ 73
4.2.4(b) Polarized Light Microscope ........................................... 75
4.2.4(c) SEM Analysis ................................................................ 78
4.2.5 Mineral Liberation study ................................................................ 81
4.2.6 Conclusion for mineral characterization study............................... 84
4.3 Analysis of Variance (ANOVA) .................................................................... 85
4.3.1 Statistical analysis .......................................................................... 85
4.3.2 Effect of significant variables towards Fe leached (%).................. 91
4.3.2(a) Effect of main variables ................................................. 91
4.3.2(b) Variables interaction towards Fe leached (%) ............... 93
4.3.3 Effect of significant variables towards Ti leached (%) .................. 96
4.3.3(a) Effect of main variables ................................................. 96
4.3.3(b) Variables interaction of Ti leached (%) ......................... 97
4.3.4 Overlay between responses ............................................................ 98
4.3.5 Responses optimization .................................................................. 99
4.3.6 Conclusion for ANOVA analysis ................................................. 101
4.4 Mechanism and leaching kinetic evaluation ................................................ 102
4.4.1 Performance of leaching............................................................... 102
4.4.1(a) Effect of acid concentration and Fe-Ti Correlation in

ilmenite leaching .......................................................... 102
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4.4.1(b) Effect of temperature and Fe-Ti correlation in
ilmenite leaching .......................................................... 105
4.4.2 Discussion on kinetic modelling .................................................. 108
4.4.2(a) Factors affecting apparent rate constants ..................... 113
4.4.2(b) Reaction rate order ....................................................... 114
4.4.2(c) Activation energy......................................................... 117
4.4.3 Overview mechanism for ilmenite leaching................................. 120
CHAPTER 5 CONCLUSION AND FUTURE RECOMMENDATIONS .... 129
5.1 Conclusion .................................................................................................... 129
5.2 Recommendations for Future Research ....................................................... 131
REFERENCES ....................................................................................................... 132
APPENDICES
LIST OF PUBLICATIONS
vi
LIST OF TABLES
Page
Table 2.1 Properties of pure titanium (Nesse, 1987).......................................... 11
Table 2.2 Typical TiO2 content of several titanium minerals (Nesse, 1987) ..... 12
Table 2.3 Physical properties of ilmenite (Cook & Kirk, 2018) ........................ 14
Table 2.4 Chemical composition of ilmenite from different origin ................... 17
Table 2.5 Summary of crystal structures of ilmenite and related oxides ........... 19
Table 2.6 Production of titanium dioxide (Nguyen and Lee, 2019) .................. 21
Table 2.7 Summary of the various processes used for the processing of
ilmenite............................................................................................... 25
Table 2.8 Effect of particle size on ilmenite leaching ........................................ 29
Table 2.9 Effect of hydrochloric acid concentration on ilmenite leaching ........ 31
Table 2.10 Effect of temperature on ilmenite leaching ........................................ 33
Table 2.11 Effect of solid liquid ratio on ilmenite leaching................................. 34
Table 2.12 Effect of reducing agent on ilmenite leaching ................................... 36
Table 2.13 Kinetic parameters for ilmenite leaching in hydrochloric acid

solution ............................................................................................... 43
Table 3.1 Lists of materials and reagents. .......................................................... 53
Table 3.2 Symbols, Actual, and Coded Levels of the Parameters Used ............ 58
Table 3.3 Design Summary ................................................................................ 59
Table 3.4 Point Types ........................................................................................ 59
Table 3.5 Design Table (randomized) ................................................................ 60
Table 3.6 Summary of overall design table with uncoded unit.......................... 61
Table 4.1 Phase quantification data obtained from XRD by Rietveld

refinement .......................................................................................... 69
vii
Table 4.2 Chemical composition of analysed samples by XRF analysis in
(wt.%) ................................................................................................. 70
Table 4.3 Summary of data from Particle Size Analysis ................................... 73
Table 4.4 Experimental design matrix and results ............................................. 88
Table 4.5 Analysis of variance for full quadratic for iron leached .................... 90
Table 4.6 Analysis of variance for full quadratic for titanium leached.............. 91
Table 4.7 Optimum leaching conditions and comparative results between

predicted and experimental .............................................................. 100
Table 4.8 Summary of effect of variables on apparent rate constants and

diffusivity in HCl leaching of ilmenite samples. ............................. 114
Table 4.9 Initial rate data (dX/dt) and at various HCl concentrations at
selected temperature ......................................................................... 116
Table 4.10 Reaction order for ilmenite sample .................................................. 117
Table 4.11 Activation energy for ilmenite sample ............................................. 119
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LIST OF FIGURES
Page
Figure 1.1 World production of ilmenite in the years 2020 and

2021(Gambogi, 2021; Geological Survey, 2021) ................................ 2
Figure 2.1 Summarization of titanium ores ......................................................... 13
Figure 2.2 Crystal structure of rhombohedral ilmenite(Kuganathan et al.,

2019). ................................................................................................. 18
Figure 2.3 Model of ilmenite crystalline structure(Sanchez-Segado et al.,

2015) .................................................................................................. 19
Figure 2.4 Illustrates various mechanisms of leaching (a) Shrinking sphere

particle model, (b) shrinking core model and (c) combination of
shrinking core-shrinking sphere models (Safari et al., 2009) ............ 40
Figure 2.5 Ti(IV) chloride speciation diagram for 0.1 Ti(IV) activity at 298 K
............................................................................................................ 41
Figure 2.6 Map showing the localities of sample in Bukit Kelip, Hulu
Dungun, Terengganu, Malaysia (Developers Guide for QGIS —
QGIS Documentation documentation, 2002) ..................................... 45
Figure 2.7 Study area in Bukit Kelip, Hulu Dungun, Terengganu (Sources:
JMG Terengganu 2014) ..................................................................... 46
Figure 2.8 Topography and river map in Bukit Kelip, Hulu Dungun,
Terengganu (Sources: JMG Terengganu 2014) ................................. 47
Figure 2.9 Geological map of Bukit Kelip, Hulu Dungun, Terengganu

(Source: JMG Terengganu 2014) ....................................................... 48
Figure 3.1 Experimental flowchart for overall analysis for ilmenite sand
sample ................................................................................................ 50
Figure 3.2 Studied area is labelled as A in geological map of Peninsular

Malaysia. Source:(Yusri & Kadir, 2018) ........................................... 52
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Figure 3.3 A flowchart depicting steps implied in the characterization of the
samples in this work ........................................................................... 54
Figure 3.4 A schematic diagram for dissolution experiment. (i) waterbath; (ii)
peristaltic pump; (iii) pH meter; (iv) pH/ORP probe; (v) ATC
probe; (vi) overhead stirrer (vii) thermometer (viii) alihn condenser
............................................................................................................ 63
Figure 4.1 Image of sample (a) ilmenite sand, IS, (b) concentrate ilmenite, CI,
and (c) tailing ilmenite (TI) ................................................................ 66
Figure 4.2 XRD patterns of ilmenite sand, concentrate ilmenite and tailing
ilmenite............................................................................................... 68
Figure 4.3 Particle Size Analysis Graph for Bulk Sample .................................. 72
Figure 4.4 Image of raw ilmenite sample under the optical microscope (200
X magnification). Abbreviation: ilm: ilmenite, rut: rutile, hem:
hematite, zr: zircon, leu: leucoxene and qtz: quartz ........................... 75
Figure 4.5 Major minerals discovered in IS under different magnification ........ 77
Figure 4.6 Photomicrographs of concentrate ilmenite, CI (A-D) and tailing

ilmenite, TI, E: 50X and F: 100X magnification has ilmenite and
subhedral colourless zircon assuming to ubiquitous in tailing
sample ................................................................................................ 77
Figure 4.7 SEM/EDX Elemental mapping of IS ................................................. 79
Figure 4.8 SEM/EDX Elemental mapping of CI................................................. 80
Figure 4.9 SEM/EDX Elemental mapping of TI ................................................. 81
Figure 4.10 Refers to (+53-63) µm size fractions. (A) Original BSE image, (B)
counted particles, (C) mineral of interest in locked form, and (D)
After removal numbers of interlock ilmenite particle, remaining of
mineral particles' interest which is liberated, FM .............................. 83
Figure 4.11 Percentage of mineral liberation obtained for each particle size
fractions of (+53-63) µm, (+63-75) µm and (+75-90) µm which
were measured using Eqs. (4) ............................................................ 84
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Figure 4.12 Pareto chart of the standardize effect for full quadratic (A)
percentage of iron leached, and (B) percentage of titanium leached
............................................................................................................ 89
Figure 4.13 Effect of independent variables towards % Fe leached ..................... 93
Figure 4.14 Combination effect of variables on % Fe leached (a)contour plot

for HCI (M) vs temperature (°C), (b) response plot for HCI (M) vs
temperature (°C), (c) contour plot for temperature (°C) vs solid
liquid ratio (g/L), (d) response plot for temperature (°C) vs solid
liquid ratio (g/L), (e) contour plot for temperature (°C) vs
concentration of reducing agent (g/g), (f) response plot for
temperature (°C) vs concentration of reducing agent (g/g), (g)
contour plot for solid liquid ratio (g/L) vs HCI (M), and (h)
response plot for solid liquid ratio (g/L) vs HCI (M)......................... 95
Figure 4.15 Effect of independent variables towards % Ti leached ...................... 97
Figure 4.16 Combination effect of variables on % Ti leached (a)contour plot

for HCI (M) vs temperature (°C), (b) response plot for HCI (M) vs
temperature (°C) ................................................................................. 98
Figure 4.17 Overlay of the models describing the relationship between process
parameters in both responses ............................................................. 99
Figure 4.18 SEM micrographs (a) ilmenite residue taken after leaching (b)
roughness surface of particle (c) spotted area with EDX spectrum
analysis ............................................................................................. 100
Figure 4.19 Effect of acid concentration on Fe and Ti dissolution. (a) titanium

extraction (%), and (b) iron extraction (%) at 90°C, solid liquid
ratio = 4 g/L, leaching time = 4h, reducing agent, iron powder =
0.4g/g................................................................................................ 104
Figure 4.20 Correlation between extraction of Fe and Ti from ilmenite samples

at temperature 90°C, solid liquid ratio = 4 g/L, t = 4h, reducing
agent, iron powder= 0.4g/g .............................................................. 105
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Figure 4.21 Effect of temperature on Fe and Ti dissolution (a) titanium
extraction %, and (b) iron extraction ([HCl]= 9M, solid liquid ratio
= 4 g/L, HCI=9M, t = 4h, reducing agent, iron powder= 0.4g/g ..... 107
Figure 4.22 Correlation between extraction of Fe and Ti from ilmenite samples

at temperature (a) 6M (b) 7M (c) 8M (d) 9M (temperature= 60°C
-90°C, solid liquid ratio = 4 g/L, t = 4h, reducing agent, iron
powder= 0.4g/g ................................................................................ 108
Figure 4.23 Kinetics analysis graph (a) fraction X (b) shrinking core model (c)
shrinking particle model (d) combination model for Fe under
different concentration(6M-9M) at temperature= 90 ˚C, size
fraction= -53=63µm, solid liquid ratio= 4g/L and reducing agent=
0.4g/g................................................................................................ 110
Figure 4.24 Kinetics analysis (a) fraction X (b) shrinking core model (c)
shrinking particle model (d) combination model for Ti under
different concentration(6M-9M) at temperature= 90 ˚C, size
fraction= -53=63µm, solid liquid ratio= 4g/L and reducing agent=
0.4g/g................................................................................................ 111
shrinking particle model (d) combination model for Fe under
different temperature (60 ˚C -90 ˚C) at HCI concentration= 9M,
size fraction= -53=63µm, solid liquid ratio= 4g/L and reducing
agent= 0.4g/g .................................................................................... 112
shrinking particle model (d) combination model for Ti under
different temperature (60 ˚C -90 ˚C) at HCI concentration= 9M,
size fraction= -53=63µm, solid liquid ratio= 4g/L and reducing
agent= 0.4g/g .................................................................................... 113
Figure 4.27 Fraction (X) of Fe dissolution with respect to time at different acid
concentration for polynomial fitting (a) fraction reacted (X) for Fe
(b) fraction reacted (X) for Ti at 90°C, solid to liquid ratio = 4 g/L,
iron powder as reducing agent= 0.4g/g, and size fraction = +53-63
µm). .................................................................................................. 116
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Figure 4.28 Logarithmic plot of (a) initial rates (dX/dt)Fe and (b) initial rates
at 90 °C as a function of acid concentration ([HCl] = 6-9 M, solid
liquid ratio = 4 g/L ,iron powder reducing agent= 0.4g/g and size
fraction= +53-63 µm). ...................................................................... 117
Figure 4.29 Arrhenius plot for Fe and Ti dissolution on ilmenite samples at 90

°C as a function of acid concentration [HCl] = 6-9 M, solid liquid
ratio = 4 g/L ,iron powder reducing agent= 0.4g/g and size
fraction= +53-63 µm ........................................................................ 119
Figure 4.30 Illustration of shrinking core model for ilmenite in hydrochloric

acid leaching system ........................................................................ 120
Figure 4.31 SEM EDX images of raw ilmenite sand before leaching conducted
.......................................................................................................... 127
Figure 4.32 SEM- EDX result of ilmenite grain particles taken after 4 hours
leaching that is covered with solid layer produced (a) spectrum 1,
(b) spectrum 2, and (c) spectrum 3. ................................................. 129
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LIST OF SYMBOLS
°C Degree Celsius
µ micron
θ Theta
. Full stop
, Comma
x Multiplication sign
+ Addition sign
÷ Division sign
% Percent sign
; Semicolon
- Hyphen
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LIST OF ABBREVIATIONS
IS Ilmenite sand
CI Concentrate ilmenite
TI Tailing ilmenite
PSA Particles size analysis
OM Optical microscope
XRD X-ray diffraction
XRF X-ray fluorescence
AAS Atomic adsorption spectroscopy
ICP Inductively coupled plasma
DOE Design of experiment
ANOVA Analysis of variance
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LIST OF APPENDICES
Appendix A -Table A Effect of HCl concentration on efficiency of Fe and Ti

leaching from ilmenite
-Table B Effect of temperature on efficiency of Fe and Ti
leaching from ilmenite
xvi
MEKANISME DAN TINDAK BALAS KINETIK BIJIH ILMENIT
MALAYSIA DALAM SISTEM LARUT LESAP ASID HIDROKLORIK
ABSTRAK
Potensi pasir ilmenit dari Sungai Cheniah, Bukit Kelip, Terengganu, Malaysia
untuk menghasilkan sintetik rutil melalui kaedah larut lesap reduktif yang
menggunakan asid hidroklorik sebagai reagen larut lesap dan besi sebagai agen
penurunan dikaji. Oleh kerana bijih berbeza dalam mineralogi dan komposisi
bergantung pada lokasi, adalah penting untuk menyiasat sifat fizikal dan kimia ilmenit
Malaysia yang digunakan dalam kajian ini. Dapatan kajian ini dapat memberi
gambaran tentang tingkah laku proses ilmenit semasa larut lesap. Mengikut analisis
pencirian, pasir ilmenit, IS dikelaskan sebagai gred rendah kerana kandungan TiO2
hanya 41.53%. selepas proses pra-rawatan dijalankan, dan sebatian lain seperti hematit
(Fe2O3, 38.09wt%) juga ditemui dalam sampel. Mineral lain juga seperti ‘gangue’
mineral seperti silikon dioksida (SiO2, 9.91wt%), magnesium oksida (MgO, 3.14
wt%), alumina (Al2O3, 2.86 wt%), mangan oksida (MnO, 1.89 wt%) telah dikesan
tetapi hanya dalam tahap surih. Sementara itu, fasa kristal dalam sampel IS, ilmenit
(01-073-2233) merupakan fasa yang paling boleh dikenal pasti dan diikuti oleh hematit
(04-002-7501), zirkon nitrat (04-011-3510) dan kuarza (01-087-2096). Daripada
analisis taburan saiz zarah, ia adalah nilai rentang yang agak tinggi yang menunjukkan
perbezaan taburan saiz. Oleh itu, ilmenite inin boleh dikategorikan bahawa sampel IS
adalah pecahan saiz pasir sederhana.
Untuk menentukan keadaan optimum proses pelarut lesapan reduktif untuk
ilmenit Malaysia, parameter seperti kepekatan asid hidroklorik, nisbah asid-kepada-
pepejal, suhu, dan kepekatan agen penurun telah dikaji menggunakan reka bentuk
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eksperimen (DOE). Hasil daripada proses larut lesap dinilai menggunakan analisis
varians (ANOVA) dan kriteria optimum ditunjukkan ialah 9M, 90°C, 0.4g/g, dan 4g/L.
Pemulihan maksimum ialah 96.42% Fe dan 97.24% Ti. Dengan membangunkan
analisis ini secara statistik yang berdasarkan model matematik, ia boleh berguna untuk
meramal dan memahami kesan keadaan eksperimen.
Untuk menjelaskan kinetik tindak balas dan mekanisme pelarut lesapan ilmenit
Malaysia dalam larutan HCl, pelarut lesapan kelompok langsung telah dilakukan dan
kesan kepekatan HCl dan suhu larut lesap dengan korelasi Fe-Ti dinilai. Kecekapan
larut lesap Fe dan Ti meningkat apabila kepekatan HCl meningkat. Daripada plot
korelasi Fe-Ti untuk 6-7M HCl, ia menunjukkan bahawa Fe larut lebih dua kali
berbanding dengan pelarutan Ti, manakala peningkatan kepekatan HCl, kadar larut
lesap untuk Ti meningkat dengan ketara. Ini boleh diperhatikan daripada cerun yang
diperolehi yang menghampiri 1. Trend yang sama juga boleh dilihat untuk kesan
suhu.Pelarut lesapan kelompok ilmenit mematuhi model kinetik “shrinking core” yang
mengatakan bahawa resapan proton melalui lapisan produk yang terhasil adalah
mekanisme yang mengawal kadar pelarutlesapan. Ini boleh disokong oleh nilai tenaga
pengaktifan yang diperolehi untuk kedua-dua Fe (32.3 kJ/mol) dan Ti (30.2kJ/mol)
iaitu di bawah 40 kJ/mol yang menunjukkan kadar kawalan resapan. Ini boleh
disimpulkan bahawa tindak balas plearutlesapan tidak dikawal sepenuhnya oleh tindak
balas kimia kerana melibatkan permukaan mineral dan kadar pelarutlesapan titanium
dan besi dan oleh itu boleh disimpulkan bahawa pelarut lesapan ini mematuhi model
teras yang mengecut
xviii
MECHANISM AND KINETIC REACTIONS OF MALAYSIAN
ILMENITE ORE IN HYDROCHLORIC ACID LEACHING SYSTEM
ABSTRACT
The potential of ilmenite sand from Sungai Cheniah, Bukit Kelip, Terengganu,
Malaysia to produce synthetic rutile through a reductive leaching method that uses
hydrochloric acid as a leaching reagent and iron as a reducing agent is studied. Because
ore varies in mineralogy and composition depending on location, it is critical to
investigate the physical and chemical properties of the Malaysian ilmenite used in this
study. The findings of this study can shed light on the behaviour of ilmenite during the
leaching process. According to the characterization analyses, the ilmenite sand, IS is
classified as low grade since the TiO2 content is only 41.53%. after pre-treatment
process conducted, and others compound such as hematite (Fe2O3, 38.09wt%) found
in the sample. Other minerals also which consider gangue minerals such as silicon
dioxide (SiO2, 9.91wt%), magnesium oxide (MgO, 3.14 wt%), alumina (Al2O3, 2.86
wt%), manganese oxide (MnO, 1.89 wt%) were detected but only in trace levels.
Meanwhile, crystalline phase in IS sample, ilmenite (01-073-2233) is the most
identifiable phase and follow by hematite (04-002-7501), zircon nitrate (04-011-3510)
and opaque mineral such as quartz (01-087-2096). From the particle size distribution
analysis, it is relatively high span value which indicates an apart of size distribution.
Thus, it can be categorized that the IS sample is medium sand size fraction. The value
of Cu is 1.8662 whilst Cc is 0.9327 by mean it can be classified as poorly graded
indicates that most of the grain size of particles in bulk sample is identical.
To determine the optimum conditions of the reductive leaching process for
Malaysian ilmenite, parameters such as concentration of hydrochloric acid, acid-to-
xix
solid ratio, temperature, and concentration of reducing agent was studied using design
of experiment (DOE). The result of the leaching process was assessed using analysis
of variance (ANOVA) and optimal criteria were pointed out to be 9M HCl, 90°C,
0.4g/g of iron powder, and 4g/L solid liquid ratio. The maximum recovery is 96.42%
Fe and 97.24% Ti. By developing this analysis statistically which is based on the
mathematical models, it could be useful for predicting and comprehending the effects
of experimental conditions.
To elucidate the reaction kinetics and mechanism of Malaysian ilmenite
leaching in HCl solution, direct batch leaching was performed and the effect of HCl
concentration and leaching temperature with Fe-Ti correlation was assessed. The
leaching efficiency of Fe and Ti was increased as the HCl concentration increased.
From the Fe-Ti correlation plot for 6-7M HCl, it showed that the Fe dissolved two-
time folds compared to Ti dissolution, while increasing the HCl concentration the
leaching rate for Ti increased significantly. This can be observed from the slope
obtained which is close to 1. Similar trend also can be seen for the effect of
temperature. The batch leaching of ilmenite particles obeyed a shrinking core kinetic
model, supporting the view that the proton diffusion through a product layer is the rate-
controlling step. This can be supported by the activation energy values obtained for
both 32.3 kJ/mol Fe and 30.2kJ/mol Ti which is below 40 kJ/mol which indicates the
diffusion control rate. This can be inferred that the dissolution reaction was not
controlled wholly by the chemical reaction involving the mineral's surface and
titanium and iron dissolution rates and therefore can be concluded this leaching were
obeying shrinking core models.
xx
CHAPTER 1
INTRODUCTION
1.1 Introduction
Titanium dioxides (TiO2) have been extensively used due to their fascinating
general features in a variety of fields that have an impact on the quality of human life.
According to the U.S. Geological Survey’s (USGS) National Minerals, since 2021,
With 37% of the world's ilmenite production in 2021, China remained the primary
producer and consumer of titanium mineral concentrates. South Africa and
Mozambique were also two of the top producers of titanium mineral concentrates.
Meanwhile, about 3.6 million tonnes of titanium mineral concentrates were imported
from China in total, a 21% increase from 2020 which can be illustrated in Figure 1.1.
Referring to Global Titanium Dioxide Market Report (2021), the demand for
titanium dioxide reached USD 16.98 billion in 2020 and is projected to increase at a
CAGR of 8.3% from 2020/21 to 2028. This suggests that it will be in high demand
from producers and consumers in the global market for nano-paints, sheets, beauty
products, photocatalysis substances, and antibacterial agents, as well as in civil
applications, self-cleaning products (Wahyuningsih et al., 2013, 2014; Guo et al.,
2014; Lakshmanan et al., 2016; Nguyen & Lee, 2019; Ihekweme et al., 2020; Yang et
al., 2020; Fouda et al., 2021; Shao et al., 2021). Plastics represent the fastest-growing
market segment of the titanium dioxide pigment, with growth rates ranging between 5
and 18 percent over the last two decades(Sasikumar et al., 2007; Zhang & Nicol, 2010;
Chia et al., 2012; Sanchez-Segado et al., 2015; Por et al.,, 2017; Jabit & Senanayake,
2018; Gambogi, 2021). Examples of some of the other uses of titanium dioxide
pigments include applications in ceramics, concrete, food, titanates, and photovoltaic
cells.
1
Figure 1.1 World production of ilmenite in the years 2020 and 2021(Gambogi,
2021; Geological Survey, 2021)
Anatase, brookite, ilmenite, leucoxene, perovskite, rutile, and sphene are some
of the minerals which encompass titanium dioxide, but ilmenite and rutile are
commonly commercialized these days (Nesse, 1987; Wahyuningsih et al., 2014;
Sanchez-Segado et al., 2015; Por et al., 2017; Jabit & Senanayake, 2018; Nguyen &
Lee, 2019). However, natural rutile supplies are rapidly depleting, necessitating the
extraction of ilmenite resources to develop titanium industries. In fact, consumption of
low-grade rutile is less beneficial contradicting ilmenite which still can be as titanium
feedstock even in a lower grade. For instance, rutile production in China has a
multitude of challenges, which include low-grade rutile, fine granularity, and features
that are similar to other valuable minerals, making the separation among it complicated
and operational costs high.
Ilmenite is a mineral that is being mined nowadays since it is one of the several
titanium oxides resources that is currently available which can be profitably exploited
since the world issued with a rutile’s shortage. The processing of ilmenite is very
2
complex due to its mineralogical complexity. There are several methods used in
processing ilmenite. From the early method pyrometallurgical process, concentrated
sulphuric acid treatment to hydrometallurgical treatment, ilmenite treatment with
hydrochloric acid or chloride process had been progressively improved to obtain the
best condition in producing titanium dioxide. The Benilite process, the Becher process,
the Murso process, and the Altair process are just a few of the suitable methods of
substitution ilmenite from rutile(Nguyen & Lee, 2019). Nevertheless, due to the high
energy consumption as well as expenditures of these processes, further
scientifical work is required in order to develop cost-effective processes and enhance
titanium dioxide production.
Meanwhile, the chloride process which requires rutile or upgraded ilmenite as
a feedstock, has a more cost-effective flowsheet and produces less waste compared to
other methods which will be discussed in chapter two. Several articles have been
published in the past few decades on the use of the leachant hydrochloric acid for
upgrading ilmenite to synthetic rutile. The majority of ilmenite leaching studies to
hydrochloric acid were carried out in order to select the optimal conditions for
upgrading ilmenite to synthetic rutile.
The presence of reductant also such as metallic iron powder to hydrochloric
acid was known to improve ilmenite leaching(Mahmoud et al., 2004; N. A. Jabit &
Senanayake, 2018; Nguyen and Lee, 2019; Daba et al., 2022). This research study is
interested in the dissolution of ilmenite in hydrochloric acid at the prospecting area.
Previous researchers emphasized enhancing the efficiency of the dissolution reaction
by study in several conditions such as particle size of the feed, concentration of acid,
temperature, solid to liquid ratio, reducing conditions and additional pre-treatment
3
process(Tsuchida, 1982; Olanipekun, 1999; Mahmoud et al., 2004; Habib et al., 2006;
Babu et al., 2009; Baba et al., 2013; Das et al., 2013; Guo et al., 2014; Hosseini et al.,
2018; Jabit & Senanayake, 2018; Nguyen & Lee, 2019; Daba et al., 2022; Kurniawan
et al., 2022). However, a fundamental understanding of the processes is still lacking,
and more research is necessary to fully understand the reaction in kinetic and its
mechanism. Therefore, the aim of the present study is to evaluate more the kinetics of
titanium and iron dissolution in concentrated hydrochloric acid solutions, as well as
the leaching mechanism.
1.2 Problem statement
Numerous researchers have been looking into the dissolution of ilmenite in
acid solutions, utilizing various methods to enhance the process, particularly in the
chloride method. Almost all of the world's heavy mineral beach sand deposits contain
minerals that are the result of ilmenite's natural weathering and alteration, and thus
contain iron in the form of iron (III). Generally, ilmenite is composed of 52.7 % TiO2
and 47.3 % FeO. However, mineral constituents of ilmenite differ from different
regions. Moreover, a weathered deposit not only influences the titanium content of the
ore but also appears to change its chemical behaviour.
Ilmenite concentrates may contain significant levels of impurities, either
internal or external to the grains, which can affect the leaching process as well as the
output especially in its market value due to TiO2 recovery. Owing to different mineral
contents, standard leaching cannot be used on all types of ilmenite deposits due to
differences in mineral content. To solve this problem, the characterization of the
ilmenite sand from Cheniah river, Dungun, Terengganu is studied and subsequently
proceed to the leaching process in different parameters which will investigate through
4
its iron and titanium extraction result. From here, the optimum condition of ilmenite
leaching can obtain which able to facilitate an additional information in designing the
leaching process as to achieve maximum recovery of TiO2.
There have been numerous studies on ilmenite dissolution kinetics in acid
solution, however, the kinetics mechanism and rate of reaction in acid solution have
not been accurately documented or truly addressed. This knowledge is vital for the
accurate design and interpretation of hydrometallurgy reactions, allowing these
processes to be improved and monitored. To propose a dissolution mechanism, the
measured kinetic parameters must support the mechanism.
The concentration of reagents and the temperature have an impact on the rate
of dissolution or leaching reactions. The order of reaction and the activation energy
are the two kinetic parameters as a result. The order of a reaction is the most crucial
kinetic parameter in determining the dissolution mechanism. It explicates how the rate
is affected by the reagent concentration. The activation energy, on the other hand, is
temperature dependent. Diffusion of reactants from the bulk solution to the ilmenite
surfaces, adsorption at the surface, formation of appropriate complexes of iron and
titanium with chloride, desorption of the products such as complex species from the
surface, and diffusion back into the bulk solution are all part of the ilmenite leaching
process. Controlling the overall dissolution rate is one of the processes, and it's critical
to figure out which steps are controlling so that the complex behaviour of ilmenite
leaching can be understood, and the hydrometallurgy operation's performance can be
optimized. As a result, the dissolution kinetics model will be investigated, as well as
the shrinking core model, shrinking particles, and mixed control.
5
1.3 Objective
The main objectives of this research work:
1. To characterize the Sungai Cheniah ilmenite as potential resources for
titanium dioxide production.
2. To determine optimum parameters in ilmenite leaching through
statistical design method for titanium extraction from ilmenite using iron as
reducing agent.
3. To elucidate the kinetics and leaching mechanism of ilmenite in
reductive leaching system.
1.4 Scope of study
In this research study, samples were explored extensively in characterization
analysis prior to the leaching procedure. Ilmenite sand sample is collected from a
preliminary studied area at Bukit Cheniah, Terengganu, Malaysia using the grab
sampling method, the practical way to collect representative samples. This exploration
is undertaken at the main river source, Cheniah river of the catchment area. After
sampling, the sample subsequently undergoes sampling method by using Jones Riffles
sampling method that is exerted for further minimization of the sample’s quantity.
Afterward, magnetic separation is implemented to distinguish between magnetic
minerals and non-magnetic minerals.
Characterization analysis is performed by outlining the ilmenite sand,
concentrate ilmenite, and tailing ilmenite through several applications such as x-ray
diffraction (XRD) and x-ray fluorescence (XRF), and then proceed with a polished
section for detailed mineralogical studies in different sizes fraction. These samples
were analysed under microscopic observation that is a polarized microscope, digital
microscope, and scanning electron microscope with energy dispersive energy, SEM-
6
EDX. Whilst, other portions of ilmenite sand are used to determine particle size
distribution, PSD. For good estimation in selecting the best size fraction as the leaching
input, a mineral liberation study is conducted by inspecting different size fractions of
ilmenite sand sample.
Concentrate ilmenite is subjected to screening to separate the sample into
selected size fraction regarded as the leaching input. Prior to testing ilmenite leaching,
the leaching experiment is designed based on the Response Surface Design method,
RSM using MINITAB 18 software. Parameters chose in this experiment are
hydrochloric acid concentration, temperature, solid to liquid ratio, and concentration
of reductant is iron powder. Batch leaching is set up and operated according to DOE
design. Batch leach tests are carried out in a 500 mL jacketed vessel where the ilmenite
particles will be completely suspended by rotating the stirrer at a high enough speed.
The solution of hydrochloric acid will then be added and heated to the required
temperature. The ilmenite samples are transferred into the reactor once the set
temperature is reached. The leaching experiments will be carried out for a total of 5
hours. The slurry will be filtered using a pump filter after the experiment is completed,
and the leaching solution will be stored in dark glass bottle samples to prevent any
further reactions. Residue and aliquot obtained from the leaching testing is examined
using inductively coupled plasma optical emission spectrometry, ICP-OES, Atomic
Absorption Spectroscopy, AAS, SEM-EDX, and XRD for iron and titanium
determination. Data acquired from these analyses were used for determining leaching
efficiency which was calculated based on the leached solution or residue analysis.
Mass balance will be calculated based on leached residue elemental analysis. The
leaching statistics (highest Ti or Fe dissolution after complete leaching) will be
7
analysed using a statistical method (ANOVA, MINITAB 18 Software) in order to
develop statistical models of the leaching process.
For kinetic analysis, a narrow size range of input leaching is selected and
performed in an optimal condition where the concentration of acid and temperature
were selected as the parameters. The operational setup procedure for this study is
similar to the previous batch leaching test adding with the withdrawal of 10mL leach
liquor from the reactor using a syringe at various time intervals and filtering through
Whatman Celulose Nitrate membrane filters with pore size of 0.45 µm. Leaching
kinetic studies are performed by emphasizing two parameters HCI concentration and
temperature whilst other parameters will be fixed as the optimum condition. Iron and
titanium determination will be tested using residue and aliquot obtained from leaching
testing by evaluating the contents of the element using ICP-OES, AAS, SEM-EDX,
and XRD. Detailed dissolution mechanism and kinetic used to formulate statistical
mathematical modelling of leaching process using the shrinking core model.
8
CHAPTER 2
LITERATURE REVIEW
2.1 Introduction
Titanium oxide is extensively used in many industries due to its valuable
features that can produce various outputs. The outstanding properties, such as excellent
temperature and corrosion resistance, high strength-to-weight ratio, biocompatibility,
and high catalytic activity, titanium and its derivative products are widely used in
aerospace, navigation, medical, and catalytic industries(Chen et al., 2017).
Meanwhile, in Malaysia, ilmenite is typically found in Perak and Selangor as a by-
product at the mining sector. Several factories located in Klang Valley, Selangor and
Kinta Valley, Perak produce by-product or also known as amang product where
ilmenite from tin ore is used as their feedstock.
Beside, Langkawi black sand that is believed has ilmenite is used to develop
titanium-based products even if the grade is low (Azman et al., 2019). In this
prospective study area, a few articles also have been reviewed on ilmenite deposits
located in Sg Cheniah, Bukit Kelip, Hulu Dungun, Terengganu (Fateh Chand, 1978;
Nazri & Hadi, 2014). Nonetheless, due to inadequate information and knowledge
regards ilmenite present, this recent study is an effort to obtain more data from the
study area through details analysis on occurrences, characteristic and extraction
process.
An exquisite deposit like ilmenite or namely known to be iron titanium oxide
is one of the listed decisive ores nowadays as it sorts of titanium oxide or titanium
which is capable of being produced commercially. This world encounters a depletion
of natural rutile resources supply and requires imperatively ilmenite ores to take place
9
for the development of titanium industries. Thus, this has led to an invention and an
effort to convert abundant ilmenite to synthetic rutile.
2.1.1 Titanium mineralogy
A valuable element suchlike titanium was first discovered by Reverend
William Gregor on the southern Cornish coast of Manaccan Cornwall in 1791(Russell,
2013). He did elaborately detail his black magnetic sand sample where according to
his analysis this sand almost has nearly the same characteristic as mineral ilmenite
(FeTiO3). An expert historian known to be M. H. Klaproth, a German chemist who
also discovered titanium element a few years later in his impure rutile, TiO2 from
Hungary. Both decided to establish a proper name for the new discovery element and
a name titanium is adapted to this new element.
Nearly all these precious inventions are mined extensively throughout the
entire world for manufacturing purposes, which turn out to be the most important
sources of the cultural growth of civilization. It is known to be the ninth of the most
profuse structural metal around 0.5% in a crust of the earth (Gázquez et al., 2014).
This element is eventuated from numerical ore deposits, mainly rutile and ilmenite
which are widely formed throughout the whole world either in crust or lithosphere.
From periodic table, titanium is denoted as a symbol of “Ti” which is
recognized as one of the transition metals. It is silver-grey material with 4510 kg/m3
of density somewhere that is quite heavy in between aluminium and stainless steel. It
behaves resistantly corrosive with a high boiling point of around 3287°C. Table 2.1
displays the properties of titanium specifically.
10
Table 2.1 Properties of pure titanium (Nesse, 1987)
Properties Identification
Atomic Number 22
Atomic Mass 47.88 u
Group Family in periodic table Group 4 (IVB) Transition metal
Colour Dark, silver grey and shiny metal
Specific gravity 4.70-4.79
Melting Point (°C) 1660.0
Boiling Point (°C) 3287.0
Specific heat (cal/g. °C) 519.0
Density (kg/m3) 4510
Streak Black
Mohs Hardness 6.0
Cleavage of Fractures None
Luster Metallic
Fracture Conchoidal to sub-conchoidal
Magnetism Paramagnetic
Crystal System Trigonal
On most occasions, titanium is largely can be obtained from rutile, TiO2
minerals. North America, Africa, Brazil, India, and Australia are the most common
countries that acquire a high enough quantity of rutile deposits. It usually can be
spotted either on a seashore or in alluvial deposits or mining through dredging and
mining like open-pit methods. Rutile is preferred to be the most economical ore for
titanium element because it contains the highest amount titanium bearing mineral
roughly around 93.0% to 96.0% of titanium content depending on its geological
factor(Survey, 2021). Table 2.2 shows the typical TiO2 content of several titanium
mineral
11
Table 2.2 Typical TiO2 content of several titanium minerals (Nesse, 1987)
Mineral Composition TiO2 content %

Rutile TiO2 (tetragonal, twinned) 97.0-98.5
Brookite TiO2 (orthorhombic) >95%
Anatase TiO2 (tetragonal, near >95%
octahedral)
Ilmenite FeTiO3 38.5-61.0
Magnetite Fe3O4 8.0-11.0
Perovskite CaTiO3 0.0-54.0
Arizonite Fe2O3·nTiO2·mH2O -
Geikielite MgTiO3 -
Titanite or sphene CaTiSiO5 -
Titaniferous (FeTi)2O -
magnetite
Out of the many minerals that encompass titanium element as their essential
component, ilmenite (FeTiO3) is also the most abundant in Earth’s crust which
comprises 31.8% to 61.0% of titanium element and significantly has a huge possibility
of the continuous production of titanium metal in the future (Nesse, 1987).
Tremendous ilmenite deposits are evolved in Canada and United State manufactured
on this economic titanium mineral (Geological Survey, 2021). Production of titanium
from ilmenite can be encountered through various methods by converting ores to
synthetic rutile.
Ilmenite and rutile have a high proportion of titanium elements as well as
leucoxene is also a primary ore for titanium resources. Another remarkable source
includes perovskite (CaTiO3), anatase, brookite, and sphene (CaTiSiO5) by which it is
clearly that titanium rarely exists in a pure form. This will lead to extraordinary work
for a producer because of the difficulty of isolating the ore into a pure titanium
concentrate with eventually capable to raise the marketing price. However, only
12
certain minerals that have a high constituent of titanium element are economical to be
processed and commercialized.
Figure 2.1 represents a summarization of titanium ores accordingly. As stated
in Figure 2.1, titanium ores can attain from three different chemical compounds
titanates, silicates, and oxides. These chemical compounds composed of titanium
oxides for instance perovskite, ilmenite, and arizonite are classified under the titanates
group. Meanwhile, silicate group such as sphene consist of silicon and oxygen with
titanium oxide.
Perovskite
Titanates Ilmenite
Arizonite
Titanium ores Silicates Sphene
Anatase
Oxides Brookite
Rutile
Figure 2.1 Summarization of titanium ores
2.1.2 Ilmenite mineralogy
Generally, ilmenite ore can be found in almost all types of rocks either in
igneous rocks, metamorphic rocks, and common heavy minerals in clastic sediments.
13
Formation of this mafic igneous rock begins when it crystallizes out of magma
relatively resulting in a denser crystal of ilmenite layer at the bottom of a magma
chamber. Some ilmenite also crystallizes in veins and cavities and sometimes occurs
in pegmatites and some other metamorphic rocks. It also has a huge resistance to
weathering process. Weathered ilmenite ore causes itself to disperse and segregates
during stream transport and accumulate with sediments.
An opaque ilmenite mineral is a black metallic mineral in hand specimens and
reddish black streaks due to intergrown hematite. It is also known to be a weak
magnetic mineral as it associates with undeveloped magnetite grains. Ilmenite with a
chemical composition of FeTiO3 has similar composition and structure to other
minerals such as hematite and corundum from which it consists of hexagonal close-
packed O atoms with ferum and titanium ions. The shape is believed in tabular shape
and tends to be elongate rectangular. It also forms in an anhedral grains or granular
masses as is common lamellar intergrowth in magnetite. Table 2.3 shows the physical
properties of ilmenite.
Table 2.3 Physical properties of ilmenite (Cook & Kirk, 2018)
Properties Identification
Chemical Classification Oxide
Colour Black
Streak Reddish Black
Mohs Hardness 5.5 to 6
Luster Metallic
Diaphaneity Opaque
Specific Gravity 4.7 to 4.8
Magnetism Weakly magnetic mineral
2.2 Natural weathering of ilmenite
A high grade of titanium dioxide pigment is frequently expended in the
manufacture of plastics, papers, and paints due to its whiteness and opaqueness.
14
However, this pigment does not pertain to titanium oxide naturally in nature and
usually is in the form of paragenesis of titanium dioxide content. For example, Ilmenite
which one of the sources of titanium dioxide may found with a association with
numerical minerals likewise chromium, zinc, copper, aluminium, silica, and calcium.
This is because ilmenite which has undergone weathering process prompt to have the
diversion of its chemical composition, and therefore most of ilmenite sources are found
in divergent percentage of titanium dioxide content.
Most in common, ilmenite undergoes minerals alteration by which it triggers
modification of the mineral itself in terms of its chemical decomposition in
crystallography. Mineral such ilmenite experiences various natural processes suchlike
oxidation, hydration, and exsolution resulting in titanium-rich by the removal of iron
from crystal lattice and namely to be altered ilmenite (Temple, 1966). In detail,
alteration of ilmenite (FeTiO3) in nature is associated with the process of oxidation
and removal of iron gradually to give a product of enrichment in TiO2.
Weathered ilmenite or altered ilmenite has different crystal structures from the
origin, especially in their particular Ti and Fe pattern which suggest following a
sequence of continuous weathered Ti mineral from ilmenite into pseudorutile, rutile,
and anatase (Temple, 1966; Sanuprava et al., 2015; Ramakokovhu et al., 2020). The
occurrence of various forms of ilmenite typically has a composition of 40-65% of
titanium dioxide (TiO2), and iron (II) oxide (FeO). Nevertheless, the proportion itself
is more dependent on its geological history. Table 2.4 shows chemical of ilmenite from
different origin.
According to the research done by (Por et al., 2017), ilmenite of 52% TiO2 is
weathered naturally by water as the main agent in weathering process and continuous
15
runs of the agent lead to the iron oxidation producing intermediate iron titanate from
which the name of pseudorutile of 65-70% TiO2 is proposed. Long exposure in the
stream water causes the weak iron in pseudorutile to migrate and decompose into
leucoxene. On the other hand, pseudorutile weathering would be transformed into
rutile as transitional minerals or anatase formation before it proceeds to be final
product, leucoxene.
Basically, there is two stages model introduced by Grey and Reid (1975) which
reveals relevant facts on alteration process for ilmenite. In the early stage of ilmenite
alteration, it encounters oxidation of all ferrous iron into ferric iron namely
pseudorutile whereby one - third of iron is vanished through leaching process.
6Fe (II)TiO3 + 3H2O + 1.5O2→ 2Fe (III)2Ti3O9 + 2Fe (OH)3 Eq. 1.0
On second stage, pseudorutile is altered by going through two processes
synchronously which is dissolution and reprecipitation process. Both of two elements
iron and titanium dissolved but once the iron is leached out the titanium will be
redeposited forming a rutile. This can be described by Eq. 2.0.
Fe (III)2Ti3O9 + 3H2O → Fe (III)Ti3O6(OH)3 + Fe (OH)3 Eq. 2.0
As stated earlier, pseudo rutile carries weak iron and cause it to be unstable in
deposit and endorse itself to vanish the iron from the grains and thus converts it to
rutile. This stage can be narrated according to the equation below:
Fe (III)2Ti3O9→ 3TiO2 + Fe2O3 Eq. 3.0
16
Table 2.4 Chemical composition of ilmenite from different origin
Reference Oxide and metal composition % (w/w)
Fe2O3
Cr2O3
Al2O3
MgO
MnO
V2O5
TiO2
P2O5
SiO2
CaO
FeO
Das et al., 50.0 85.7 38.6 30.1 0.2 - 0.8 - - 1.6 -
2013
Olanipekun, 44.0 100.6 45.3 1.5 3.0 - - - - - -
1999
Tsuchida, 52.0 60.6 27.2 - 0.4 - 3.0 0.1 - 2.3 -
1982
Mahmoud, et 41.1 28.6 24.4 - 0.6 0.4 0.3 0.3 0.1 0.6 0.1
al., 2004
Zhang & 44.6 - 35.2 3.2 5.4 0.2 0.7 - 2.0 2.5 0.1
Nicol, 2010
Mehdilo & 32.9 44.6 - 5.9 3.6 - 2.1 - 2.2 2.5 -
Irannajad,
2012
El-Hazek et 44.1 21.4 28.5 0.7 0.8 0.1 1.1 0.2 0.9 0.9 0.2
al., 2007
Li et al., 2008 47.2 5.5 34.2 2.7 6.2 0.1 0.6 - 1.0 1.4 -
Guo et al., 45.9 17.1 31.6 2.8 1.2 - - - 0.1 1.0 -
2014
Li et al., 2008 49.7 12.9 35.9 5.2 0.1 - 1.2 - 0.1 3.1 0.5
2.3 Crystal structure of ilmenite
To comprehend the process of creating an output like titanium dioxide from
ilmenite, it is compulsory to analyse the FeTiO3 crystal structure. Table 2.5 shows
summary of crystal structures of ilmenite and related oxides. Ilmenite somehow has
some resemblance to normal spinel structure, which is cubic in contrast with the
hexagonal structure of ilmenite, as shown in Figure 2.2. Ideally, FeTiO3 exhibits a
rhombohedral structure that sort of alternative octahedral FeO6 and TiO6 layers. In
Figure 2.3, the oxygen is hexagonally packed that is bonded by metal ions like Fe2+
that are tetrahedrally coordinated whereas Ti4+ adopts itself vigorously on octahedral
sites.
17
As the cations in octahedral sites act very energetically, the ilmenite crystal
structure occupies alternating layers which give a rise to alternation structure on it by
the substitution of various cation elements such as Fe3+, Cr3+, and Mn3+. In this
alternate structure, there is also competition for other divalent ions such as Mg2+ and
Ca2+ to take place which may replace Fe2+ depending on the number of charges at the
octahedral sites. Thus, the general formula of ilmenite can be expressed as
(Fe,Mg,Mn,Ti)O3. Some ilmenite is also scattered by fine zircon and monazite and
extremely difficult to separate physically. This will reduce the value of ilmenite for the
synthetic rutile production which is why the ilmenite deposits with higher
concentrations of zircon and monazite are undesirable for mineral beneficiation.
Figure 2.2 Crystal structure of rhombohedral ilmenite(Kuganathan et al., 2019).
18
Figure 2.3 Model of ilmenite crystalline structure(Sanchez-Segado et al., 2015)
Table 2.5 Summary of crystal structures of ilmenite and related oxides
Type of Formula System Cell constant

mineral (Å)
Ilmenite FeTiO3 Rhombohedral a =5.0881±
0.0005
c = 14.29±
0.0005
Hematite α-Fe2O3 Rhombohedral α = 5.035
c = 13.72
Magnetite Fe3O4 Cubic (fcc-inverse α = 8.33-8.38
spinel)
Pyrophanite MnTiO3 Rhombohedral a = 5.137
c = 14.29
Geikielite MgTiO3 Rhombohedral a = 5.054
c = 13.898
19
2.4 Diversity of raw materials for titanium production
Titanium can be found naturally in oxide or mixed oxides with variable
impurities. Ideally, mineable ore of titanium deposits comes from volcanic origination
genesis which comprises one or more types of elements on it. However, under nature
circumstances, the grade titanium ore can be arisen gradually when the ore is
weathered due to the liberation of ores itself creating higher of titanium content.
This world currently consumes the ores for generating titanium dioxide
pigment which is about 90% to 95% of the ore global titanium ore extraction whereas
the rest is for producing titanium metal. Commercial production of TiO2 pigment can
be made in either the sulphate process or the chloride process. Nevertheless, the type
of raw materials for the feedstocks precisely needs to consider producing high grades
of titanium dioxide pigment and reduce huge consumption of energy with less waste
production. Table 2.6 depicts the type of raw materials that are used to produce
titanium dioxide pigment.
According to Table 2.6, only five raw materials from the top are used in
producing titanium dioxide materials. Natural ilmenite, leucoxenized ilmenite, and
ilmenite can be found in nature whilst synthetic rutile and titanium slag are not
originated from nature, and it is man-made that require several stages to produce TiO2
outputs. Titanium slag is produced by ilmenite smelting concentrate that is usually
applied to low-grade ilmenite concentrates that are high in iron oxide.
20
Table 2.6 Production of titanium dioxide (Nguyen and Lee, 2019)
Raw material TiO2 content (%) Usage in

Natural rutile 92-98 Chloride process
Synthetic rutile 89-93 Chloride process
Leucoxenized ilmenite 55-65 Chloride process
Titanium slag 75-85 Sulphate process
Ilmenite 37-54 Sulphate process
Anatase 90-95 None
Brookite 90-100 None
Perovskite 40-60 None
Sphene (titanite) 30-42 None
Titanomagnetite 2-20 None
2.5 Manufacture of titanium dioxide
Normally, there are two main processes used to produce a high grade of
titanium dioxide from deposit ores namely chloride process and sulphate process. The
chloride process is the prevalent process as it generates superior pigment rather than
the sulphate process. However, sulphate process capable to treats multivariable grades
of ores on the same period and successfully can eliminate the iron and other impurities
simultaneously. Later will explicate more in the next section.
Several studies have been made on the hydrometallurgical processing of either
low-grade or high-grade ilmenite covers immensely by hydrochloric acid leaching
(chloride process), and sulphuric acid leaching as well for ilmenite up-gradation. More
than 60% of TiO2 in the world are generated through the chloride route and the rest
from the sulphate process either in natural or synthetic rutile or titanium-rich slag.
Considering cost-efficacy and relatively better waste management, the chloride
process is observed to be more proﬁtable than the traditional sulphate process. The
huge waste output of iron sulphate is produced from the traditional sulphate process
21
and thus reduces the quality of products due to the high concentration of iron present
in raw materials.
2.5.1 Sulphate process
The sulphate process was the first industrial process that is introduced for
manufacturing titanium oxide pigment in 1915 in Norway(Lakshmanan et al., 2016).
This process is called sulphate process due to the consumption of the main leaching
agent, sulphuric acid (H2SO4) in order to terminate undesirable elements from ilmenite
ore (FeTiO3) into a high grade of titanium dioxide.
The sulphate route is perceived to be less environmentally friendly but acid
recycling or neutralization, combined with other by-product developments can make
it as clean as the chloride route. This conventional sulphate process is ordinarily having
a feedstock with varied types of outputs either in low-grade ilmenite (44% TiO2) or Ti
slag (>70% TiO2) and subsequently does not require a distinct grade of TiO2 to upgrade
the ilmenite into synthetic rutile. Therefore, incompatible kinds of ilmenite ores have
been processed simultaneously using this method.
The sulphate process is run as a batch process that sort of only a few units of
operations. The steps for this process involve three main stages:
1. Digestion: Normally, the ore is grounded or being as titanium slag which is
subsequently digested in concentrated sulphuric acid producing titanyl sulphide
(TiOSO4) at the condition of 150-180°C to dissolve the titanium and iron according to
Eq. 4.0.
FeTiO3 + 2H2SO4 → TiOSO4 + FeSO4 + 2H2O Eq. 4.0
22
2. Precipitation: the ferric ions in feedstock solution are reduced with scrap iron
to ferrous sulphate. Iron sulphate is removed from the solution The titanium liquor is
then concentrated and hydrolysed to produce titanium dioxide hydrated as shown in
equation below.
𝑇𝑖𝑂𝑆𝑂4 + 𝐻2 𝑂 = 𝑇𝑖𝑂2 𝑛. 𝐻2 𝑂 + 𝐻2 𝑆𝑂4 Eq. 5.0
3. Calcination: after successfully removing the iron, the titanyl sulphate is
hydrolysed to titanium dioxide hydrate. The precipitate is then chemically purified,
filtered, and calcined at 800 to 1100°C to produce titanium dioxide formation of pure
TiO2 crystals.
𝑇𝑖𝑂2 𝑛. 𝐻2 𝑂 = 𝑇𝑖𝑂2 + 𝑛𝐻2 𝑂 Eq. 6.0
2.5.2 Chloride process
The chloride process was first commercialized in the United States in 1958.
The process is continuous and is usually conducted in a fluidized bed reactor. The
chloride route produces a purer product with a tighter range of particle size. The main
process steps are as follows:
1. Chlorination: Dry ore is fed into a chlorinator together with coke and
chlorine to make titanium chloride. The chlorination reaction is exothermic and is
carried out at approximately 900°C in a reducing atmosphere. atmosphere. The basic
reactions can be written as follows:
TiO2 + 2Cl2 + C → TiCl4 + CO2 Eq. 7.0
2. Condensation and purification: volatile chloride species that are used as
titanium tetrachloride (TiCl4) are purified by fractional distillation
23
3. Oxidation: The next step involves the oxidation of titanium chloride by
burning it in oxygen together with another combustible gas. By adding seed crystals,
the titanium dioxide is formed as a fine solid in a gas stream and is filtered out of the
waste gases. Crystal growth is controlled by adding nucleating agents to the gas stream
and the products are cooled by mixing with chlorine gas. The product is then washed
and dried before milling and surface treatment.
TiCl4 + O2 → TiO2 + 2Cl Eq. 8.0
2.6 Process of upgrading ilmenite
Apart from the chloride and sulphate processes, ilmenite ores also can be
upgraded into “synthetic rutile” products by involving a combination of
hydrometallurgical and pyrometallurgical processes suchlike Becher and Benilitte
processes. Table 2.7 displays numerical processes of upgrading along with their pros
and cons. Each of the processes gives different outcome circumstances either
favourable or on the other side of it. Thus, there is always extendible improvement that
drives research to develop innovative processes for ilmenite beneﬁciation.
24
Table 2.7 Summary of the various processes used for the processing of ilmenite.
Process Pyro-treatment Leaching Advantages Disadvantages

Becher Oxidation of a) NH4CL Allowing High energy
process Iron to Fe2O3 b)0.5M diverse ilmenite consumption,
and reduced to H2SO4 ores into the emission of CO2
metallic Fe at feed and multistep iron
1200 ºC conversion
Benilite Convert Fe (III) 18 – 20M Simple one step Limited ilmenite
process to Fe (II) by HCl conversion type as feed
carbo thermo
reduction
Kataoka Conversion to H2SO4 Less corrosive Large iron
process ferrous form compared to sulphate waste is
HCI acid produced
Laporte Iron conversion 18% HCI Ease for Despite lower
process to FeO with leaching FeO temperature,
lower emission of CO2 is
temperature and still high
controlled CO2
pressure
Auspact Magnetization 25% HCl Magnetic Higher acidity
process occurs at 800 – separation for needs to leach of
1000 ºC higher >97% the remaining
TiO2 magnetic iron
2.7 Design of experiment (DOE)
A strategic plan and a well-executed experiment can provide a ton of
knowledge regarding the influence on a response variable. Design of experiments
(DOE) is used to evaluate input factors and to determine their effect on outputs
(response) which also allows ascertaining an interaction between selected factors. The
design of experiments (DOE) technique is a structured and systematic tool for
determining any circumstance in which the response depends on the amount of one or
more independent variables. DOE is designed to solve complicated situations in which
more than one variable influence response and two random variables connect.
In this case study, the design of the experiment (DOE) is performed to acquire
the optimum conditions for Malaysian ilmenite sand in a hydrochloric acid leaching
25
system. DOE was done by using Minitab 19 software. The MINITAB program
interface is intended to be simple straightforward. There are several other effective
programs available, but rarely used since they are difficult to run. Despite its obvious
simple structure, MINITAB covers a wide variety of sophisticated methods.
MINITAB facilitates the majority of the statistical models and techniques which most
users require to design and evaluate experiments (Arnold, 2006). The effect of
concentration of hydrochloric acid, acid to solid ratio, temperature, and concentration
of reducing agent was studied with the aid of the software.
2.7.1 Evaluation of MINITAB data
Screening designs, factorial designs, response surface designs, mixture
designs, and Taguchi designs are among the five types of designs available in Minitab
(Arnold, 2006). The response surface design (RSM) was chosen because the goal of
the scoping study was to optimize the interesting responses that are influenced by the
variables or known to be the factors (Donkoh et al., 2012). RSM is more likely a
beneficial design than other designs. For instance, screening design can evaluate more
variables in the very least experimental runs, but it cannot interpret the interaction
between variables since it only can run with two levels. Unlike RSM which can apply
intermediate level can evaluate the main effects, two-factor interactions, and terms that
can measure the curvature induced in the response by each variable (Arnold, 2006).
Analysing data from the RSM technique is used for modelling curvature in
data and classifying factor settings that optimize response. Surface design is typically
used after a factorial or fractional factorial experiment has defined the most significant
aspects (factors) in the process. Two types of response surface designs that are Central
Composite designs (CCD) and box-Behnken designs. CCD is being used to describe
the design before analysing data. A complete quadratic model can be accommodated
26
by Central Composite designs. Since it can encompass details from a properly planned
factorial experiment, these designs are commonly used when the design plan demands
sequential experimentation (Rostamiyan et al., 2015). Box-Behnken designs, on the
other hand, tend to have fewer design points than central composite designs. It can
estimate first and second-order coefficients efficiently but cannot provide factorial
experiment runs. In contrast to central composite designs, which can add up to five
levels per factor, Box-Behnken designs only can have three levels per factor.
After the experiment takes place, a model from the experimental data is
constructed as the mathematical description of how the response behaves as a function
of the input variable or variables. In this case study, analysis of variance (ANOVA) is
the model used to determine whether survey or experiment results are significant
which can figure out whether either test needs to reject the null hypothesis or accept
the alternate hypothesis(Arnold, 2006). This is a computational approach with the
primary goal of estimating the relative influence of every factor on the overall response
(Shivprakash & Harsha, 2017). At last, a confirmation test is performed to validate
the optimal process parameters obtained through process parameter design.
2.8 Factor affecting direct leaching
2.8.1 Particle size
The author, Olanipekun (1999) has published a kinetic study of the leaching of
Nigerian ilmenite in a chloride solution at temperatures ranging from 70 to 90°C. In
his study, titanium and iron dissolution were explored in 7.2 M HCl solution at 70°C
using three particle size fractions: 20-37, 37-53, and 53-74 µm. The result shows that
the highest dissolutions rate of both metals shown at the finest particles, in the case
study was 20–37µm.
27
Similar views by several authors (El-Hazek et al., 2007; Samal, 2011; Mehdilo
& Irannajad, 2012; Ramadan et al., 2016) where an average of fine particles was
inversely proportional to the rate of dissolution of titanium and iron. This is because
the decrease in particle size which consists of large surface area will expose more to
the leaching solution (Ramadan et al., 2016). Under ideal leach conditions, coarser
fractions showed up to a 10% reduction in dissolution(Van Dyk et al., 2002; El-Hazek
et al., 2007). On the other hand, Table 2.8 show the effect of particle size on ilmenite
leaching by other authors. It discovered the optimum particle size to get greater
extraction of titanium and iron in ilmenite leaching.
28
Table 2.8 Effect of particle size on ilmenite leaching
Optimum size fraction

Maximum
Parameter(s)
extraction (%)
References
(µm)
Fe Ti
Period (hr)
S/L (g/L)
HCI (M)
Fraction
stir rate
T (°C)
(rpm)
(µm)
Size
20-37 70 1:300 500 5 7.2 67 62.0 20-37

Olanipekun,
37-53 60.0 52.0

53-74 54.0 46.0
1999
104-107 80 1:20 * 5 12 * * 61-74

al., 2007
Hazek et
84-89
61-74
El-
37-43
74 rtpa 1:20 * 2 6 * * 74
Samal,
2011
200 95 1:4 * 1 1.3 92 10 100

Mehdilo
150 89 7
, 2012
100 88.3 3.9

75 75 2.3
+1000 70 1:6 300 3 6.5 47.5 45.4 63
710-1000 48.1 46.0
Ramadan et al., 2016
500-710 50.9 47.8

355-500 54.6 51.7
250-355 58.3 55.4
150-250 63.0 60.0
90-150 65.3 63.2
63-90 71.2 66.0
-63 72.4 68.1
75-90 80 1:4 * 5 7 78.2 62.3 53-63
63-75 78.2 72.8
Jabit,
2017
53-63 80.0 82.5

45-53 53.0 97.0
rtpa -room temperature
* - not reported
2.8.2 Acid concentration
According to(Wahyuningsih et al., 2013) controlling the concentration of
hydrochloric acid encourages iron dissolution and could dissolve titanium at the same
time. The precipitation of TiOCl2, which does not occur at high acidity, (Samal, 2011)
discovered that the leaching percentage of titanium was lower than that of iron at low
29
acidity. Meanwhile, (El-Hazek et al., 2007) high acid concentration (12M) leaching at
80°C is recommended to prevent titanium hydrolysis at a high solid to liquid ratio
(S/L). Other researchers revealed that high acid concentrations enhanced titanium and
iron dissolution which can be referred at Table 2.9. It also mentioned that the
maximum leaching percentage of these metals was obtained at a specific HCl
concentration, depending on other factors (Olanipekun, 1999; El-Hazek et al., 2007;
Das et al., 2013). In the HCl range of 0.75–1.5M at 50°C, the leaching solution of pre-
treated titanium slag was quite turbid and difficult to filter.When the HCl concentration
was higher than 1.5M, the filtrate became clearer and had fewer finely suspended
particles, but precipitation occurred in this solution after a few days, according to
Middlemas et al (2013). The hydrolysis of dissolved titanium appears to occur at either
low acidity or low temperature.
Some studies had also analysed the effect of HCl concentration on the selective
leaching of iron from ilmenite over titanium (Mahmoud et al., 2004; Lasheen, 2005;
Guo et al., 2014; Gireesh et al., 2015; Ramadan et al., 2016). Mahmoud et al., (2004)
discovered that under reducing conditions, almost all the iron was dissolved in 30 wt%
HCl, while titanium was barely dissolved. According to Guo et al., (2014) and
Ramadan et al., (2016), the concentration of 20 wt. % HCl was at optimum acid
concentration for selective iron leaching and therefore raising the amount of TiO2 in
the residue. Meanwhile, referring to the literature Guo et al., (2014), a leaching
solution containing more than 220 g/L HCl should only be used to produce a product
comprising upwards of 92 % TiO2. Other researchers noted that as the acid
concentration increased from 2 to 12M, the iron leaching efficiency increased, but the
solubility of TiO2 appeared to be negligible in this acid concentration range(El-Hazek
et al., 2007; Gireesh et al., 2015).
30
Table 2.9 Effect of hydrochloric acid concentration on ilmenite leaching
Parameter(s) Extraction (%)
Optimum HCI (M)

Period (hr)
Size (µm)
S/L (g/L)
HCI (M)
Stir rate
T (°C)
(rpm)
References Fe Ti
Olanipekun, 1999 7.2 70 1:300 500 5 53-74 52.5 42.5 9.6

8.4 70.0 60.0
9.6 82.5 75.8
Mahmoud et al., 2004 5.2 110 1:7.23 400 6 -75 64.3 72.2 6.9
6.2 85.7 97.4
6.9 88.0 99.4
8.6 89.4 99.9
10.3 87.9 99.9
Lasheen, 2005 4.0 90 1:5 350 4 * 17.5 0.5 12.0
5.0 19.0 0.6
6.0 21.0 0.7
7.0 23.0 0.7
8.0 27.0 0.8
9.0 32.0 0.9
10.0 40.0 1.0
12.0 55.4 1.2
El-Hazek et al., 2007 7.0 80 1:20 350 5 74 25.0 50.0 12.0
8.0 78.0 78.0
9.0 80.0 82.0
10.0 84.0 85.0
11.0 85.0 87.0
12.0 92.0 92.0
Li et al., 2008 3.5 100 1:10.5 * 4 100- 85.1 82.0 6.9
5.2 200 9.4 94.0
6.9 93.3 100.0
8.7 93.1 100.0
Jonglertjunya & 1.5 90 1:18 250 2 106- 1.8 0.1 3.5
Woranart, 2009 2.0 150 2.6 0.4
2.5 2.9 0.7
3.0 4.1 0.9
3.5 6.0 1.8
Samal, 2011 1.0 rtp 1:20 350 1 -74 12.0 5.0 6.0
2.5 32.0 12.0
5.0 48.0 48.0
6.0 54.0 54.0
8.0 50.0 52.0
9.0 46.0 44.0
10.0 42.0 41.0
Wahyuningsih et al., 1.0 95 1:50 * * * 55.0 9.0 5.0
2013 2.0 67.0 10.0
3.0 78.0 13.0
4.0 69.0 17.0
5.0 77.0 19.0
Middlemas, 2013 0.5 50 1:10 * 4 45-53 52.5 42.5 2.0
1.0 70.0 60.0
1.3 82.5 75.8
1.5 64.3 72.2
2.0 85.7 97.4
Guo et al., 2014 6.2 108 1:10 * 7 74-200 88.0 99.4 9.0
7.2 89.4 99.9
9.0 87.9 99.9
Gireesh et al., 2015 3.3 50 1:10 * 8 * 17.5 0.5 9.8
6.5 19.0 0.6
9.8 21.0 0.7
* - not reported
31
2.8.3 Temperature
As the temperature increased from 25°C to 80°C, the possibility of acquiring
titanium and iron from ilmenite leaching significantly increased(El-Hazek et al., 2007;
Baba et al., 2013; Das et al., 2013a; Fouda et al., 2021). A great ilmenite leaching
efficiency can be obtained at elevated temperatures (>80°C), however, there were
several drawbacks under these circumstances, including increased HCl vapor loss and
the hydrolysis of solubilized titanium (Tao et al., 2012; Baba et al., 2013; Das et al.,
2013a).
Meanwhile, Lasheen,(2005) and El-Hazek et al.,(2007) stated that the poor
leaching efficiency of iron and titanium at room temperature was attributable to
ilmenite's low reactivity, whereas the leaching percentage of iron expanded more
progressively than titanium because the temperature is raised from 20°C to 50°C due
to partial hydrolysis of titanium.
According to Gireesh et al., (2015), a higher temperature of reaction
will increase ion mobility and therefore will improve the interaction between reactants
in solids and liquids. Interestingly, raising the reaction temperature above 100°C tends
to affect titanium leaching owing to excessive polymerization and hydrolysis of
titanium without adversely impacting iron (El-Hazek et al., 2007; Fouda et al., 2021).
The hydrolysis reaction of TiOCl2 is expected to increase at higher temperatures, so
perhaps the percentage of TiO2 recovered from ilmenite residue using moderate HCl
solution increased with raised temperature (Mahmoud et al., 2004; Jonglertjunya &
Woranart, 2009; Guo et al., 2014).
32
Table 2.10 Effect of temperature on ilmenite leaching
References Parameter(s) Maximum
temperature (°C)
extraction (%)
Optimum
Fe Ti
S/L (g/L)
HCI (M)
Fraction
Stir rate
Period
T (°C)
(rpm)
(µm)
Size
(hr)
Olanipekun, 70 7.2 1:300 500 5 hrs 53-74 50.0 46.0 90
1999 80 69.0 60.0
90 84.0 75.0
Mahmoud et al., 85 6 1:7.2 400 6 <75 46.2 49.2 110
2004 95 3 47.2 51.2
105 48.4 52.7
110 88.0 99.4
Lasheen, 2005 50 4 1:5 350 4 * 5.0 0.0 90
60 7.0 0.2
70 12.0 0.5
80 17.0 0.8
90 19.0 1.2
El-Hazek et al., 50 12 1:20 350 5 74 78.0 99.0 80
2007 80 98.0 98.0
100 98.0 96.0
Sasikumar et al., 30 3.5 1:100 * 1 * * 43.0 75
2007 50 45.0
70 48.0
Li et al., 2008 80 6.9 1:5.5 * 4 100-200 89.1 94.0 100
90 3 91.9 98.0
100 93.3 100.0
Tao et al., 2012 70 4 1:25 800 4 * 81.0 * 90
80 92.0
90 99.4
100 99.7
Das et al., 2013 60 5 * * 4 <75 91.3 91.1 70-80
70 98.7 95.8
80 98.8 96.3
Baba et al., 2013 70 3.7 1:1 480 2 90-125 * 54.0 80
80 58.0
90 65.0
Guo et al., 2014 30 6.5 1:5 500 8 <74 * 30.0 110
70 70.0
110 110.0
Gireesh et al., 40 9.7 1:10 * 8 * 62.0 * 70
2015 50 78.0
60 83.0
70 90.0
* - not reported
2.8.4 Solid to liquid ratio
Another paramount factor influencing the ilmenite leaching efficiency is the
solid to liquid ratio or ilmenite to HCI concentration ratio. As depicted in Table 2.12,
the optimal condition of solid-liquid ratio is 1:10.8 (Mahmoud et al., 2004) compare
33
to (El-Hazek et al., (2007) using solid-liquid ratio of 1:8 but only with a higher
concentration of HCI with additional 100g of iron as reductant. Li et al., (2008) also
found that utilizing a low solid-liquid ratio (1:7.3) yields 93.6% of iron extraction yet
took longer retention time because of using low HCI concentration respectively.
Table 2.11 Effect of solid liquid ratio on ilmenite leaching
References Parameter(s) Maximum
Optimum condition S/L

extraction
(%)
ratio (g/L)
Period (hr) Fe Ti
S/L (g/L)
HCI (M)
Fraction
Stir rate
T (°C)
(rpm)
(µm)
Size
RA
Mahmoud et 1:6.1 110 6 400 6 hr * 75 86.6 97.3 1:10.

al., 2004 1:7.2 88.0 99.4 8
1:8.8 89.8 99.5
1:10.8 90.1 99.6
1:11.5 90.4 99.7
El-Hazek et 1:7 80 12 350 2.5 100 74 42.0 * 1:8
al., 2007 1:8 >12 hr g 95.0
Fe
Li et al., 1:4.4 100 6.93 * 4 hr * 100-200 91.6 97.0 1:5.5

2008 1:5.5 93.3 98.5
1:7.3 93.6 98.8
1:11 93.9 99.0
* - not reported
34
2.8.5 Reducing agent
Reduction in solution can significantly increase the reactivity of ilmenite ore
during leaching with hydrochloric acid(Mahmoud et al., 2004). The existence of
metallic iron powder in ilmenite leaching as a reductant enhanced the production of
titanium and iron (Wahyuningsih et al., 2013). Nevertheless, the additional of a huge
amount of iron powder had a detrimental effect on ilmenite leaching because iron
dissolution rises the acid intake, and therefore monitoring the quantity of iron powder
used is essential in reductive leaching (El-Hazek et al., 2007; Wahyuningsih et al.,
2013, 2014). According to Mahmoud et al., (2004) a small excess of a reductant during
the reductive leaching process could reduce Ti (IV) to Ti(III), significantly reducing
the tendency for Fe(II) ions to be oxidized to Fe (III). This is due to the breaking up of
the grain structure caused by the reductive dissolution of ferric iron, the reactivity of
ilmenite ore rising, causing further diffusion of acid protons to pores created in the ore
particles.
In this process, dissolved Ti (IV) is hydrolysed and precipitated, resulting in
largely ferrous chloride in the leaching solution and high purity TiO2 in the ilmenite
residue.Besides, Das et al., (2013) discovered that the leaching efficiency of titanium
and iron was in the order CaCl2 >MgCl2 > NaCl in his study on the leaching of ilmenite
ores by HCl solution in the presence of these chloride salts as the reducing agents. The
CaCl2 was concluded to be the most effective salt because of its high solubility.
Meanwhile, Gireesh et al., (2015) reported that leaching efficiency of ilmenite and the
leaching residue can be enriched progressively by the presence of sulfate salts for
instance CaSO4, MgSO4, NaSO4, and K2SO4 where divalent sulfate metals (Ca and
Mg) giving better performance rather than monovalent sulfate metals (Na and K).
35
Table 2.12 Effect of reducing agent on ilmenite leaching
Parameter(s) Maximum
extraction (%)
Optimum condition RA
Fe Ti
Pulp Density (w/w)

References
Stir rate (rpm)
Period (hr)
Size (µm)
S/L (g/g)
HCI (M)
T (°C)
RA
Mahmou none 70 9.8 * * 6 75 4.0 88.6 92.6 More

d et al., CaCl2 3.3 96.4 96.6 effective
2004 (460 with
g/L) additional
of CaCl2
CaCl2 5 4 87.0 90.0 High
(405 chlorine
g/L)
ion
CaCl2 98.0 96.0 concentrat
(500
g/L) ion can
acquired a
better
leaching
outcome
CaCI 99.0 98.0 Better
(745g/L) leaching:
MgCl2 90.0 88.0 CaCI>
(543g/L) MgCl2>
NaCI 59.0 57.0 NaCl
(359g/L)
Mahmou none 11 6 1:7.3 400 6 75 * * 29.0 Additional
d et al., 0 Fe tends
2004 to produce
0.075g 98.0 more
Fe extraction
powde of
r titanium
in residue.
El- 100g 80 12 1:10 350 2.5 74 * 94.0 * Low iron

Hazek Fe extraction
et al., without
2007 Fe.
* - not reported
36
2.9 Kinetic study of ilmenite leaching
Kinetic studies are frequently utilized to determine the ideal reaction rate
model, which can primarily be explained by the mechanism reaction of the experiment
under study. The word “kinetic” is describing the study of chemical reactions’ rates on
the reactant and the product formed which allows for the prediction of reaction
conditions. This kinetic study is also capable to elucidate a piece of essential
information from the mechanistic reaction which some circumstances condition how
chemical reactions take place, factors that control the reaction rates, divulging some
uncertainty of intermediate occurring, and indeed is very important for further
enhancement of productivity the process being studied. On the other hand, such
information acquired from this knowledge can also give a well understanding of the
mineral behaviour and perceive the way it is weathered.
Exploitation of valuable minerals from impurities is a crucial part many of
fields for instance hydrometallurgy, geochemistry, pyrometallurgy, and other fields
related to the processing of this creature. In industry, a piece of knowledge in terms of
its kinetic reaction and mechanism of dissolution can assist in the prototype,
development, and optimization of processes for the extraction of the metals. To obtain
a very systematic and optimum condition in the leaching of ilmenite studies, the
essential information in kinetic of the dissolution behaviour of titanium and iron in
concentrated acid should be considered which has been done by a few authors. Despite
that, merely of them are considerable uncertainty data and still required further
analysis to cope with the hesitation.
37
2.9.1 Selection of leaching kinetic models
Over the past few years ago, several models were introduced as new attention
to give shed light on the leaching operation which subsequently gives a great
significant development in valuable mineral extraction. These models include kinetic
models, reaction models, thermodynamic models, empirical and semi-empirical
models, variable activation energy models, geochemical models and thermodynamic
models were used regarding the attention studied.
In the hydrometallurgical process, and efficiency of the kinetic leaching
process is influenced by numerical factors, for instance mineralogy, area of the surface,
the concentration of reactants, formation of product layers, and temperature. By using
a small range of size fraction samples, it is capable to give a clear vision and more
comprehensibility on kinetic reaction study, especially regarding the response of
substance presents and the most convenient way for valuable metals recovery.
Methods used in this study to assess the relationship between leaching
efficiency and leaching parameters were demonstrated using three models. Under the
premise that the particles are homogeneous and spherical, the shrinking sphere,
shrinking core, and a combination of internal diffusion and chemical reaction models
are the kinetic models for the dissolution of sized particles. Figure 2.4 shows the three
models used in this case study.
In the shrinking sphere model shown in Figure 2.4(a), the rates are controlled
by a chemical reaction at the surface of the reacting particles, where it is an analogous
to the situation where the product completely dissolves in the liquid and the reaction
occurs on the exposed surface of the particle. Whereas in the shrinking core model
shown in Figure 2.4(b), the rates are controlled by mass transfer through a thickening
38
product layer on the surface. This condition is where the particles are dissolved as they
react to liquid reactant giving itself to be to be shrinking and a gelatinous layer
formation around the surface of the unreacted core. The other model, shown in Figure
2.4(c), illustrates the combination of chemical and diffusion reactions. These equations
can be written as integrated rate equations for the reaction involving H+ ions for the
reaction A(aq) + bB(s) = products as follows:
For the shrinking core model:

1 − 3(1 − 𝑋)2/3 + 2(1 − 𝑋) = 6𝑏[𝐻 + ]𝐷𝐻+ 𝑟 −2 𝑝−1 𝑡 = 𝑘𝑝1 𝑡 Eq. 9.0
1 − 3(1 − 𝑋)2/3 + 2(1 − 𝑋) = 6𝑏[𝐻 + ]𝑏𝑢𝑙𝑘 𝐷𝐻+ 𝑟 −2 {(1 − 𝜀)𝑝}−1 𝑡 Eq. 10.0
= 𝑘𝑝1 𝑡
For the shrinking particle model:

1 − (1 − 𝑋)1/3 = 𝑏[𝐻 + ]𝑏𝑢𝑙𝑘 𝑘𝑟 −1 𝑝−1 𝑡 = 𝑘𝑠𝑠 𝑡 Eq. 11.0
For the combination models:

− ln(1 − 𝑋) = 𝑘𝑝1 𝑡 Eq. 12.0
where X = fraction dispersed at time t, kss, kpl = apparent rate constant, [H+]
= acid concentration in bulk solution (mol cm-3), DH+ = H+ diffusion coefficient
through the product layer (cm2 -1s), r = initial particle radius (cm), = molar density of
the dissolving metal in the initial particle (mol cm-3), = particle porosity, b =
stoichiometric factor
39
Figure 2.4 Illustrates various mechanisms of leaching (a) Shrinking sphere
particle model, (b) shrinking core model and (c) combination of shrinking core-
shrinking sphere models (Safari et al., 2009)
2.9.2 Kinetic study of hydrochloric acid leaching
According to Van Dyk et al., (2002), when ilmenite encounters the
hydrochloric acid solution, as predicted by the chemical reaction Equation 13, both
iron and titanium dissolve. At this point, the rate is determined by the rate of the
chemical reaction. In hydrochloric acid solutions, Ti(IV) polymerizes.
When the titanium concentration in the solution exceeds 10–3M, Ti(IV)
polymerizes, and the diffusion of polymerization away from the reaction interface
becomes the rate limiting step in leaching which can be referred to in Figure 2.5. Over
a certain duration of time, the titanium concentration in the leaching solution attains a
certain level, leading to the formation of TiOCl2 in the pores of the particles as fine
particles.
40
As a result, the rate-determining step was switched to the diffusion of the active
species through the product layer(Van Dyk et al., 2002). The researcher also
discovered that at high solid to acid ratios, the diffusion of hydrogen ions to the
reaction interface became the rate-limiting step due to the formation of a TiO2.H2O
precipitate in the existing product layer.
𝐹𝑒𝑇𝑖𝑂3 + 4𝐻𝐶𝐼 = 𝐹𝑒𝐶𝐼2 + 𝑇𝑖𝑂𝐶𝑙2 + 2𝐻2 𝑂 Eq. 13.0
Figure 2.5 Ti(IV) chloride speciation diagram for 0.1 Ti(IV) activity at 298 K
Besides, (Olanipekun, 1999) reported a kinetic study on the leaching of a
Nigerian ilmenite using a hydrochloric acid solution at temperatures ranging from 70
to 90°C. The researcher mentioned that throughout the reaction, two diffusion
processes are involved: (i) diffusion of H+ and (ii) diffusion of Ti4+ and Fe2+ obtained
by the surface chemical reaction at the unreacted core. But since H+ diffuses faster
than Ti4+ and Fe2+, the reaction rate is controlled by the diffusion of titanium (VI) and
iron (II) through the product layer.
41
Another reports mentioned that the dissolution rate of hydrochloric acid
solution is diffusion controlled and follows the shrinking core model, with an apparent
activation energy of 17 kJmol–1(Ramadan et al., 2016). The analysis of kinetic data on
the leaching of rutile ore in HCl solution revealed that the dissolution mechanism
followed a diffusion controlled shrinking core model (Baba et al., 2013). According
to (Tsuchida, 1982) discovered that in the range of temperature between 30–50°C, the
dissolution rate of titanium from ilmenite was well demonstrated by the rate equation
based on the rate-determining step of surface chemical reaction, whereas at >60°C, the
surface chemical reaction became so fast that the dissolution rate was limited by
diffusion through the product layer. The rates after 4 hours at 70°C or 3 hours at 80°C,
nevertheless, deviated from the rate equation attributed to the formation of hydrous
titanium (IV) oxide on the ore's surface. Table 2.13 summarizes the published kinetic
parameters for ilmenite leaching in hydrochloric acid solution.
42
Table 2.13 Kinetic parameters for ilmenite leaching in hydrochloric acid solution
Origin Condition Models Activation energy References

(kJ/mol)
Japan 11.3-11.6M Shrinking 81.2 (Ti), 73.2 (Fe) (Tsuchida,
HCl, 30-80°C, particle/core 1982)
S/L=5/200
Jos 7.2-9.6M HCl, Shrinking 67.1 (Ti), 62.4 (Fe) (Olanipekun,
Plateau, 70-90°C, core 1999)
Nigeria S/L=0.5/150
Banglades 6 M HCl + Shrinking 16.5a (Ti), 21.8a (Fe) (Habib et al.,
h 0.5M CH3- particle/core 66b (Ti), 90b (Fe) 2006)
H2O, 45–
110°C, S/L=
2/100
Nigeria 2M HCl, Shrinking 38.4 (Ti) (Baba et al.,
80°C, S/L = particle 2013)
1/100
Abu 20% HCl, 40– Shrinking 17.6 (Ti) (Ramadan et
Ghalaga, 110°C, core al., 2016)
Egypt S/L=1/6
Western 4-9M, 60- shrinking 90.1 (Ti), 71.9 (Fe) (N. A. Jabit
Australia, 80°C, S/L= core and
Australia 2/25 Senanayake,
2018)
a is low temperature, b is high temperature
2.10 Research background on prospecting area
Bukit Kelip is a mountainous area that is in a sub-district of Terengganu,
Malaysia namely Hulu Dungun, and approximately 150km from the south of the
capital Kuala Terengganu which connects it through the Jerangau – Jabor highway. Its
geographical factor is 768 meters above sea level and surrounded by floras like rubber
and oil palm cultivation in the north of the mountainous area.
Ilmenite sands were obtained from the head of Dungun province situated at the
Malaysian state of Terengganu (latitude 04°38’49.5” N, longitude 103°03’56” E) with
an above sea level is 768 meters. The sample collection was carried out at the main
river source, the Cheniah river of Kelip Hill, which flows towards the northern part of
43
the area, as illustrated in Figure 2.6-2.9. The stream system has a dendritic pattern and
is predominantly used for agriculture (rubber and oil palm activities).
According to the annual JMG report 2014, a reconnaissance evaluation for
metallic mineral resources was carried out by the Department of Mineral and
Geoscience Malaysia (JMG). This area was selected based on previous studies
showing favorable ilmenite anomalies with an estimated reserve is 3060 tonnes (Nazri
& Hadi, 2014). This geochemical anomaly is found at the main river of the study area,
Sungai Cheniah which flows to the north of Bukit Kelip as shown in Figure 2.8 (Nazri
& Hadi, 2014). As claimed by JMG’s report, estimation has been made for the quantity
of ilmenite which is around 83.2% to 95.7% with average content is 91.87%. On the
other hand, chemical analysis shows an average value for TiO2 is 40.78% whilst P2O5
is 0.05%.
The general geology of Bukit Kelip and its vicinity is composed of sedimentary
rock, metamorphic rock, and intrusive diorite as shown in Figure 2.9. Sedimentary is
an aged rock of the early carbon that belongs to the Sungai Perlis Formation. The
Sungai Perlis Formation is composed of carbonated slabs of sandstone, limestone,
sandstone, and conglomerate which overlain Diorite Kelip. The diorite rock is named
Diorite Kelip after the hill of the study area. The corollary rocks are extending north
and south with a size of medium grainy and dark grey. The main fault is also in the
same direction. The contact zone between the Sungai Perlis layer of Perlis and the
intrusive rocks of the diorite produced the hormone rock in the study area.
44
Figure 2.6 Map showing the localities of sample in Bukit Kelip, Hulu Dungun,
Terengganu, Malaysia (Developers Guide for QGIS — QGIS Documentation
documentation, 2002)
45
Figure 2.7 Study area in Bukit Kelip, Hulu Dungun, Terengganu (Sources: JMG
Terengganu 2014)
46
Figure 2.8 Topography and river map in Bukit Kelip, Hulu Dungun, Terengganu
(Sources: JMG Terengganu 2014)
47
Figure 2.9 Geological map of Bukit Kelip, Hulu Dungun, Terengganu (Source:
JMG Terengganu 2014)
48
CHAPTER 3
MATERIALS AND METHODOLOGY
3.1 Study description
Sample was examined throughout the characterization analysis. Multiple
analyses were used to characterize samples taken from Cheniah river, Kelip hill,
Terengganu, as a crucial aspect in meeting the needs of ilmenite leaching criteria. The
ilmenite morphology, chemical composition, mineral phases, particle size distribution,
and mineral liberation of ilmenite samples are all evaluated in this study. This
characterization survey's information and analysis aided in the identification and
design of an appropriate treatment method for this ilmenite sand.
Prior to testing ilmenite leaching, a leaching experiment is designed using
MINITAB 19 software applying the Response Surface Design method (RSM). Batch
leaching is set up and run-in accordance with Design of Experiment (DOE)
specifications. The data collected from these investigations were used to calculate
leaching efficiency, which was calculated based on leached solution and residue
analysis. To develop statistical models of the leaching process, the leaching statistics
(highest Ti or Fe dissolution after complete leaching) will be analyzed using a
statistical method that is analysis of variance (ANOVA). Leaching kinetic studies are
carried out by focusing on two parameters: HCI concentration and temperature, with
the rest of the parameters set to the optimum condition. Dissolution mechanism and
kinetics are described in detail, as well as statistical mathematical modeling of the
leaching process. Figure 3.1 shows a flowchart of the overall analysis for the ilmenite
sand sample.
49
1 2 Determination of leaching efficiency & significant parameters
Sampling by panning method at Sampling by Coning Magnetic

Magnetic Batch leaching design using Response
Separator
Bukit Kelip, Terengganu & Quartering method Surface Methodology (RSM)
Characterization on Non- Concentrate

bulk sample Magnetic
Leaching parameters:
Characterization
on concentrate Temperature, HCl Concentration, S/L
Mineral Liberation Physical Characterization
ratio, time, reducing agent (RA)
Studies on tailing
PSA
Optical microscope
Mineral Phases
SEM/EDX Grinding using XRD
Identification
Ring Mill
< 75µm
Characterization on Residue
Elemental leaching solution
composition XRF
Vacuum filtration
pump
50
3 Determination of mechanism, kinetic and rate of determining step
Parameters for kinetics Batch leaching design using

ICP
AAS
} Fe &
Ti
Drying
Fractional Factorial Design

Leachate taken at Characterization
Temperature, HCl Concentration on residue
interval time
SEM/EDX
ICP
AAS
} Ti & Fe
Figure 3.1 Experimental flowchart for overall analysis for ilmenite sand sample
3.2 Site description
Ilmenite sands were acquired from the head of Dungun province in the
Malaysian state of Terengganu (latitudes 04°38'49.5" N, longitude 103°03'56" E, at an
elevation of 768 meters above sea level). The specimens were taken at the main river
source, Kelip Hill's Cheniah stream, woth reference to Figure 3.2, the site sampling is
labelled as A. According to the Mineral and Geoscience Department Malaysia report
in 2014, a part of this particular earth’s surface is made up of sedimentary rocks,
metamorphic rocks, and intrusive diorite rocks. Carbonaceous slate, phyllite, siltstone,
conglomerate, and sandstone constitute most of the sedimentary and metamorphic
rocks which dominate the geological setting of the study field Meanwhile, based on
this Figure 3.2, the geology of Terengganu is roughly made of carboniferous marine
shales, sandstones, limestones and volcanics with Eastern Belt- I type granitoids.
51
Figure 3.2 Studied area is labelled as A in geological map of Peninsular
Malaysia. Source:(Yusri & Kadir, 2018)
52
3.3 Materials and reagents
There are few materials and chemical reagents used during this project.
Table 3.1 Lists of materials and reagents.
Chemical Formula Purity Manufacture Uses

Name
Epoxy Resin - - Eurochemopharma Sdn .Bhd Polished
section
Epoxy - - Eurochemopharma Sdn. Bhd Polished
Hardener section
Hydrochloric HCI 37% Merck, Germany Acid leaching
acid fuming
Iron powder Fe 99% GoodFellow Cambridge Reducing
agent
3.4 Characterization analysis
3.4.1 Sample preparation
The ilmenite sand (IS) was prepared as illustrated in Figure 3.3 before initiating
the interpretation on characterization analysis. IS was applied to the Jones Riffles
sampling method to predetermine the chosen randomly ilmenite from a wide fraction
in order to minimise sample quantity and corroborate the sample's homogeneity and
representativeness. The IS was examined for particle size analysis using a
representative sample. Another fraction of the sample is being prepared for
morphological study, elemental composition, mineral liberation, and phase
identification. Next, using the magnetic separation method, magnetic samples,
concentration ilmenite (CI), and non-magnetic samples, tailing ilmenite (TI), were
recovered. Since the samples were gathered were in a broad size fraction, it would still
have to be reduced to less than 75 m using a ring mill for subsequent characterization
study such as x-ray diffraction (XRD) and x-ray fluorescence (XRF). These samples
were then filtered using sieves with 75 size openings to get range sizes less than 75 m,
53
and the samples were processed in accordance with each analytical requirement, as
stated more in the next section.
Figure 3.3 A flowchart depicting steps implied in the characterization of the

samples in this work
3.4.2 Morphological studies
Preliminary morphological studies were done via Stereo Zoom Microscope
(Kunoh Robo) for optical images of the samples. Pulverized samples were mounted
with mixture matrix of epoxy resin and hardener with ratio of hardener to resin is 1:1
54
respectively and left overnight for completely hardened before proceeding to polishing
step. Initial polished were done with a rotary grinder (Metaserv) using 180, 240, 320,
400, 600, 800, 1000, 1200, and 2000 grit size of sandpapers and subsequently using
oil-based lubricant on the Metaserv grinder polisher. This samples then were visualize
under optical microscope, Stereo Zoom Microscope (Kunoh Robo) for surface
morphological studies. Colour, size and shape exhibit by mineral grains under
microscope can indicate the type of mineral present yet it is less accurate technique for
understanding the morphology and phases of substances. Thus, sample is required to
be analysed with FESEM/EDX (Zeiss Supra 35VP-24-58) as to bridge the gap of
mineral abundance and liberation. All the samples were coated with carbon to make
the mineral surface conductive. In this case study, back scattered electron (BSE)
images were made used for mineral identification by physically, whilst EDX is utilized
providing elemental composition of the samples. Mineral phases were also defined by
elemental mapping study offering such information of elemental distribution present
in different colours that constitute in the samples.
3.4.3 Particle size distribution (PSD)
Ilmenite sand sample was subjected to particle size distribution (PSD) which
is vital in determining optimum size of feed for leaching process and for obtaining
maximum efficiency of the leaching. This analysis was conducted with screens from
500 µm to 53 µm in the laboratory. Cumulative size distribution such as D10, D30, D50,
D60 and D90 were procured from particle size distribution. Further analysis by
quantitively was done by calculating the coefficient of uniformity (Cu) and the
coefficient of curvature (Cc) mathematically using equation 14 and equation 15. The
span value (Y) meanwhile for distribution of the sample is defined as equation 16.
55
𝐷60
Cu =
𝐷10 Eq.14
(𝐷30 )2
Cc =
(𝐷60 X𝐷10 ) Eq.15
𝐷90 − 𝐷10
Span value (Y) =
2𝐷50 Eq.16
3.4.4 Mineral phase identification using X-Ray Diffraction (XRD)
The mineralogical phases of the samples in powdered form with size fraction
between 0 to 20µm are examined by X-Ray diffraction (XRD) using (Bruker D8
Advanced X-ray Diffractometer) giving quantitative data in terms of weight percentage
of the phases present. The XRD was operated at a generator voltage 40kV and 30mA
current with diverge range of 2 from 20º to 70º. The recognition of minerals of the
samples is performed using PANalytical X’Pert Highscore Plus software by which the
most suitable PANalytical ICSD databases will match to measured profile offering to
mineral phase identification. In order to refine theoretical line profile to the experimental
data profile, Rietveld method is executed for every samples. Once mineral phases
identified, the data is imported to OriginPro 8.6 Software to plot graph intensity (a.u)
versus 2(º).
3.4.5 Elemental composition using X-Ray Fluorescence (XRF)
An ascertainment of elemental composition of the samples were done via X-
Ray Fluorescence (Axio Max) with maximum volt of up to 60 kilovolts and 160
microamps (µA) and equipped with several crystals such as PE002, LiF200, PX1, and
Ge 111. Samples were required to pulverize below than 75µm using ring mill grinder
and each sample was ground into 50µm grain size using a motorized grinding machine
56
and was further ground manually to a finer grain size of 20µm, suitable for X-ray
fluorescence (XRF) analysis. The specimen for the XRF analysis was made by igniting
0.5g of sample and 5.0g of spectroflux at 1100˚C for 20 minutes, before it was cast
into a glass disc, 32mm in diameter.
The specimen was analysed for 10 major elements using a fully automated
PanAlytical Axios Max (Holland) XRF spectrometer, with a standard elemental setup.
The calibration technique was employed. The 10 element curves were constructed
using 30 high quality international standard reference materials, comparable in
composition to the samples. For minor and trace elements, each sample is formed into
pressed-powder pellet using 1 gram of sample baked with 6 grams of Boric acid in a
32mm diameter round shaped disc with the sample placed at the centre and Boric acid
as a binder around it. The sample was pressed with a hydraulic press machine at 15
tonnes for 2 minutes. The XRF analysis was done by scanning for the presence of
elemental peaks using the Omnian software.
3.4.6 Mineral Liberation studies
Three different size fractions were chosen, which are (-90 +75) µm, (-75 +63)
µm, and (-63 +53) µm respectively. Each sample is observed under scanning electron
microscope via energy dispersive x-ray analysis (SEM/EDX) by taking image at
different spots of the sample. Then, summation of interest minerals was counted with
ImageJ software using equation 17 aiming to evaluate degree of liberation of interest
minerals.
FM Eq.17
% Mineral Liberation = x 100
FM + LM
57
Where:
FM= Total area of mineral particles (of interest) which are liberated
LM= Total area of mineral particles (of interest) in locked form
3.5 Batch Leaching experiment
In this experiment, design of experiment (DOE) is performed to determine the
optimum conditions for Malaysian ilmenite sand in hydrochloric acid leaching system.
DOE was done by using Minitab 18 software. The effect of concentration of
hydrochloric acid, acid to solid ratio, temperature, and concentration of reducing agent
were studied by the aid of the software. The actual and coded values of the parameters
(factors) are presented in Table 3.2. As the objective of the scope study is to optimize
the interested responses which is influenced by the variables (factors), response surface
design is selected as illustrated in Table 3.3-3.6
Table 3.2 Symbols, Actual, and Coded Levels of the Parameters Used
Variable Units Lowest Low Center High Highest

level level Level level level
( -2) (-1) (0) (+1) (+2)
Temperature °C 60 70 80 90 100
HCI % 6 7 8 9 10
concentration
Solid to liquid g/L 4 6 8 10 12
ratio
Concentration of g/g 0 0.1 0.2 0.3 0.4
reducing agent
58
Table 3.3 Design Summary
Factors: 4 Replicates: 1
Base runs: 31 Total runs: 31
Base blocks: 1 Total blocks: 1
Table 3.4 Point Types
Cube points: 16
Center points in cube: 7
Axial points: 8
Center points in axial: 0
59
Table 3.5 Design Table (randomized)
Run Blk A B C D
1 1 1 -1 -1 1
2 1 0 0 -2 0
3 1 0 0 0 0
4 1 -1 -1 1 -1
5 1 1 1 1 1
6 1 1 -1 1 -1
7 1 -1 1 1 1
8 1 0 0 0 0
9 1 0 0 0 0
10 1 -1 1 1 -1
11 1 0 0 0 0
12 1 0 0 0 0
13 1 0 -2 0 0
14 1 -2 0 0 0
15 1 1 -1 -1 -1
16 1 0 0 2 0
17 1 0 2 0 0
18 1 1 1 -1 1
19 1 1 1 1 -1
20 1 0 0 0 0
21 1 1 1 -1 -1
22 1 -1 -1 -1 -1
23 1 1 -1 1 1
24 1 -1 -1 1 1
25 1 -1 1 -1 1
26 1 2 0 0 0
27 1 0 0 0 2
28 1 -1 -1 -1 1
29 1 -1 1 -1 -1
30 1 0 0 0 -2
31 1 0 0 0 0
60
Table 3.6 Summary of overall design table with uncoded unit
StdOrder RunOrder PtType Blocks Temperature HCI (M) S/L ratio RA

(g/L) (g/g)
10 1 1 1 90 7 6 0.3
21 2 -1 1 80 8 4 0.2
28 3 0 1 80 8 8 0.2
5 4 1 1 70 7 10 0.1
16 5 1 1 90 9 10 0.3
6 6 1 1 90 7 10 0.1
15 7 1 1 70 9 10 0.3
27 8 0 1 80 8 8 0.2
29 9 0 1 80 8 8 0.2
7 10 1 1 70 9 10 0.1
26 11 0 1 80 8 8 0.2
30 12 0 1 80 8 8 0.2
19 13 -1 1 80 6 8 0.2
17 14 -1 1 60 8 8 0.2
2 15 1 1 90 7 6 0.1
22 16 -1 1 80 8 12 0.2
20 17 -1 1 80 10 8 0.2
12 18 1 1 90 9 6 0.3
8 19 1 1 90 9 10 0.1
31 20 0 1 80 8 8 0.2
4 21 1 1 90 9 6 0.1
1 22 1 1 70 7 6 0.1
14 23 1 1 90 7 10 0.3
13 24 1 1 70 7 10 0.3
11 25 1 1 70 9 6 0.3
18 26 -1 1 100 8 8 0.2
24 27 -1 1 80 8 8 0.4
9 28 1 1 70 7 6 0.3
3 29 1 1 70 9 6 0.1
23 30 -1 1 80 8 8 0.0
25 31 0 1 80 8 8 0.2
3.6 Batch leaching
Batch leach experiments is carried out in a 500 mL jacketed vessel glass reactor
with overhead magnetic stirrer (IKA RW20 digital) to agitate the slurry which can be
illustrated in Figure 3.4. The ilmenite particles will be completely suspended by rotating
the stirrer at a high enough speed (400rpm). Water bath (XMTX704) is used to heat the
reactor where peristaltic pump is used to transport the heated water through tubing.
61
During the tests, alihn condenser with circulating water is used to reduce evaporation of
the solutions from the reactor. A thermometer was connected to another neck to obtain
real-time temperature.
The solution of hydrochloric acid will then be added and heated to the required
temperature. The ilmenite samples are transferred into the reactor once the set
temperature is reached. The leaching experiments will be carried out for a total of 4
hours. The slurry will be filtered using a pump filter after the experiment is completed,
and the leaching solution will be stored in dark glass bottle samples to prevent any
further reactions.
For kinetic analysis, a narrow size range of input leaching is selected and
performed in optimal condition where concentration of acid and temperature were
selected as the parameters. Operational setup procedure for this study is similar to the
previous batch leaching test adding with withdrawn of 10mL leach liquor from the
reactor using syringe at various time intervals and filter through Whatman Celulose
Nitrate membrane filters with pore size of 0.45 µm.
62
(vi)
(viii)
(vii)
(v)
(iii)
(iv)
(i)
(ii)
Figure 3.4 A schematic diagram for dissolution experiment. (i) waterbath; (ii)
peristaltic pump; (iii) pH meter; (iv) pH/ORP probe; (v) ATC probe; (vi) overhead
stirrer (vii) thermometer (viii) alihn condenser
3.6.1 Analytical measurement for leaching analysis
3.6.1(a) Determination of iron and titanium in leaching solution
After leaching process is completed, an aliquot of the solution is taken and
analysed for Fe and Ti concentrations using Inductively Coupled Plasma Atomic
Emission Spectroscopy (ICP-OES). An Agilent 5100/5100 VDV ICP-OES model was
used as the instrument. To get the concentration within the linear calibration range,
each leach liquor was diluted 25 times which used to determine concentration of
titanium in aliquot.
Meanwhile iron content is ascertained through Atomic Absorption
Spectroscopy (AAS). AAS standard are prepares by 1, 2, 3, 4, 5mg/L where 5mg/L is
the sensitivity check between 0.16 to 0.17. The leaching data (maximum Ti or Fe
dissolution after complete leaching) will be analysed using a statistical method Minitab
63
to develop statistical models of the leaching process and assess the interaction of
alteration factors with leaching efficiency.
3.6.1(b) Leaching residue
To remove any remaining HCl, the residues will be washed with de-ionized
water, and the process is repeated until all contaminants have been eliminated. The
residues were dried for 24 hours at 105 degrees Celsius. The residue samples will be
stored in a desiccator after drying before being analyzed. Analysis is performed on the
leaching residues (SEM/EDX). Carbon was applied to the samples to create a
conductive mineral surface. Backscattered electron (BSE) images were produced in this
study to be used for mineral identification physically, while EDX is used to provide the
elemental composition of the samples. Mineral phases were also defined by elemental
mapping research, which provided information about elemental distribution in the
samples' vivid colors. In addition, elemental composition of the residue was done via
Micro X-Ray Fluorescence spectrometry.
64
CHAPTER 4
RESULT AND DISCUSSIONS
4.1 Introduction
In this research study, bulk sample, ilmenite sand (IS) was explored extensively
in characterization analysis prior to the leaching procedure. First, The IS sample
undergoes sampling method by using Jones Riffles sampling method that is exerted for
further minimization of the sample’s quantity and subsequently proceed with pre-
concentration process. Preconcentration process is the process wherein the
concentration of an intended mineral is acquired by rid of gangue material as quickly as
practical. Magnetic separation is implemented to distinguish between magnetic minerals
and non-magnetic minerals which is one of the preconcentration process.
The process of magnetic separation involves attracting magnetic materials with
a magnet to separate the components of mixtures. Non-magnetic substances are
separated from magnetic ones through using magnetic separation process. Therefore,
two output were produce which are magnetic samples and non-magnetic samples.
Magnetic samples were labelled as concentration ilmenite (CI), meanwhile for
non-magnetic samples referred as tailing ilmenite (TI), as shown in Figure 4.1. Three
samples that are IS, CI and TI were evaluated its morphology, chemical composition,
and mineral phases which were discussed later in mineral characterization part. These
samples were ground in iron ring mill for comminution purpose and subjected for
screening and sieving to obtain different size fraction for particle size distribution and
mineral liberation analysis.
After obtaining information from characterization analysis, the CI sample is
undertaken for screening process for acquiring narrow range size fraction of feedstock
65
for batch leaching analysis. For batch leaching experiment, four parameters are applied,
HCI concentration, temperature, solid to liquid ratio and concentration of reducing
agent. These experiments were designed based on Response Surface Method (RSM)
using Minitab 19 software. After the experiment completed, liquor solution and residue
obtained from the experiment were tested for determination of iron and titanium content
as the outputs and evaluate input factors used analysis of variance (ANOVA) and find
its optimal leaching conditions.
Kinetic studies are utilized to determine the ideal reaction rate model, which
primarily be explained by the mechanism reaction of the experiment and in fact able to
understand which species are existed at certain period in the leaching experiment. This
kinetic study elucidates essential information from the mechanistic reaction which some
circumstances condition how chemical reactions take place, factors that control the
reaction rates which were explained in this chapter. Two factors were discussed in this
study, HCI concentrations and temperature. The effect of both factors, kinetic, reaction
rate order, activation energy and finally the mechanism take place were discussed
further in this chapter.
Figure 4.1 Image of sample (a) ilmenite sand, IS, (b) concentrate ilmenite, CI,
and (c) tailing ilmenite (TI)
66
4.2 Mineral Characterization
4.2.1 Mineral phase identification
Three samples were tested using XRD to characterize mineral phases. The
samples are ilmenite sand (IS), concentrate ilmenite (CI), and tailing ilmenite (TI). From
Figure 4.2, it shows crystalline phase in IS sample, wherein ilmenite (01-073-2233) is
the most identifiable phase and follow by hematite (04-002-7501). Others phases also
found in the sample, such as zircon nitrate (04-011-3510) and opaque mineral such as
quartz (01-087-2096) were also recorded by XRF spectra. This data is somehow
correlative to chemical composition details given in Table 4.1, where the XRF data is
shown which will be discussed in the next section.
Apart from the raw ilmenite sample, CI also depicts similar minerals but
different in diffraction patterns or inorganic crystal structure database (ICDD) number
which is shown in Figure 4.2. From the figure, ilmenite (04-006-6597) displays the
highest crystalline phase located at 2θ that is 32.344° which can assume that both
samples for IS and CI have a similar major phase that is ilmenite. The diffraction peaks
of both samples were matched well with the standard XRD pattern of hexagonal
structure of FeTiO3 (01-073-2233 & 04-006-6597). Other magnetic mineral phases were
also detected such as hematite (04-002-7501), and zircon nitrate (04-011-3510).
On the other hand, the diffractogram graph as depicted in Figure 4.2 clearly
shows that the TI sample has a major component of silica (SiO2, 98-005-4679), which
can be categorized as gangue phase that is also supported by XRF data in Table 4.1. To
confirm the XRD data, the Rietveld refinement technique, utilizing PANalytical X’Pert
Highscore Plus software, has been used to stipulate a better model fit data by certifying
the Goodness of Fit (GoF) as in Table 4.1 where samples IS, CI and TI perform positive
67
outcomes whereby GoF for all is less than 5 that is 2.08, 1.50 and 2.78 respectively with
weighted profile factor (Rwp) are less than 10 either. Overall, it can be concluded that
every pattern of the samples’ peak was said to be well-matched and fit each other.
Figure 4.2 XRD patterns of ilmenite sand, concentrate ilmenite and tailing
ilmenite
68
Table 4.1 Phase quantification data obtained from XRD by Rietveld refinement
Sample Compound Rexp Rp Rwp GoF

IS Ilmenite (01-073-2233), hematite (04- 1.49 1.91 3.10 2.08
002-7501), zircon nitrate (04-011-3510)
and quartz (01-087-2096)
CI Ilmenite (04-006-6597), hematite (04- 1.43 1.44 0.64 1.50
002-7501) and zircon nitrate (04-011-
3510)
TI Quartz (01-087-2096) 3.89 7.88 9.84 2.78
4.2.2 Chemical composition discovery through XRF analysis
In general, ilmenite theoretically has a variable titanium content in the range of
40% to 60% of TiO2 in the earth’s crust which used for TiO2 production(Shao et al.,
2021). As can be compare with the XRF data which can be referred from Table 4.2, the
IS is formed by the following variation minerals; 39.14wt% of TiO2, 34.44wt% of Fe2O3
17.87wt% of SiO2 is still within the range of ilmenite theoretical value(Shao et al.,
2021). Meanwhile, it can be suggested that there is also possible of impurities presents
in IS such as 1.73wt% MnO, and 2.436wt% MgO which can be refer in Table 4.2. The
TiO2 recovery ascended significantly after a magnetic field was introduced to IS, which
tends to result the CI from 39.14 wt.% to 41.53 wt.%.
According to this analysis, it is confirmed that the CI is primarily comprised of
titanium dioxide (TiO2, 41.53 wt.%), hematite (Fe2O3, 38.09wt%) and silicon dioxide
(SiO2, 9.91wt%)). This CI possesses the desired mineral, the TiO2, and is suitable to be
used as the feedstock or input for the leaching process since gangue minerals present
are also in low amounts compare to the IS. Compounds such as magnesium oxide (MgO,
3.14 wt%), alumina (Al2O3, 2.86 wt%) and manganese oxide (MnO, 1.89 wt%) were
detected but only in trace levels that not less than 5% will be dissolved during the acid
leaching process whilst TiO2 content will be enriched in the final product.
69
Therefore, the XRF result as displayed in Table 4.2 pointed out that the CI
representing a successful detachment of non-magnetic mineral (tailing ilmenite) from
magnetic mineral (concentrate ilmenite) in the magnetic separation process, such that
the concentrate ilmenite has more titanium dioxide (41.53 wt.%) in the sample
compared to ilmenite sand (39.14 wt%). Moreover, the study of non-magnetic minerals
called the TI exposes the highest content of quartz (SiO2, 85.86%), low titanium dioxide
(TiO2, 2.11wt%) content and other several chemical compositions are also observed
exhibiting lower content suchlike hematite (Fe2O3,1.98wt%), magnesium oxide (MgO,
0.22wt%), alumina (Al2O3, 3.17wt%) and manganese oxide (MnO, 00.8wt%).
Table 4.2 Chemical composition of analysed samples by XRF analysis in

(wt.%)
Major analysis (wt %)
Compound IS CI TI
TiO2 39.14 41.53 2.11

Fe2O3 34.44 38.09 1.98
SiO2 17.87 9.91 85.86
Na2O 0.08 0.09 0.07
MgO 2.43 3.14 0.22
Al2O3 2.77 2.86 3.17
P2O5 0.08 0.06 0.10
K2O 0.10 0.05 0.40
CaO 0.75 0.84 0.55
MnO 1.73 1.89 0.08
Total of minor trace elements 0.58 1.53 5.44
4.2.3 Particle size distribution (PSD)
The test is aspired to separate the sample according to the size fraction as it varies
in particle mass of the samples. Sieving gives an information on particles that passed or
70
retained in set of sieves that are arranged accordingly and particle size distribution of
the sample. In this case study, particle size analysis is vital in determining optimum size
of feed for leaching process and for obtaining maximum efficiency of the leaching. This
analysis unlikely to give such information on shape of the particles whether it angular
or rounded. Nevertheless, the particle shape can be examined under microscope which
will be explained later in optical microscope analysis.
The sieve analyses were conducted with screens from 500 µm to 53 µm in the
laboratory. The plot of the particle size distribution of bulk sample by sieving is shown
in Figure 4.3 while Table 4.3 gives a summary of the of data obtained. Particle size such
as D10, D30, D50, D60 and D90 were obtained from particle size distribution graph for
instance D10 is grain diameter (mm) corresponding to 10 percent passing on the particle
size distribution curve. The letter D denotes the apparent diameter for any size of the
sample and the subscript is the finer percentage out of the total size of the sample.
Further analysis by quantitively was done by calculating the coefficient of uniformity
(Cu) and the coefficient of curvature (Cc). By referring to the Figure 4.3, the value of
coefficient of uniformity (Cu) and the coefficient of curvature (Cc) can be calculated
mathematically as shown below:
𝐷60 Eq. 18
𝐶𝑢 =
𝐷10
(𝐷30 )2 Eq. 19
𝐶𝐶 =
𝐷60 𝑋 𝐷10
From the particle size distribution curve in Figure 4.3, the result shows that the
grain size of the bulk sample has over 90% (D90) of the particles below 0.315 mm and
size 50% (D50) passing 0.18 mm aperture sieve size whilst 10% (D90) passing of
71
0.106mm, respectively. From these values, the width of the particle size distribution,
expressed as span value, is reported as 1.225. This relatively high span value indicates
an apart of size distribution. Thus, it can be categorized that the bulk sample is medium
sand size fraction. The value of Cu is 1.8662 whilst Cc is 0.9327 by mean it can be
classified as poorly graded. According to Unified Soil Classification System (USCS),
poorly graded sample indicates that most of the grain size of particles in bulk sample
is identical (American Society of Testing and Materials, 2005)
100
90
Summation Percentage (%)
80
70
60
50
40
30
20
10
0
0.010 0.100 1.000
Particle Size (mm)
Figure 4.3 Particle Size Analysis Graph for Bulk Sample
72
Table 4.3 Summary of data from Particle Size Analysis
Particle Size Analysis
D90 0.3105
D60 0.1904
D50 0.1700
D30 0.1346
D10 0.1020
Uniformity Coefficient (Cu) 1.8662
Coefficient of Gradation (Cc) 0.9327
Span Value 1.2265
4.2.4 Ore morphological studies
4.2.4(a) Optical light microscope
Preliminary visual inspection was performed on IS for mineral identification
(e.g. colour, shape, size, texture, and mineral association) directly through the reflected
light microscope (Stereo Zoom Microscope Kunoh Robo). Within this case study, an
image of IS is magnified at a certain level, offering a great image as the first perspective
on mineral morphology and phases of the sample as shown in Figure 4.4. A
representative image of ilmenite as displayed in Figure 4.4 suggested that this sample
has minerals such as ilmenite (dark metallic particle), rutile (dark brown), zircon (light
reddish colour), and colourless quartz. By referring to this figure which has been closed
to 200 times of magnification, it also exhibits that the sample has small variation in size
in such a circumstance that the particles are almost of the same sizes. This has been
mathematically proven through data acquired from particle size distribution analysis,
where it is classified as either a poorly graded sample or a uniformly graded sample
since these particles appeared to be of identical size.
73
As can be seen in Figure 4.4, most of the particles depict angular shapes and
medium sphericity. Part of it also shows very low sphericity, which bears a resemblance
to flaky shapes with a very sharp edge. These features can draw a first deduction on its
history of events such as weathering effect, transportation, and depositional condition
of the IS (Goldich, 1998). Considering the shapes of the grains, ilmenite sand has the
least weathering as it has been less crushed artificially along the river in a very short
distance and deposited upstream untimely. Nonetheless, ilmenite sand may alter due to
the weathering effect which can be seen in this figure wherein the red arrow (labelled
leu) shows mineral of ilmenite with half-completed of leucoxenization interchanging
the major and minor element of the original ilmenite sand composition. This elemental
chemistry of ilmenite sand is also discussed in elemental composition analysis through
XRF study evinces that the presence of this ilmenite sand (IS) is variant among common
ilmenite sand composition since it is associated with various minerals. For instance, it
can be suggested that rutile and ilmenite make up a portion of the TiO2 accordance with
the XRF analysis.
74
Figure 4.4 Image of raw ilmenite sample under the optical microscope (200 X
magnification). Abbreviation: ilm: ilmenite, rut: rutile, hem: hematite, zr: zircon, leu:
leucoxene and qtz: quartz
4.2.4(b) Polarized Light Microscope
Further evaluation of the morphological study was also viewed under the
polarized light microscope. In general overview, some minerals were easily identifiable
as it appeared in colours and transparency, such as yellowish to colourless quartz, which
can be seen in Figure 4.6. Ilmenite appears to be greyish to dark-coloured metallic
ilmenite, as shown in Figure 4.5 and 4.6, while rutile in dark brown. Other typical trace
minerals were also identified in the samples, for instance, hematite (dark reddish
colour), magnetite (solid black colour), leucoxene (combination of minerals), and
anatase (dark blue), as exhibited in Figure 4.5 and 4.6. Figure 4.5 IS encompassing
several opaque and non-opaque mineral variations, also with opaque variants vastly
outnumbering than the non-opaque. As depicted in photomicrographs Figure 4.5(A) and
4.5(B), the sample is mainly dominated by opaque minerals such as magnetite (mag),
ilmenite(ilm), and a few quartzes (qtz) as the non-opaque minerals. Meanwhile, the CI
75
as shown in both Figure 4.6(A) and 4.6(B) has mineral grains that are mostly the same
as in the IS exclude for minerals such as quartz as it is a non-magnetic mineral.
Both Figure 4.5 and 4.6 are predominantly composed of sub-rounded to sub-
angular grains where most of the grains were dark shaded colour. Blue anatase (anat)
features are shown in both figures as angular to subangular corners and identified by its
blue grain boundaries. Both possess rutile (rut) granules that are recognizable by their
distinctive yellowish-brown interference colour. As can be viewed from Figure 4.5 and
4.6, this ilmenite sand is genuinely altered. The mineralogical texture of the altered
ilmenite grains shows a subparallel fractured row of exsolution lamella. This ilmenite
alteration is primarily in the form of subangular grains however, some also contain
exsolved laths, some fractured shown in Figure 4.6(C, D) and irregular bodies with the
interlocking of hematite, as can be seen in Figure 4.5(C). Further alteration of the grains
has occasionally resulted in a new crystalline mass such as anatase as shown in Figure
4.5(A, B) and 4.6(A, B) and leucoxene, depicted in Figure 4.6(B).
The alteration of titanium-bearing minerals such as leucoxene is illustrated from
the figure has a potential to have a great combination of rutile and ilmenite. The
formation of leucoxene after the ilmenite is not interrogated, as there are all the
transitional varieties in the ores(Chernyshev et al., 2010). Despite that, these deposited
minerals might have gone through erosion and transferred through streams that transport
the minerals, causing the ilmenite sample to be altered. In the meantime, it also can be
suggested that abundant quartz was spotted in the non-magnetic sample as shown in
Figure 4.6 since the appearance under the microscope is non-opaque and colourless to
yellowish colour with subrounded and low sphericity shapes and only small numbers of
ilmenite particles visible here.
76
Figure 4.5 Major minerals discovered in IS under different magnification
Figure 4.6 Photomicrographs of concentrate ilmenite, CI (A-D) and tailing

ilmenite, TI, E: 50X and F: 100X magnification has ilmenite and subhedral
colourless zircon assuming to ubiquitous in tailing sample
77
4.2.4(c) SEM Analysis
Another aspect of the present study is scanning electron microscopy (SEM) by
evaluating the mineral constituents or chemical composition of the IS, CI, and
TI. Scanning electron microscopy with energy dispersive X-ray spectrometry (SEM–
EDX mapping) allows for analysing elemental morphology and mineral composition
of the sample. Based on Figure 4.7, the EDX spectrum (full area scan) displays a
detailed morphology in terms of the shape where subrounded shapes and moderate
sphericity are the majorities among the IS grains. It comprehends major elements such
as titanium and iron, which coincide with XRF data, presenting higher numbers of
TiO2 (39.14%) and Fe2O3 (34.44%). This IS is predominantly comprised of higher
titanium and iron grains, proved through the generalities number of grains appeared in
copper brown colour indicates the iron grains meanwhile titanium, turquoise colour
grains in Figure 4.7, where titanium content is 29.88 wt% and Fe content 31.37wt%.
Via EDX analysis through Backscattered Images (BSI), CI is also observed
revealing more information regarding the mineral content as shown in Figure 4.8. For
CI, it has a high multiplicity in compliance with the morphology. As specified in the
EDX spectrum data, CI grains substantially encompass titanium (31.45 wt%) and iron
(31.97 wt%). It could be seen that the CI contains more magnetic minerals, compare
to IS. This elemental mapping revealed that the CI composed of primarily of titanium
followed by iron, and then very least of silicon, aluminium, and magnesium. The EDX
spectrum is also implied to ilmenite tailing proffering that the sample constitute of
silicon element as depicted in Figure 4.9.
78
Figure 4.7 SEM/EDX Elemental mapping of IS
79
Figure 4.8 SEM/EDX Elemental mapping of CI
80
Figure 4.9 SEM/EDX Elemental mapping of TI
4.2.5 Mineral Liberation study
This analysis is more precise as it analyses mineral composition at each size
fraction of the IS, which is based on BSI images from SEM compared to XRF and
XRD techniques representing the overall composition of the IS. Considering such
information from this assessment can ease and save costs for mineral plants operation
by proffering the minerals content at each particle size fraction(Ismail et al., 2016). It
can reduce the difficulty of handling size reduction of input separating associated
81
minerals and cut expenditure for the operation as well (Olubambi et al., 2008; Ismail
et al., 2016).
A good estimation of the optimum size reduction to the liberation correlation
was achieved with the help of SEM-EDX and Fiji ImageJ 1.53e software. Figure 4.10
demonstrates the 53μm size fractions discriminate between liberated ilmenite and
unliberated ilmenite of the sample tested in this project. The liberation degree
assessments were carried out using Equation 17 (refer at chapter 3) and the statistics
of the analysis methods are shown in Figure 4.11.
The first mineral liberation study for the IS is introduced after grinding to a
size of -90 +75μm. Based on the results obtained, approximately 42.70% of mineral
liberation was discerned at 75μm, as well as further grinding up to 63μm (-75 +63μm)
slightly an increment value of mineral liberation, that is, 47.80% of the available
ilmenite phase. Meanwhile, at the 53μm (-63 +53μm) particle size shows the highest
mineral phase liberation, which is nearly 68.71%.
According to this assessment, the sample exhibits unliberated particles the most
is 75μm size fraction where it is the largest size being analysed and is not suitable to
be as the leaching input. This scope analysis aiming size fraction which consists of
minerals that are more liberated from the non-valuable mineral, which gives a
significant quality in determining the efficacy of future processes for the recovery of
valuable minerals. Hence, the most accurate size fraction as leaching input is sample
of 53μm particle size which will be used to study the mechanism and kinetic reactions
of Malaysian ilmenite ore in hydrochloric acid leaching systems.
82
Figure 4.10 Refers to (+53-63) µm size fractions. (A) Original BSE image, (B)
counted particles, (C) mineral of interest in locked form, and (D) After removal
numbers of interlock ilmenite particle, remaining of mineral particles' interest which
is liberated, FM
83
Mineral liberation study %
100
90
80
70
Mineral Liberation %
60
50
40
30
20
10
0
53 63 75
Particle size (µm)
Liberated particles Locked particles % Mineral liberation
Figure 4.11 Percentage of mineral liberation obtained for each particle size
fractions of (+53-63) µm, (+63-75) µm and (+75-90) µm which were measured using
Eqs. (4)
4.2.6 Conclusion for mineral characterization study
The Cheniah river contains a diverse assortment of minerals, in this case,
ilmenite sand (IS) found as discrete minerals in grains, but some exist with trace
elements which encompass of 39.14 wt% of TiO2. The TiO2 recovery increased
significantly ever since a magnetic field was implemented on the IS samples, leading
to a CI sample of 41.53 wt. % TiO2. The most recognized phase in both IS and CI are
ilmenite, magnetite, and rutile, but CI detects another compound, hematite.
Meanwhile, TI contains a significant amount of silica classified as gangue phase
corroborated with the XRF data. IS had a small size variance which was quantitatively
verified through particle size distribution analysis data, categorized as a poorly graded
sample since particles appeared to be about the similar size. Most are angular in shape,
84
with medium sphericity and flaky geometries with a sharp edge proving the weathering
effects and formation of leucoxenization minerals. In mineral liberation analysis, 63-
53µm range size fraction has the least unliberated particles among other size fractions,
resulting in a significant quality in determining the efficacy of future processes.
Even after ilmenite sand undergoes the pre-concentration process, the magnetic
separation, the concentrate ilmenite still has unacceptable content of gangue minerals
suchlike silicates and impurities which can be clarified as the low grade of ilmenite
since the TiO2 content is only 41.53%. Alternatively, direct leaching technique able to
upgrade this ilmenite sample, and thus future assessment will be conducted to study
on the mechanism and kinetic reactions of Malaysian ilmenite ore in hydrochloric acid
leaching system by using concentrate ilmenite with the size range of -63 +53μm as the
leaching input.
4.3 Analysis of Variance (ANOVA)
4.3.1 Statistical analysis
Minitab 18 statistical software was used to analyse experimental leaching data
and generate the best model through analysis of variance (ANOVA). Table 4.4
represents the experimental design matrix coded and uncoded unit variables and result
of dependent variables. A test for significance of the individual model coefficients with
a lack of fit test was performed to fit a good model. The significance of each component
and factor interaction was determined using through its P-value which were represents
in Figure 4.12, in pareto charts, meanwhile Table 4.5 and 4.6, describing the analysis of
variance (ANOVA) for each response. According to Figure 4.12, all the main factors
for response percentage iron and titanium leached are pass the lines indicating great
significancy of the variables towards response.
85
Analysis of variance (ANOVA) as depicted from the tabulated data, the Table
4.5 and Table 4.6, illustrate that the overall P-value for linear models are less than the
level of significance (α=0.05). Some interaction between independent variables
expresses as significant interaction such as X1X2, X1X3, X1X4 and X2X3 in response iron
leached whilst for response titanium leached, X1X3. The greater F-value and lower the
P value, which is lower than 0.05, the greater the significance of the related coefficient.
The F-value for quadratic model 17.03 for response iron leached and 13.13 for response
titanium leached indicate that’s the model is significant.
As claimed by Gunst, et al., (1996), a good fit of a model requires a correlation
coefficient of at least 0.80, whereas a high R2 value indicates higher agreement between
the estimated and observed outcomes within the range of experimentation. Both
responses indicate that models suffer no lack-of-fit as the P-value is lower than the level
of significance (0.05). The correlation coefficient for iron leached (R2=0.9575) clearly
illustrates the model equation's proximity to the experimental data. The adjusted
determination coefficient (R2=0.9202) is equally high, implying that the model is
relevant. Same goes to correlation coefficient for response percentage of titanium
leached (R2=0.9052) and adjusted coefficient (R2=0.8815). The nearer the adjusted R2
value is to one, the higher the correlation between the experimental and predicted
values(Gunst et al., 1996). In fact, results shows that each response has a better statistical
model where its R2 adjusted are closer to R2.
Following ANOVA, the chosen model was validated, and a regression model
equation was developed. The models’ equation of two-way interactions that represents
for each response were expressed as variables for coded units as given in Equation 20
and Equation 21 where X1, X2, X3 and X4 correspond to independent variables of
86
temperature (˚C), HCI concentration (M), solid to liquid ratio (g/L) and concentration
of reducing agent (g/g) respectively. As a result, the mathematical models can estimate
the outcomes in the range of variables under consideration. The coefficient of multiple
determinations, R2. The high R2 value implies that the cubic equation can represent the
system within the experimental region.
%𝐹𝑒 𝑙𝑒𝑎𝑐ℎ𝑒𝑑 = −315 + 6.03𝑋1 + 35.4𝑋2 − 17.39𝑋3 + 427𝑋4
− 0.01778𝑋1 2 − 0.093𝑋2 2 − 0.526𝑋3 2 − 57.2𝑋4 2
− 0.411𝑋1 𝑋2 + 0.1654𝑋1 𝑋3 − 2.35𝑋1 𝑋4 + 1.183𝑋2 𝑋3
− 22.2𝑋2 𝑋4 + 1.11𝑋3 𝑋4 Eq.20
%𝑇𝑖 𝑙𝑒𝑎𝑐ℎ𝑒𝑑 = −237 + 1.33𝑋1 + 38.4𝑋2 − 7.3𝑋3 + 716𝑋4
− 0.0206𝑋1 2 − 0.08𝑋2 2 − 0.580𝑋3 2 − 136𝑋4 2
− 0.067𝑋1 𝑋2 + 0.345𝑋1 𝑋3 + 1.63𝑋1 𝑋4 − 1.08𝑋2 𝑋3
− 65.5𝑋2 𝑋4 − 25.8𝑋3 𝑋4 Eq.21
87
Table 4.4 Experimental design matrix and results
Coded level of Uncoded level of variables Dependent
Block
variables variables
Run X1 X2 X3 X4 T [HCI] [S/L] [RA] % Fe % Ti
(˚C) (M) (g/L) (g/g) leached leached
1 1 1 -1 -1 1 90 7 6 0.3 91.01 82.74
2 1 0 0 -2 0 80 8 4 0.2 90.06 81.87
3 1 0 0 0 0 80 8 8 0.2 85.73 71.44
4 1 -1 -1 1 -1 70 7 10 0.1 35.05 17.53
5 1 1 1 1 1 90 9 10 0.3 88.57 73.81
6 1 1 -1 1 -1 90 7 10 0.1 79.11 65.93
7 1 -1 1 1 1 70 9 10 0.3 76.42 63.68
8 1 0 0 0 0 80 8 8 0.2 84.37 70.31
9 1 0 0 0 0 80 8 8 0.2 80.90 67.42
10 1 -1 1 1 -1 70 9 10 0.1 75.29 62.74
11 1 0 0 0 0 80 8 8 0.2 83.42 69.52
12 1 0 0 0 0 80 8 8 0.2 87.46 72.88
13 1 0 -2 0 0 80 6 8 0.2 79.31 66.09
14 1 -2 0 0 0 60 8 8 0.2 68.30 52.54
15 1 1 -1 -1 -1 90 7 6 0.1 88.40 7.37
16 1 0 0 2 0 80 8 12 0.2 66.16 50.89
17 1 0 2 0 0 80 10 8 0.2 93.01 84.55
18 1 1 1 -1 1 90 9 6 0.3 95.35 86.68
19 1 1 1 1 -1 90 9 10 0.1 89.00 74.17
20 1 0 0 0 0 80 8 8 0.2 87.46 72.88
21 1 1 1 -1 -1 90 9 6 0.1 92.06 83.69
22 1 -1 -1 -1 -1 70 7 6 0.1 64.73 49.79
23 1 1 -1 1 1 90 7 10 0.3 80.29 66.91
24 1 -1 -1 1 1 70 7 10 0.3 56.84 40.60
25 1 -1 1 -1 1 70 9 6 0.3 91.46 83.15
26 1 2 0 0 0 100 8 8 0.2 90.54 82.31
27 1 0 0 0 2 80 8 8 0.4 89.45 74.54
28 1 -1 -1 -1 1 70 7 6 0.3 82.38 68.65
29 1 -1 1 -1 -1 70 9 6 0.1 87.80 73.17
30 1 0 0 0 -2 80 8 8 0 79.04 65.87
31 1 0 0 0 0 80 8 8 0.2 85.32 71.10
88
Figure 4.12 Pareto chart of the standardize effect for full quadratic (A) percentage
of iron leached, and (B) percentage of titanium leached
89
Table 4.5 Analysis of variance for full quadratic for iron leached
Source DF Adj SS Adj MS F-Value P-Value

Model 14 4397.44 314.10 17.03 0.000
Linear 4 3493.68 873.42 47.36 0.000
X1 1 1324.62 1324.62 71.83 0.000
X2 1 882.58 882.58 47.86 0.000
X3 1 1072.27 1072.27 58.14 0.000
X4 1 214.20 214.20 11.61 0.004
Square 4 200.47 50.12 2.72 0.067
X12 1 90.45 90.45 4.90 0.042
X22 1 0.25 0.25 0.01 0.909
X32 1 126.83 126.83 6.88 0.018
X42 1 9.36 9.36 0.51 0.486
2-way interaction 6 703.30 117.22 6.36 0.001
X1X2 1 270.60 270.60 14.67 0.001
X1X3 1 175.03 175.03 9.49 0.007
X1X4 1 88.27 88.27 4.79 0.044
X2X3 1 89.49 89.49 4.85 0.043
X2X4 1 79.12 79.12 4.29 0.055
X3X4 1 0.78 0.78 0.04 0.839
Error 16 295.08 18.44
Lack-of-Fit 10 262.65 26.27 4.86 0.033
Pure Error 6 32.43 5.40
Total 30 4692.52
DF= Degree of freedom, SS= sum of square, MS= mean square, R2=0.9575, adj.
R2=0.9202, pred. R2=0.7748
90
Table 4.6 Analysis of variance for full quadratic for titanium leached
Source DF Adj SS Adj MS F-Value P-Value

Model 14 7136.41 509.74 13.13 0.016
Linear 4 4856.29 1214.07 7.46 0.001
X1 1 834.51 834.51 5.13 0.038
X2 1 2370.23 2370.23 14.57 0.002
X3 1 724.16 724.16 4.45 0.051
X4 1 927.39 927.39 5.70 0.030
Square 4 279.79 69.95 0.43 0.785
X12 1 121.16 121.16 0.74 0.401
X22 1 0.20 0.20 0.00 0.972
X32 1 153.74 153.74 0.95 0.345
X42 1 53.15 53.15 0.33 0.576
2-way interaction 6 2000.33 333.39 2.05 0.118
X1X2 1 7.23 7.23 0.04 0.836
X1X3 1 763.65 763.65 4.70 0.046
X1X4 1 42.68 42.68 0.26 0.615
X2X3 1 75.25 75.25 0.46 0.506
X2X4 1 685.56 685.56 4.22 0.057
X3X4 1 425.96 425.96 2.62 0.125
Error 16 2602.23 162.64
Lack-of-Fit 10 2579.72 257.97 68.74 0.000
Pure Error 6 22.52 3.75
Total 30 9738.64
DF= Degree of freedom, SS= sum of square, MS= mean square, R2=0.9453, adj.
R2=0.8974, pred. R2=0.706
4.3.2 Effect of significant variables towards Fe leached (%)
4.3.2(a) Effect of main variables
The results were obtained through ANOVA, and the influence of experimental
conditions for all factors on the percentage iron leached were significant, that is
concentration of HCI, solid liquid ratio, concentration of reducing agent, and
temperature as displayed in Figure 4.13. As shown in this plotted figure, a low
91
percentage of iron were observed at moderate temperature but raised starting from 80°C
to 100°C. This might be linked to an increase in mass transfer rate or diffusion rate,
which can also contribute to greater metal dissolution. Another dependent variable that
considered as significant factor is concentration of hydrochloric acid. As can be seen
from the same figure, the increment value consumption of hydrochloric concentration
increases the percentage recovery of iron dissolved.
This figure also depicts the influence of solid-to-liquid ratio on percentage iron
leached throughout four hours in the range of 4 to 12g/L. The influence of the solid-to-
liquid ratio on the iron leach percentage was studied. As illustrated in this figure,
lowering the solid-to-liquid ratio will increase the percentage iron leached. By mean of
this, as the solid-to-liquid ratio decreases, metal impurities can be effectively distributed
and interacted with acid, increasing the proportion of iron leached. Furthermore, the
high concentration of hydrochloric acid significantly increase the availability of Cl- to
react with metal impurities by providing increased contact between sample and acid
(Olanipekun, 1999; Das et al., 2013b). It also displays the percentage of iron leached at
various reducing agent concentrations in this case iron powder, as well as the current
concentration of reducing agent. Iron powder is one of the reducing agents which
provide H+ ion to accelerate the leaching in reducing agent. As indicated in Figure 4.13,
after 4 hours, a low proportion of iron was leached when a significant huge amount of
reducing agent was used. This might be because of present of catalyst; the iron powder
requires to dissolve its iron content first and later will reduce all iron from sample from
Fe3+ dissolved to Fe2+ nevertheless still increase the value of iron leached.
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Figure 4.13 Effect of independent variables towards % Fe leached
4.3.2(b) Variables interaction towards Fe leached (%)
Interaction between independent variables is determined through significancy
and effectiveness of two- way interactions between independent variables. The
outcomes are demonstrated graphically in the three-dimensional space on right side
and two-dimensional space of the left side as contour plots which were displayed in
Figure 4.14. As can be seen from the Figure 4.14a and 4.14b, the maximum leaching
of iron is at the highest temperature, 100°C with the highest value of hydrochloric acid
concentration at a fixed value of solid liquid ratio 0.8g/L and 0.4g/g of iron reductant.
Contradict to the rate iron leached response which decreases at low level concentration
of hydrochloric acid and lower temperature. An increment value hydrochloric acid can
93
possibly give a better leaching of iron in elevated temperature compare contrast to
consumption of lower temperature.
It can be observed that the lowest consumption of solid liquid ratio with highest
temperature indicates the highest value of iron leached. In fact, more than 90% of iron
leached can be obtained at 70°C at least amount of solid liquid ratio that is 4 grams of
sample per one litre of hydrochloric acid as shown in Figure 4.14c and 4.14d. Surface
plot from Figure 4.14d illustrates that intensifying the hydrochloric acid content with
reduce number of solid liquid ratio can potentiality to procure highest recovery of iron
leached. But at the same time, discerned here that lower consumption of hydrochloric
acid content can also raise the amount of iron leached even only lower usage of solid
liquid ratio that is 4g/L.
Figure 4.14f shows the 3D response surface relation between temperature and
reducing agent on iron recovery of ilmenite. It was obvious that the highest iron
recovery was achieved at the high level of temperature and at all range of reducing
agent yet still able to obtain 80 to 90% of iron when applies 0.4g/g of iron powder. A
correlation between solid liquid ratio and HCI concentration is also discussed in this
study which can be refer in Figure 4.14e and Figure 4.14f. The highest outcomes of
iron leached in interaction between HCI concentration and solid liquid ratio at
moderate concentration of hydrochloric acid with low consumption of sample per one
litre of hydrochloric acid.
94
Figure 4.14 Combination effect of variables on % Fe leached (a)contour plot for
HCI (M) vs temperature (°C), (b) response plot for HCI (M) vs temperature (°C), (c)
contour plot for temperature (°C) vs solid liquid ratio (g/L), (d) response plot for
temperature (°C) vs solid liquid ratio (g/L), (e) contour plot for temperature (°C) vs
concentration of reducing agent (g/g), (f) response plot for temperature (°C) vs
concentration of reducing agent (g/g), (g) contour plot for solid liquid ratio (g/L) vs
HCI (M), and (h) response plot for solid liquid ratio (g/L) vs HCI (M).
95
4.3.3 Effect of significant variables towards Ti leached (%)
4.3.3(a) Effect of main variables
As can be observed in the displayed Figure 4.15, titanium levels were low at
low temperature but increased as the temperature rose, yet it degrades a bit when
reaching at l00°C. The influence concentration of hydrochloric acid on the rate of
titanium dissolving was evaluated in the range of 6-10 M. The findings reported in
Figure 4.15 are as expected, increment value of titanium leached can be with higher
implementation of hydrochloric concentration.
This figure also portrays how well the effect of the ratio of sample weight
expressed in gram to the volume of leaching solution represented in litters had on the
leaching of ilmenite. The proportion of titanium which disperses in an acidic solution
is proportionally increased by a decrement in the solid weight of the sample. This has
cause attempting to reach a significant level at the sample's very lightest weight.
Comparable patterns can be observed for the concentration of the reducing agent. The
percentage of titanium recovery in the leached solution is at its highest with highest
consumption of reducing agent and degrade with applying a small quantity of iron
powder.
96
Figure 4.15 Effect of independent variables towards % Ti leached
4.3.3(b) Variables interaction of Ti leached (%)
The relationship between temperature and HCI concentration is depicted in
figure 4.16a and 4.16b. According to the findings, to generate better dissolution of
titanium, it's indeed necessarily need to use at elevated temperature and simultaneously
preserving with plenty consumption of HCI concentration. It is also evident from the
low P-value of this interaction through ANOVA analysis indicating the significance
of the two-way interaction of temperature and the HCI concentration.
97
Figure 4.16 Combination effect of variables on % Ti leached (a)contour plot for
HCI (M) vs temperature (°C), (b) response plot for HCI (M) vs temperature (°C)
4.3.4 Overlay between responses
Overlaid contour graph of HCI concentration versus temperature that has been
plotted as shown in Figure 4.17. This was done with the intention of illustrating the
best feasible variables for multiple responses. The white area graph demonstrates the
combination values of HCI, which signifies the most fitted values for both response
variables while all other parameters are statistically controlled. This plot is displayed
when the other parameters are held constant.
It is possible to deduce from this figure that whenever the reducing agent is
sustained at 0.4g/g and the solid-to-liquid ratio is sustained at only 4g/L. The
possibility to accomplish 90% to 95% of the iron leached and 80 to 90% of titanium
leached when the leaching assessment is carried out at any condition of the white area.
For instance, fixing 9M concentration of HCI at temperature of 90°C. Therefore,
higher chances to get at least 90% of iron dissolution and more than 80% of titanium
when fixing those parameters.
A declaration has been made to proof the overlaid plot graph by conducting
one experiment by fixing the variables; 0.4g/g reducing agent, 4g/L solid-to-liquid
ratio, 9M concentration of HCI and 90°C temperature. From the experiment
conducted, it has proved conclusively about 97.24% of iron and 96.24% of titanium
98
has been accomplished even it is beyond the estimation but still acceptable. Therefore,
presumption from the graph is valid and can be accepted.
Figure 4.17 Overlay of the models describing the relationship between process
parameters in both responses
4.3.5 Responses optimization
The optimal conditions were measured by using Minitab software and Table
4.7 indicates that the experimental responses were linked directly with the predicted
values. As an outcome, the models were identified as suitable for process prediction
and optimization. Experiment was organized at the optimal variables suggested to
check the model’s validity and the result were outline in the Table 4.7 showing that
the prediction is justified. The percentage of iron leached is characterized by using
AAS whilst the recovery of titanium leached is tested using ICP-OES. From the
experimental outcomes, it indicated that the optimum conditions generated by the
Minitab software were relatively reliable.
These estimations also been tested by using SEM-EDX analysis on leaching
residue after leaching, as illustrated in Figure 4.18. Figure 4.18(a) is a
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photomicrograph of SEM displays the ilmenite particles residue. It can be observed
that porous texture of the particle surface area as shown in Figure 4.18(b) and possibly
due the effect of ilmenite leaching.
Table 4.7 Optimum leaching conditions and comparative results between

predicted and experimental
Leaching condition Leaching efficiency (%)
Temperature HCI Solid Concentration Predicted Experimental

concentration to of reducing Ti Fe Ti Fe
liquid agent
ratio
90 9 4 0.4 93.84 91.9 96.42 97.24
Figure 4.18 SEM micrographs (a) ilmenite residue taken after leaching (b)
roughness surface of particle (c) spotted area with EDX spectrum analysis
100
4.3.6 Conclusion for ANOVA analysis
The influence of temperature, acid concentration, reducing agent, and solid to
liquid ratio on iron and titanium recovery of ilmenite was examined using CCD under
RSM in this research. Minitab software was used to create a selected model showing
iron and titanium recovery stated as a function of these four variables. A statistical
analysis (ANOVA) was performed to investigate the influence of the individual factors
as well as their interactions. The analysis indicated that the effects of the individual
factors, as well as some of the interactions among the variables, were statistically
significant. The predicted iron and titanium leached values using model equations
agreed well with the experimental data. The projected models are presented as 2D
contour plots and 3D response surface plots to acquire a better understanding of the
effect of the variables on the iron and titanium leaching process.
Response surface methodology was used to examine the ilmenite leaching
process by optimising acid content, temperature, reducing agent concentration, and
solid-to-liquid ratio. The optimal criteria were pointed out to be 9M, 90°C, 0.4g/g, and
4g/L. The maximum recovery for Fe and Ti are 96.42%Fe and 97.24%Ti and as for
validation, SEM-EDX has done on ilmenite’s residue. As a result, this work
demonstrated that developing statistically based mathematical models for leaching
processes might be valuable for predicting and understanding the impacts of
experimental conditions. It is vital to remember that RSM does not explain the
mechanism of the examined leaching process, but just the effects of factors on response
and interactions between variables. As demonstrated by this study, this is critical for
optimising operational conditions.
101
4.4 Mechanism and leaching kinetic evaluation
4.4.1 Performance of leaching
4.4.1(a) Effect of acid concentration and Fe-Ti Correlation in ilmenite

leaching
The effect of HCl concentration on the leaching efficiency of Fe and Ti was
studied by varying the HCl concentration between 6 and 9 M, using a particle size
fraction of +53 to 63µm, 4 g/L solid to liquid ratio at 90°C for 4 hours. Figure 4.19
shows the leaching curves whilst Table A (Appendices A) lists the proportions of Fe
and Ti dissolved at various acid concentrations throughout the period. Ilmenite is
significantly affected by the concentration of the leachant, however in no case was the
fraction of titanium and iron leached beyond 97.70% and 74.70%, respectively at
highest temperature which is 90°C. Similar trend was reported by (Olanipekun, 1999;
Mahmoud et al., 2004; Jabit & Senanayake, 2018) who discovered that when acid
concentration increased, leaching efficiency for Ti and Fe accelerated simultaneously.
Figure 4.20 illustrates the correlation between Fe and Ti dissolution at various
acid concentrations under constant condition selected. According to the results, the Fe-
Ti correlation is affected by the concentration of HCl. The linear relationship was true
at 6M HCl concentration until it deviated after 1 hour of leaching. The slope (0.5)
indicates that iron dissolved two orders of magnitude more than titanium until
equilibrium was reached after 60 minutes. A similar trend can be seen at 7M HCl,
while 8M and 9M have a higher correlation. It demonstrated a linear relationship for
the dissolving of Fe-Ti with slopes that generate a slope of 0.7 that is exceedingly close
to 1 by means both iron and titanium dissolved at almost in equal amount. However,
when the leaching time exceeded 60 minutes, the result showed some deviation from
102
its linearity. Based on this observation, the leaching behavior of ilmenite varied below
7M HCl. Fe was leached first, followed by Ti, and their rates of leaching were
comparable for the first 60 minutes before Ti began to slow, resulting in lower
dissolution than Fe. This leaching behavior could be attributed to the hydrolysis and
precipitation of dissolved Ti, which reduced Ti leaching efficiency. This demonstrates
that different reactions occurred as a result of changes in solid composition and
solution concentration(Van Dyk et al., 2002)
103
Figure 4.19 Effect of acid concentration on Fe and Ti dissolution. (a) titanium extraction
(%), and (b) iron extraction (%) at 90°C, solid liquid ratio = 4 g/L, leaching time = 4h,
reducing agent, iron powder = 0.4g/g.
104
Figure 4.20 Correlation between extraction of Fe and Ti from ilmenite samples at
temperature 90°C, solid liquid ratio = 4 g/L, t = 4h, reducing agent, iron powder=
0.4g/g
4.4.1(b) Effect of temperature and Fe-Ti correlation in ilmenite leaching
The ilmenite sample with size fraction of 53-63 µm was used to study the effect
of temperature on Fe and Ti leaching efficiency at 60°C,70°C, 80°C, and 90°C.
According to El-Hazek et al., (2007) and Mirazimi et al., (2013), as the temperature
rises from 25°C to 80°C, the extraction of Fe and Ti from ilmenite leaching increases
significantly. Figure 4.21 reveals that the leaching temperature has a significant
influence on how effectively Ti and Fe dissolves from ilmenite sand.
Based on this study, it can be seen from the data in these figures, both metals
at the same concentration were extensively dissolved the most at 90°C. Fe recovery
increased to 97.7% at the leaching temperature of 90 °C as opposed to 77.3% at
temperature of 70 °C when other parameter is fixed to 9M HCI, 4g/L of solid liquid
ratio and 4.4 g/g iron powder as reducing agent. Meanwhile for the Ti recovery in the
105
same conditions, the leaching recovery reached 74.7% in contrast to 41.4% at low
temperature of 60 °C.
Generally, a reaction's rate is increased as temperature goes up. The average
energy of the reactant molecules will ascend as the temperature rises. Consequently, a
higher proportion of molecules will possess the minimal amount of energy required
for an effective collision in which in this case the reaction between reactants sample
ilmenite and leaching acid, the hydrochloric acid. However, due to increased rates of
corrosion and HCl vapor loss, tests at higher temperatures would be less
acceptable(Tao et al., 2012; Baba et al., 2013; Das et al., 2013b).
As shown in Figure 4.22, Fe-Ti correlation for 60°C shows that the iron
dissolved more than titanium in accordance with the slope (0.48). Whereas at 70°C
and 80°C, both show quite similar trends because both slopes are around 0.6. At first
20 minutes, these two slopes portray a greater dissolution on titanium rather than iron
and nevertheless the result drifted when the leaching time was prolonged. Meanwhile
for 90°C, it possesses the greatest correlation, rather than other temperature since the
linear relationship for the dissolution of Fe-Ti produces a slope that profoundly close
to 1. It can also be explained that both iron and titanium are dissolved at nearly similar
quantities. Therefore, it can be encapsulated that all temperature is deviated from its
linearity, with slopes are less than 1.
106
Figure 4.21 Effect of temperature on Fe and Ti dissolution (a) titanium extraction
%, and (b) iron extraction ([HCl]= 9M, solid liquid ratio = 4 g/L, HCI=9M, t = 4h,
reducing agent, iron powder= 0.4g/g
107
Figure 4.22 Correlation between extraction of Fe and Ti from ilmenite samples at
temperature (a) 6M (b) 7M (c) 8M (d) 9M (temperature= 60°C -90°C, solid liquid
ratio = 4 g/L, t = 4h, reducing agent, iron powder= 0.4g/g
4.4.2 Discussion on kinetic modelling
Kinetics can be viewed as a tool for evaluating the rate of chemical reactions
and comprehending whether different methods are influenced. Kinetics is related to
profitability and requirements engineering, and it has a wide range of applications,
including estimating the quantity and volume of reaction materials, designing reactors,
controlling, controlling, and scaling up the process (Faraji et al., 2022).
Three models were utilized to demonstrate the processes implemented in this
study to evaluate the association between leaching efficiency and leaching parameters.
The kinetic models for the dissolution of sized particles are the shrinking sphere,
shrinking core models, and a mix of internal diffusion and chemical reaction
model under the assumption that the particles are homogeneous and spherical.
108
The rates are determined by a chemical reaction at the surface of the responding
particles in the shrinking sphere model, whereas mass transfer through a thickening
product layer on the surface dictates the rate in the shrinking core model. Meanwhile
the other model is a combination of chemical and diffusion reactions. These models
can be written in the form of integrated rate equations for the reaction with H + ions
for the reaction A(aq) + bB(s) = products as follows:
For the shrinking particle model:

1 − (1 − 𝑋)1/3 = 𝑏[𝐻 + ]𝑏𝑢𝑙𝑘 𝑘𝑟 −1 𝑝−1 𝑡 = 𝑘𝑠𝑠 𝑡 Eq.22
For the shrinking core model:

1 − 3(1 − 𝑋)2/3 + 2(1 − 𝑋) = 6𝑏[𝐻 + ]𝐷𝐻+ 𝑟 −2 𝑝−1 𝑡 = 𝑘𝑝1 𝑡 Eq.23
1 − 3(1 − 𝑋)2/3 + 2(1 − 𝑋) = 6𝑏[𝐻 + ]𝑏𝑢𝑙𝑘 𝐷𝐻+ 𝑟 −2 {(1 − 𝜀)𝑝}−1 𝑡 Eq.24
= 𝑘𝑝1 𝑡
For the combination models:

− ln(1 − 𝑋) = 𝑘𝑝1 𝑡 Eq.25
where X = fraction dispersed at time t, kss, kpl = apparent rate constant, [H+]
= acid concentration in bulk solution (mol cm-3), DH+ = H+ diffusion coefficient
through the product layer (cm2 s-1), r = initial particle radius (cm), = molar density of
the dissolving metal in the initial particle (mol cm-3), = particle porosity, b =
stoichiometric factor.
The kinetic reaction for the effect of temperature is shown in Figure 4.23 and
Figure 4.24. The kinetic rate for the effect of HCI is shown in Figure 4.25 and
Figure4.26. These plotted graphs are based on the equations above Equation 22 until
109
Equation 25 as a function of time for the ilmenite sample can be deduct that only
shrinking core model gave a highest correlation (R2≈1) for the time period of 0 to 4
hours both for Fe and Ti dissolution as depicted in Figure 4.23 -4.26. The slopes of the
linear relationships of these plots provide a value for kpl or known as apparent rate
constant. These figures demonstrate that the shrinking core model fits the data the best,
with an R2 value that is very close to 1.
shrinking particle model (d) combination model for Fe under different
concentration(6M-9M) at temperature= 90 ˚C, size fraction= -53=63µm, solid liquid
ratio= 4g/L and reducing agent= 0.4g/g
110
Figure 4.24 Kinetics analysis (a) fraction X (b) shrinking core model (c) shrinking
particle model (d) combination model for Ti under different concentration(6M-9M)
at temperature= 90 ˚C, size fraction= -53=63µm, solid liquid ratio= 4g/L and
reducing agent= 0.4g/g
111
shrinking particle model (d) combination model for Fe under different temperature
(60 ˚C -90 ˚C) at HCI concentration= 9M, size fraction= -53=63µm, solid liquid
112
shrinking particle model (d) combination model for Ti under different temperature
(60 ˚C -90 ˚C) at HCI concentration= 9M, size fraction= -53=63µm, solid liquid
4.4.2(a) Factors affecting apparent rate constants
All the rate constants, kpl values are derived from the shrinking core models’
slopes are listed in Table 4.8. The dissolution of iron is four to five times Ti dissolution
as referred to kpl values from the Table 4.8. The increment value of kpl as the
temperature and HCl concentration were set up in elevated quantity which following
to the conventional tendency. Out of this, it is possible to deduce that the apparent rate
constant is influenced by the factors temperature and HCI concentration as well.
113
Table 4.8 Summary of effect of variables on apparent rate constants and
diffusivity in HCl leaching of ilmenite samples.
HCI (M) Temperature (˚C) Kpl (min-1)

Fe Ti
9 60 0.0969 0.0197
9 70 0.1072 0.0292
9 80 0.1528 0.0557
9 90 0.2434 0.0957
6 90 0.1033 0.0236
7 90 0.1324 0.0475
8 90 0.1680 0.0753
4.4.2(b) Reaction rate order
Initial rates of metal dissolution (%) as a function of time can be used to discover
reaction orders, and these orders can then be applied to suggest potential reaction
processes. A reduction in surface area or the deposition of an insoluble product layer on
a particle surface, which affects the diffusion of reactants to the surface and
products from the surface, is ordinarily the consequence of a decrement in the reaction
rate of particles over time at given concentrations of reagents.
Ilmenite and HCl reactions affect the kinetics of ilmenite dissolution and
gradually alter the reagent concentrations. Therefore, by using initial slope at t=0 is
preferable since it offers the reaction rate equivalent to the initial concentration of
reagents. To determine the reaction orders (n), Equation 26 below is used where the
initial rate (RM) to the concentration of a reactant, in this case H+. [M] is the
concentration of dissolved metal in solutions, X is the dissolved percentage of metal
after time t, and kap is the apparent rate constant. The rate RM is a derivative at time zero
(dx/dt) t=0 where it can be obtained by fitting a polynomial equation to the data of the
responded fraction (X) against time (t) data as shown in Figure 4.27.
𝑑[𝑀] 𝑑𝑋 Eq.26
𝑅𝑀 = 𝑜𝑟 = 𝑘𝑎𝑝 [𝐻 + ]𝑛
𝑑𝑡 𝑑𝑡
114
Figure 4.28 is displayed in logarithmic plots of (dX/dt) Fe and (dX/dt) Ti as a
function of acid concentration [H+]. This plot measures up the log initial rates (RM) at
time zero to the log [Y], whereas when all other influences were held constant, it
yielded a line with a slope (n) that can be attributed to the reagent Y's reaction order
where can be expressed in equation below:
𝐿𝑜𝑔𝑅𝑀 = 𝑛𝐿𝑜𝑔[𝑌] + 𝐿𝑜𝑔𝑘𝑎𝑝 Eq.27
For instance, the slopes of the lines as can be seen in Figure 4.28(a) and (b)
correspond to the reaction orders for the dissolution of titanium and iron, respectively,
and are 3.1 and 0.6, respectively. The reaction order (n) obtained from experiments
were listed in Table 4.10.
115
Figure 4.27 Fraction (X) of Fe dissolution with respect to time at different acid
concentration for polynomial fitting (a) fraction reacted (X) for Fe (b) fraction
reacted (X) for Ti at 90°C, solid to liquid ratio = 4 g/L, iron powder as reducing
agent= 0.4g/g, and size fraction = +53-63 µm).
Table 4.9 Initial rate data (dX/dt) and at various HCl concentrations at selected
temperature
Temperature (°C) HCI concentration Initial rates (dX/dt) (min-1)

(M) Fe Ti
90 6 0.5145 0.3659
7 0.5299 0.5982
8 0.5797 0.7967
9 0.6438 1.3857
116
Figure 4.28 Logarithmic plot of (a) initial rates (dX/dt)Fe and (b) initial rates at
90 °C as a function of acid concentration ([HCl] = 6-9 M, solid liquid ratio = 4 g/L
,iron powder reducing agent= 0.4g/g and size fraction= +53-63 µm).
Table 4.10 Reaction order for ilmenite sample
Temperature (°C) HCI concentration Reaction order (n)

(M) Fe Ti
90 6-9 0.6 3.1
4.4.2(c) Activation energy
The minimal adequate amount of energy that perhaps a reactive molecule needed
to revolutionize into a product is regarded as activation energy. The lowest relative
quantity of energy required to stimulate or activate molecules or atoms in allowing for
them to interact in a chemical reaction or transformation is another way to define it. The
activation energy for a reaction can be calculated using the Arrhenius equation. The
117
Arrhenius plot of Ln dX/dt as a function of -1000/RT, as seen in Figure 4.29, can be
used to determine the activation energy, and listed in Table 4.11.
This research study has demonstrated that a temperature increases of 10 °C
causes double or triple the rate of a chemical process. The activation energy, or the
minimal amount of energy required for a process to proceed is degrading as temperature
increases. A greater portion of the reactant molecules have the minimal energy needed
to collide and react because of the increase in particle kinetic energy brought on by the
absorbed heat. Highlight here, a phenomenon that is meant by the term lower activation
energy because of the reactant molecules having a higher kinetic energy at higher
temperatures due to the presence of vibrational, transitional, rotational, and other
energies. At the state of temperature 90°C which low activation energy obtained that is
32 kJ/mol and 30 kJ/mol for iron and titanium.
118
Figure 4.29 Arrhenius plot for Fe and Ti dissolution on ilmenite samples at 90 °C
as a function of acid concentration [HCl] = 6-9 M, solid liquid ratio = 4 g/L ,iron
powder reducing agent= 0.4g/g and size fraction= +53-63 µm
Table 4.11 Activation energy for ilmenite sample
Temperature (°C) HCI concentration Activation energy (kJ/mol)

(M) Fe Ti
90 6-9 32.335 30.224
119
4.4.3 Overview mechanism for ilmenite leaching
The mechanism for hydrochloric acid leaching of ilmenite, which was
collected from Cheniah river in Dungun, Terengganu, Malaysia was also studied. The
dissolution rates of titanium and iron were investigated by using the shrinking core
model for reaction control, are assumed that the ilmenite particle is homogeneous
spherical solid phase. From this analysis, the batch leaching kinetics of ilmenite in HCI
solutions obeys the shrinking core model, with the rate of dissolution controlled by
diffusion of proton through product layer. The flow mechanism of ilmenite in
hydrochloric acid leaching can be illustrated as in Figure 4.30 where thickening
product layer is formed on the surface.
Figure 4.30 Illustration of shrinking core model for ilmenite in hydrochloric acid
leaching system
The possible chemical reactions involved in the reactions are proposed here to
demonstrate the extraction mechanisms. The hydrochloric acid is utilized to
disintegrate the ilmenite fraction as follows:
𝐹𝑒𝑂. 𝑇𝑖𝑂2 + 4𝐻𝐶𝐼 = 𝐹𝑒𝐶𝐼2 + 𝑇𝑖𝑂𝐶𝐼2 + 2𝐻2 𝑂 Eq. 28
This can also be illustrated by referring to Figure 4.30 where during the first
period of leaching, hydrochloric acid penetrates the ilmenite particle in the formed H+
120
causing acid protons to diffuse into the ilmenite protons. After 20 minutes of leaching,
the reducing agent, iron powder is added to the solution which causes the formation of
nascent agent, H+ and ferrous chloride, FeCl2 which can be referred to in Equation 29.
This nascent hydrogen somehow formed as hydrogen gas, and some react with iron
species which causes the reduction of Fe3+ to Fe2+ (Mahmoud et al., 2004). Iron
reduction can be considered complete once the solution changed from red yellowish
to violet. This transformation color can also indicate the reduction of Ti4+ from TiOCl2
to Ti3+ from TiCl3. This reduction Ti4+ /Ti3+ takes place due to reaction itself with HCI,
iron powder, and the nascent hydrogen. The reactions of additional hydrogen and
reaction of nascent can be described in equation bellows:
𝐹𝑒 + 2𝐻𝐶𝐼 = 𝐹𝑒𝐶𝐼2 + 2𝐻 Eq. 29
𝐻 + 𝐻 = 𝐻2 Eq. 30
2𝑇𝑖𝑂𝐶𝐼2 + 2𝐻𝐶𝐼 + 2𝐻 = 2𝑇𝑖𝐶𝐼3 + 2𝐻2 𝑂 Eq. 31
2𝑇𝑖𝑂𝐶𝐼2 + 2𝐻𝐶𝐼 + 𝐹𝑒 = 2𝑇𝑖𝐶𝐼3 + 𝐹𝑒𝐶𝐼2 + 2𝐻2 𝑂 Eq. 32
Meanwhile the existence of Ti3+ from TiCl3 will keep dissolved the Fe3+ to Fe2+
into the solution even no more reaction of nascent hydrogen and the iron powder to be
filled in. The reaction can be ascribed in Equation 33 below. This reduction is even
further active since the consequences of the broken grain structure of the ilmenite due
the reaction itself between ilmenite with acid proton from the beginning. All the reaction
can be claimed that the reaction is chemically controlled.
𝑇𝑖𝐶𝑙3 + 𝐹𝑒𝐶𝑙3 + 𝐻2 𝑂 = 𝑇𝑖𝑂𝐶𝑙2 + 𝐹𝑒𝐶𝐼2 + 2𝐻𝐶𝑙 Eq. 33
121
However, it doesn’t until after 60 minutes of leaching as it starts to control
through diffusion reaction of the mass transport through a thickening product or solid
layer on the surface, which more fits to Equation 23 and Equation 24. It can also be
illustrated in Figure 4.31 which means that the gradual removal of Ti3+ from the solution
was the sign of ongoing oxidation to the Ti4+ state. As stated by Mahmoud et al., (2004),
the hydrolysis of the dissolved titanium species is liable to the decrease in the total
titanium concentration in the solution after it reaches its highest point. TiOCl2 exists as
the most common species of titanium at the HCl concentration being used. The
hydrolysis of TiOCl2 can be explained through equation 34. At this stage, the Ti4+ is in
solid form corresponds that is in appearance of white hydrated TiO2 precipitates on
ilmenite particles where it can be proved in Figure 4.32.
𝑇𝑖𝑂𝐶𝐼2 + 𝐻2 𝑂 = 𝑇𝑖𝑂2 + 2𝐻𝐶𝐼 Eq. 34
The kinetic equations as functions of time revealed that it only gives perfectly
straight lines from 0 to 60 minutes meaning it does follow the model for Equation 22
(Refer to Figure 4.23-4.26). Again, this can be illustrated by referring to Figure 4.31
where this can be claimed that the reaction is chemically controlled. Nevertheless, it
doesn't happen until 60 minutes of leaching since this begins to control by mass transport
through a thickening product or solid layer on the surface via diffusion reaction. This
can be inferred that the dissolution reaction was not controlled wholly by the chemical
reaction for involving on the mineral's surface and titanium and iron dissolution rates
have a good correlation with the diffusion kinetic Equations 23 and 24.
These presumptions can also be affirmed using SEM/EDX analysis before (refer
Figure 4.31) and after leaching (refer Figure 4.32). Figure 4.31 illustrates particles of
the raw ilmenite sand before used as a feed. According to EDX data, this raw ilmenite
122
consists of severe types of elements such as at particle A appears in grey colored grain
consisting mainly of silica while particle B can be indicated it is ilmenite due to the
reasonable content of iron and titanium in the grain.
After 4 hours of leaching, the observation on the surface of ilmenite residue
has been made as shown in Figure 4.32. It can be seen that there is a solid layer forms
on the surface of the particles, that prevents further ilmenite dissolution. Through this
evidence, it can be confirmed that shrinking core model can be implemented into this
leaching analysis where the rate of reaction is under diffusion controlled after certain
period of time of leaching. The overall activation energy of the reaction was
determined to be 32.3 kJ/mol Fe and 30.2kJ/mol Ti where it can encapsulate that the
diffusion of Fe2+ ions out of the ilmenite into the lattice appears to be the source of this
activation energy.
123
Figure 4.31 SEM EDX images of raw ilmenite sand before leaching conducted
124
Figure 4.32 SEM- EDX result of ilmenite grain particles taken after 4 hours
leaching that is covered with solid layer produced (a) spectrum 1, (b) spectrum 2, and
(c) spectrum 3.
125
CHAPTER 5
CONCLUSION AND FUTURE RECOMMENDATIONS
5.1 Conclusion
Mineral characterisation has conducted on the ilmenite sand (IS) located from
the catchment area, Cheniah River, Kelip Hill, Hulu Dungun, Malaysia.
Characterization of raw ilmenite sand was done by XRF, XRD, OM, SEM analyses.
As determined through this data research, chemical analysis reveals that IS has
39.14wt% of TiO2, 34.44wt% of Fe2O3 17.87wt% of SiO2 is still within the range of
ilmenite theoretical value. IS had a small size variance which was quantitatively
verified through particle size distribution analysis data, categorized as a poorly graded
sample since particles appeared to be about a similar size. Most are angular in shape,
with medium sphericity and flaky geometries with a sharp edge proving the weathering
effects. This characterization study's data and information assist in the IS discovery
and creates a design of a viable treatment procedure that will be developed in future
work for the local mineral exploitation. The TiO2 recovery increased significantly ever
since a magnetic field was implemented on the IS samples, leading to a CI sample of
41.53 wt. Even after IS undergoes the pre-concentration process, the magnetic
separation, the CI still has unacceptable content of gangue minerals which can be
clarified as the low grade of ilmenite.
Alternatively, direct leaching technique is applied to upgrade this ilmenite
sample, in a hydrochloric acid leaching system with the presence of reducing agent by
using CI with the size range of -63 +53μm as a feed. In this part, the leaching
experiment was design based on RSM using Minitab 19 software. The leaching
experiment's parameters were HCI concentration, temperature, solid-to-liquid ratio,
and reducing agent concentration (iron powder). The results of the ANOVA analysis
126
showed that some of the interactions between the variables and the effects of the
individual components were statistically significant. The best parameters were
identified as 9M HCl, 90°C, 0.4g/g iron powder, and 4g/L solid liquid ratio. For Fe
and Ti, the maximum recovery is 96.42% and 97.24%, respectively. For validation,
SEM-EDX was used to assess the leaching residue. As a result, this work demonstrated
that developing statistically based mathematical models for leaching processes might
be valuable for predicting and understanding the impacts of experimental conditions.
To explain the mechanism of the examined leaching process, two parameters
is selected, temperature and HCI concentration. From this analysis, the batch leaching
kinetics of ilmenite in HCI solutions perfectly match a shrinking core model. It reveals
that it only gives perfectly straight lines from 0 to 60 minutes meaning it does follow
the model. This can be claimed that the reaction is chemically controlled. However,
after 60 minutes of leaching, it starts to control through diffusion reaction of the mass
transport through a thickening product or solid layer on the surface. The shrinking core
model can describe the rate of reaction, providing evidence that it is diffusion
controlled. The overall activation energy of the reaction was determined to be 32.3
kJ/mol Fe and 30.2kJ/mol Ti. The diffusion of Fe2+ ions out of the ilmenite lattice
sodium ions into the lattice appears to be the source of this activation energy.
127
5.2 Recommendations for Future Research
To understand more on the reaction of ilmenite in hydrochloric acid leaching,
other parameters also should be considered such as stirring rate, pulp density, leaching
time, type of reducing agent and variety of size fractions. Extensive study in the present
of mineral or chemical species in selected period should be considered as to elucidate
leaching mechanism.
128
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134
APPENDICES
APPENDIX A TABLE OF PARAMETERS ON EFFICIENCY OF FE

AND TI LEACHING FROM ILMENITE
Table A Effect of HCl concentration on efficiency of Fe and Ti from ilmenite
Ilmenite dissolution
HCI (M)
0.25h 0.5h 0.75h 1h 2h 3h 4h

Fe Ti Fe Ti Fe Ti Fe Ti Fe Ti Fe Ti Fe Ti
6 20.1 8.7 35.6 15.7 52.1 23.0 62.9 27.7 69.3 37.9 75.5 43.6 78.9 43.7
7 24.7 12.3 41.0 24.2 55.6 29.0 65.5 33.1 74.2 46.7 81.9 57.4 86.5 61.9
8 28.6 21.3 48.9 31.2 63.5 37.2 72.7 43.7 82.2 59.3 86.2 67.9 92.4 72.8
9 44.0 39.5 66.6 50.5 77.3 59.8 83.7 66.2 93.7 67.7 96.0 72.4 97.7 74.8
Table B Effect of temperature on efficiency of Fe and Ti leaching from ilmenite

Ilmenite dissolution
T (°C)
0.25h 0.5h 0.75h 1h 2h 3h 4h

Fe Ti Fe Ti Fe Ti Fe Ti Fe Ti Fe Ti Fe Ti
60 14.3 7.3 37.3 13.7 51.2 20.0 58.2 24.9 67.5 34.4 74.3 39.3 77.3 41.5
70 11.6 10.2 21.1 19.0 41.1 26.6 53.5 31.6 69.4 39.9 75.4 44.3 82.9 50.8
80 21.9 21.8 45.8 30.1 61.5 42.5 69.8 48.6 82.4 53.1 85.1 59.2 88.7 63.4
90 44.0 39.5 66.6 50.5 77.3 59.8 83.7 66.2 93.7 67.7 96.0 72.4 97.7 74.8
LIST OF PUBLICATIONS
1. Ibrahim, S.A., Jabit, N.A., Ismail, S. and Ariffin, K.S., 2022. Distinctive
characteristics of Cheniah river sand from Dungun, Terengganu Malaysia.
Materials Today: Proceedings, 66, pp.3008-3013.
Proceeding of the 14th AUN/SEED-Net Regional Conference on Materials 2021 &
4th International Postgraduate Conference on Materials, Minerals & Polymer (RCM &
MAMIP 2021)
Distinctive characteristics of Cheniah river sand from

Dungun, Terengganu Malaysia
Siti Asmidar Ibrahim a, Nurul’Ain Jabit a*, and Suhaina Ismail a, Kamar Shah
Ariffina
a
School of Materials & Mineral Resources Engineering, Universiti Sains Malaysia
(USM) Engineering campus, Malaysia
Abstract.
Mineral ilmenite sand deposit in the Hulu Dungun, Terengganu, Malaysia, has prompted a huge interest in their
viability as a new resource survey of titanium dioxide feedstock in Malaysia. In accordance with this necessity, this
study is executed to conduct mineral characterisation on the ilmenite sand (IS) located at the catchment area,
Cheniah River, Kelip Hill, Hulu Dungun, Malaysia. Characterization of raw ilmenite sand was done by X-Ray
Fluorescence (XRF) for exploring elements in the sample. Digital microscopy (DM) for optical imaging purpose
with polarizing filterand Scanning Electron Microscope (SEM) analyses were developed for surface morphological
studies. As determined through this data research, chemical analysis reveals that IS has the highest amount of 44.0%
TiO2, and come after with 37.8% Fe2O3, 12.0% SiO2 and other impurity elements such as Mn, V, Cr and Mg. DM
images has the same point of view regarding to the mineral constituents from XRF data wherein majority of the IS
grains display black dark to steel grey colour as the ilmenite and few of colourless quartz. Meanwhile, the surface
morphology from both analyses, DM and SEM can be concluded that IS has heterogenous surface. Most of the IS
grains have angular shape with moderate sphericity and few subrounded and high sphericity. Nearly all of the IS
are found to be associated with iron oxide as displayed through Backscattered image (BSE) from SEM-EDX
analysis. This characterization study's data and information assist in the ilmenite sand discovery and creates a
design of a viable treatment procedure which will be developed in future work for the local mineral exploitation.
Keywords: Ilmenite sand, titanium dioxide, mineralogical characterization

Introduction
Ilmenite, known colloquially as iron titanium oxide, is among the most significant ores
presently. It is one of several titanium oxides resources that can be profitably exploited[1], [2]. Adding
with Global Titanium Dioxide Market Report (2021), the market rate for titanium dioxide reached
approximately USD 16.98 billion in 2020 and is anticipated to be expand at an 8.3% compound annual
growth rate (CAGR) from 2020/21 to 2028, indicating that it might be in bounteous producers and
consumers by industries around the world for material properties, paints, sheets, beauty products, self-
cleaning products, sunscreen, photocatalytic substances, and other value propositions [1]–[6]. In
actuality, natural rutile supplies, particularly are among the most common sources of titanium dioxide,
have rapidly depleted, prompting the immediate extraction of ilmenite ores for the development of
titanium industries [7]–[10].
Ilmenite contains 40 to % 80% TiO2, whereas other titanium minerals, including such brookite
(TiO2), perovskite (CaTiO3), sphene (CaTiSiO4), and geikielite (MgTiO3) can indeed be encountered in
mineral sand deposits. Rutile comprises 95% TiO2, anatase has more than 95% TiO2, and leucoxene
possesses up to 65% TiO2. Ilmenite (FeTiO3) is perhaps the most critical asset for the production of
titanium dioxide products in the world [11], [12]. Nonetheless, it includes numerical proportions of
impurities including SiO2, MnO, CaO, even V2O5, which can be construed as TiO2 of low grade.

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MECHANISM AND KINETIC REACTIONS OF

MALAYSIAN ILMENITE ORE IN

SITI ASMIDAR BINTI IBRAHIM

UNIVERSITI SAINS MALAYSIA

SITI ASMIDAR BINTI IBRAHIM

Thesis submitted in fulfilment of the requirements

whole De’Abraham family members for the encouragement which insisted me in

helped me during this study.

TABLE OF CONTENTS ........................................................................................... ii

LIST OF TABLES ................................................................................................... vii

LIST OF FIGURES .................................................................................................. ix

LIST OF SYMBOLS .............................................................................................. xiv

LIST OF ABBREVIATIONS ................................................................................. xv

LIST OF APPENDICES ........................................................................................ xvi

ABSTRAK .............................................................................................................. xvii

ABSTRACT ............................................................................................................. xix

CHAPTER 1 INTRODUCTION .......................................................................... 1

1.1 Introduction ...................................................................................................... 1

1.2 Problem statement ............................................................................................ 4

1.3 Objective .......................................................................................................... 6

1.4 Scope of study .................................................................................................. 6

CHAPTER 2 LITERATURE REVIEW .............................................................. 9

2.1 Introduction ...................................................................................................... 9

2.1.1 Titanium mineralogy ...................................................................... 10

2.1.2 Ilmenite mineralogy ....................................................................... 13

2.2 Natural weathering of ilmenite ....................................................................... 14

2.3 Crystal structure of ilmenite ........................................................................... 17

2.4 Diversity of raw materials for titanium production ........................................ 20

2.5 Manufacture of titanium dioxide .................................................................... 21

2.5.1 Sulphate process ............................................................................. 22

2.5.2 Chloride process ............................................................................. 23

2.6 Process of upgrading ilmenite ........................................................................ 24

2.7.1 Evaluation of MINITAB data ........................................................ 26

2.8 Factor affecting direct leaching ...................................................................... 27

2.8.1 Particle size .................................................................................... 27

2.8.2 Acid concentration ......................................................................... 29

2.8.3 Temperature ................................................................................... 32

2.8.4 Solid to liquid ratio......................................................................... 33

2.8.5 Reducing agent ............................................................................... 35

2.9 Kinetic study of ilmenite leaching ................................................................. 37

2.9.1 Selection of leaching kinetic models .............................................. 38

2.9.2 Kinetic study of hydrochloric acid leaching .................................. 40

2.10 Research background on prospecting area ..................................................... 43

CHAPTER 3 MATERIALS AND METHODOLOGY .................................... 49

3.1 Study description ............................................................................................ 49

3.2 Site description ............................................................................................... 51

3.3 Materials and reagents .................................................................................... 53

3.4 Characterization analysis................................................................................ 53

3.4.1 Sample preparation ......................................................................... 53

3.4.2 Morphological studies .................................................................... 54

3.4.3 Particle size distribution (PSD) ...................................................... 55

3.4.4 Mineral phase identification using X-Ray Diffraction (XRD) ...... 56

3.4.5 Elemental composition using X-Ray Fluorescence (XRF) ............ 56

3.4.6 Mineral Liberation studies ............................................................. 57

3.5 Batch Leaching experiment ............................................................................ 58

3.6 Batch leaching ................................................................................................ 61

3.6.1 Analytical measurement for leaching analysis ............................... 63

3.6.1(a) Determination of iron and titanium in leaching

CHAPTER 4 RESULT AND DISCUSSIONS ....................................................... 65