Development of TiO2-based

Photocatalyst Material from Natural

Mineral Indonesia
Dr. Eng. Osi Arutanti, M.Si
Research Center for Chemistry

Guest Lecture Series, 18 April 2023

Hello!
Dr. Eng. Osi Arutanti, M.Si
Researcher, Research Center for Chemistry Development of Immobilized TiO2
National Research and Innovation Agency Photocatalytic
EDUCATION
• B.S. in Physics, Institute Technology Bandung (2005)
• M.S. in Physics, Institute Technology Bandung (2010) Functionalized and Nanostructured
• Dr. Eng. in Chemical Engineering, Hiroshima University (2012) Tungsten Oxide for Photocatalyst and
PROFESSIONAL EXPERIENCE Photocatalysis
2015.10 – 2015.11 Visiting researcher, Department of Physics,
Institute Technology Bandung
Nano Dispersion of Magnetic Materials
2015.12 - 2017.03 Postdoctoral researcher, Department of Chemical
Engineering, Hiroshima University
Functionalized and Nanostructured TiO2-
2017.08 - 2017.12 Postdoctoral researcher, Department of Physics, based Photocatalyst Material and Their
Research Center for Nanoscience and
Photocatalytic Application
Nanotechnology

2018 – Present Permanent Researcher, Research Center for

Chemistry, Indonesia Institute of Sciences

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Outline

Photocatalyst & TiO2 as

Photocatalytic Photocatalyst Challenge & Potential

1 3 5

2 4 6

Mineral Clasification Recovery TiO2 Conclussion

3
Global Issue

Domestic and Industrial waste in the form of suspension, dissolved

organic, and inorganic
Waste
(Soil Pollution)
Nerve disorders Conventional Method
Asthma, bronchitis
Preliminary
Kidney Disorders
Treatment
Global Issue Water Pollution Advanced Primary
`treatment treatment

Cancer Cough, sore throat

Skin diseases Congenital diseases Tertiary Secondary

treatment treatment
Emission
(Air Pollution)

PHOTOCATALYSIS
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Photocatalyst and Photocatalytic
Photocatalytic is one of advanced oxidation process which can be defined as “acceleration of
reaction in the presence of photon and catalyst”.

Mechanism of photocatalytic Photocatalytic reaction involves 3

photon hv + semiconductor → h+ + e- major steps:
CB e- + O2 → O2-
h+ + H2O → h+ + OH Absorption of photon

O2- Production of e- and h+ and

+ R → H2O + CO2
their migration to the
OH
OH surface
eh-+
R : Organic compounds Decomposition of R by both O2-
VB CB : Conduction band and OH produced at surface
H2O VB : Valence band

OH* ≈ 2.8 eV => The highest potential energy, it is capable of breaking down other organic compounds
Eg ≈ λ nm => The absorption ability can be adjusted by controlling the wavelength
+ R → H2O + CO2 => No by-products are produced

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Photocatalyst and Photocatalytic

Organic Borate
Degradation minerals

CO2 Reduction Sulfide

minerals
APPLICATIONS

Metal Oxide
Silicate
minerals

H2 Evolution Others

Anti bacterial
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Mineral Classifications
Silicate Minerals Sulfide Minerals Metal Oxide

Zeolite, Montmorillonite, diatomite,
sepiolite, kaolin, palygorskite, and
halloysite.
Zeolite => Volcanic :
▫ Pores structure
▫ Electron donor / acceptor
Sphalerite (Zn), chalcopyrite, and
pyrite (FeS2) => Volcanic
▫ High adsorbent
▫ Strong magnetic
▫ Heavy metal adsorption
Hematite (Fe2O3), Magnetite (fe2O4),
and Ilmenite (FeTiO3) => Mining
▫ Low toxicity
▫ Light absorption
▫ Recyclability
▫ Resistant

Lampung, Jawa Barat, Jawa Tengah, Sumba Island Indonesia

Jawa Timur, Nusa Tenggara Timur,
dan Sulawesi (447.490.160 ton) -
ESDM

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Metal Oxide – based Photocatalyst
 Abundant
 Non-toxic
TiO2
 Thermal stability
 Less Expensive

Others Pulp & paper Plastic Paint & coating

(18%) (10%) (27%) (55%)

Existing Market Industry

Photocatalyst Photocatalyst
By grade
materials commonly materials commonly Rutile: Pigment (>75% in 2020)
used in Indonesia used in research Anatase: Ceramics, Cosmetic, Pharmacy
worldwide
Development of TiO2-based Photocatalyst material for
established photocatalytic Technology
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Titanium Dioxide
As demand increases, availability decreases,
CAGR 5-7,8% (2021 – 2028)
resulting in higher selling prices.
6.1 million metric tons (2016)
7.8 million metric tons (2022)

Revenue share
~42%
Asia Pacific (2020)
Titanium Dioxide
(TiO2)

Agriculture Personal care Food & beverages

Automotive Pharmaceutica Construction Titanium is starting to be classified as Critical Raw
Material (CRM)
Environment EndlUser Energy
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Titanium Dioxide
The summary of exports and imports comparison of industrial raw materials in Indonesia (Ministry of Trade 2022).

Ilmenite as a byproduct of Tin mining activities has not been optimally processed (4000 ton/year)

Ban on ilmenite export

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Recovery TiO2 from Ilmenite
Ilmenite (FeTiO3) -> 40-65% TiO2
Oxidation & Thermal reduction at high temperature
Reduction
Additional carbon material to remove oxide iron

Pretreatment
Mechanical Grinding / Milling to enhance the specific
Activation
surface area an changing the crystal structure

Hydrothermal
conversion

Sulfuric acid
FeTiO3 +H2SO4 = TiSO4 + FeSO4 + 2H2O
Ilmenite Particle size, time,
temperature, ratio
Hydrochloric acid concentration
FeTiO3 +4HCl = TiCl2 + FeCl2 + 2H2O
Leaching
C2H2O4 + H2O = H3O+ + C2HO4--
Oxalic acid
C6H8O7 + H2O = H3O+ + C6H7O--
Hydrometallurgical FeTiO3 + 4H3O+ = TiO2+ + Fe2+ + 6H2O

Caustic leaching FeTiO3 +8NaOH + O2 = 4Na2TiO3 + 2Fe2O3 + 4H2O

General steps to recovery TiO2 from ilmenite

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Recovery TiO2 from Ilmenite

Recovery TiO2 rutile from Ilmenite Recovery TiO2 rutile from Ilmenite Recovery TiO2 rutile from Ilmenite
by solid state reaction. by Betcher method. by Chloride method. 12
Recovery TiO2 from Ilmenite

Recovery TiO2 rutile from Ilmenite by sub molten salt.

FeTiO3 + 2Na2CO3 = 2Na2TiO3 + FeO + 2CO2 => Decompose anosovite into alkali titanate
Na2TiO3 + 2 HCl = 2NaCl + TiO2 + H2O => Dissolved impurity

Incorporating Na2CO3 and utilizing a microwave can result

in a reduction in processing time
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Challenge And Potential

SWOT
During 10 years, only 74 publications
(28% articles, and 72% conference
proceedings) the technology that has been
developed is not yet suitable for the
industrial market

Ilmenite is the second most

abundant by-product after
Quartz 4000ton/year
Existing technology can
High demand produce TiO2 with high purity

opening up broad opportunities for

cooperation in technology development
as well as the utilization of processed
products
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Potential Ilmenite from Banten Mulyono et.al , AIP 2017
Table of synthesizrd TiO2 chemical
composition from EDS
 TiO2 Preparation Table of ilmenite chemical composition Oxides Mass (%)
200 mesh ilmenite was used Oxides Amounts (wt %) TiO2 91.47
650°C, 120 FeTiO3 61.90
Ilmenite + NaOH Ilmenite
FeO 3.38
min. TiO2 12.53 SiO2 2.24

Ilmenite + 45% 85°C, 90 SnO2 7.70

min. TiOSO4
H2SO4 SiO2 2.00 Table of band gap energy (Eg).

MnO 2.96 Oxides Eg (eV)

TiOSO4 + NH4OH 90°C, 90 TiO(OH)2 10 um

(pH 1.0) min. Others 12.91 TiO2 2.47

SEM image of Synthesized
Washed & ilmenite.
TiO(OH)2 Neutral pH TiO2 Merck 3.18
dried 500 °C, 1h TiO2 Ktechnique 3.28

TiO2 M (merck)
TiO(OH)2 TiO2 TiO2 K (technique)
TiO2 S (from ilmenite)
Photocatalytic
activity was
influenced by the
presence of impurity
Small amount of Fe incorporated
into TiO2 crystal structure Fe and Si
10 um

XRD patterns of TiO2 merck (99.00%

SEM image of the
purity) and synthesized TiO2 from
recovery TiO2. Photodecomposition of RhB 15
ilmenite (91.47%).
Potential Ilmenite from Banten Aristanti et.al , IOP conf. series 2018

 TiO2 Preparation Table of ilmenite chemical composition

Table of synthesizrd TiO2 chemical composition
Oxides Amounts (wt %)
200 mesh ilmenite was used
Fe2O3 67.46 Oxides Mass (%) Dc (nm) Band gap
750°C, 30 min.
Ilmenite + NaOH Ilmenite (eV)
TiO2 29.30
TiO2 M (Merck) A* 11.61 3.22
85°C, 90 min.
Ilmenite + 42.5% H2SO4 TiOSO SiO2 1.34
TiO2 A (pH 1.0) A* + α.Fe2O3 19.60 2.96
4 SiO2 0.97
90°C, 90 min. TiO2 B (pH 1.5) A* + α.Fe2O3 13.26 2.92
TiOSO4 + NH4OH TiO(OH)2
MnO 0.94
pH was varied : 1.0; 1.5; and 2.0 TiO2 C (pH 2.0) A* + α.Fe2O3 7.42 2.88
MgO 0.91
Washed &
TiO(OH)2 Neutral pH V2O5 0.39
dried
500 °C, 1h
TiO(OH)2 TiO2 CaO 0.38
The impurity (α.Fe2O3)
P2O5 0.15
increased by increasing pH value

Photocatalytic activity was influenced by the

presence of α.Fe2O3

The presence of impurity enhanced the photon

adsorption from UV to visible light

XRD patterns of the synthesized Photodecomposition 16

TiO2 of RhB
Potential Ilmenite from Banten Aristanti et.al , IOP conf. series 2019

 TiO2 Preparation
200 mesh ilmenite was used
350°C
650°C, 120 min.
Ilmenite + NaOH Ilmenite

85°C, 90 min. 450°C

Ilmenite + 42.5% H2SO4 TiOSO
4
90°C, 120 min.
TiOSO4 + NH4OH (pH = 1.0) TiO(OH)2 550°C
Washed &
TiO(OH)2 Neutral pH
dried
650°C 15.38 %
TiO(OH)2 T °C, 1h
TiO2 rutile phase
T annealing was varied : 350, 450, 550, 650, and 750 °C
750°C 89.57 %
rutile phase

XRD patterns of the synthesized of TiO2

Table of ilmenite chemical composition
Oxides Dc Eg (eV)
Rutile phase was detected when the annealing
(nm) temperature at start from 650°C
350 5.66 2.7
Annealing temperature influenced the crystal size
450 8.8 2.73
of the synthesized TiO2
550 11.31 2.63
650 53.41 2.4 The presence of Fe2O3 decreased the Eg of the
750 104.89 2.08 synthesized TiO2
Photodecomposition of RhB and
Methylene Blue
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Potential Ilmenite from Bangka Belitung
 Preparation of photocatalyst

XRD, XRF, DRS-UV,

Photocatalysis

Various Na2CO3

 Photocatalysis measurement

Photocatalyst Analyse Different 2 lamp

(0.5 g) resources:
Dark
(30 min.)
UV and white lamp

Organic dye solution Light irradiation UV Spectro

(100 ppm) (120 min.)

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Potential Ilmenite from Bangka Belitung Submitted

Table 1. XRF analysis results of ilmenite before and after treatment for ratio ilmenite and soda ash 1:1.

Component TiO2 Fe2O3 Cr2O3 MnO Al2O3 MgO SiO2

Before
53.50 34.40 1.80 1.80 1.00 1.00 1.10
Contain (%)
After
55.70 10.10 1.40 0.30 0.80 0.60 8.60
1:1 Contain (%)
Component Ti Fe Cr Mn Al2 Mg Si
Before
32.00 24.10 1.20 1.40 0.50 0.60 0.50
Contain (%)
After
33.40 7.10 0.90 0.20 0.40 0.40 4.00
5:3 Contain (%)

 Rutile and anatase phase has been detected

 Percentage of TiO2 and SiO2 increased after treatment
process around 4% and 681%, respectively
 Percentage of Fe2O3 decreased after treatment process of
around 70%
 Optimization of treatment process still needed
Figure 1. XRD peaks of the prepared TiO2-based photocatalyst. 19
Optical Proeprties

Ilmenite 5:3 1:1

Figure 2. Bandgap energy of the prepared photocatalyst which calculated by Kubelka-munk

equation.

 Bandgap energy of the prepared photocatalyst increased from 1.57 to 1.89 and 2.48 depend
on the mass ratio
 Ti Concentration influenced the change of band gap energy
 Current Eg value still lower than pure TiO2 anatase (3.1 – 3.2 eV)
 Theoretically, the current prepared photocatalyst could be activated under visible light

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22 November 2022 I
Photocatalytic Activity

Low grade TiO2 commercial Ilmenite

5:3 1:1

Figure 4. Comparison photocatalytic performance of 1:1 under different light sources.

 Ilmenite does not have the photocatalytic ability

 Currently prepared photocatalyst active under
UV light
 Founded a suitable white lamp is still needed
Figure 3. Photodegradation og 100 ppm Wantex under white lamp irradiation.
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Various Roasting Times Submitted

XRD patterns of the synthesized of TiO2

 2.6 was the optimum concentration to produce the higher TiO2 rutile
 Basedon the photocatalytic activity
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Conclusion

 In Indonesia, the development of TiO2-based photocatalysts derived from

ilmenite as a sustainable technology is highly feasible.

 The design and development of methods to recovery TiO2 from ilmenite are
still widely open.

 In the process of recovery TiO2 from ilmenite, the pre-treatment process and
acid leaching play a very important role.

 A processing method of recovery TiO2 from ilmenite using a short and

efficient acid treatment is highly needed to meet the demands of the industry.

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THANK YOU

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