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Study of Titanium Dioxide (TiO 2 ) Extraction Process from Ilmenite Banten
To cite this article: Lavita Indriani Br. Ginting et al 2023 IOP Conf. Ser.: Earth Environ. Sci. 1201 012092
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Study of Titanium Dioxide (TiO
2) Extraction Process from Ilmenite Banten
Lavita Indriani Br. Ginting1,2*, Azwar Manaf¹, Widi Astuti², Yayat Iman Supriyatna², Fathan Bahfie²
1 Department of Physics, University of Indonesia, Depok, Indonesia
2 Research Center of Mining Technology, National Research and Innovation Agency, South Lampung, Lampung, Indonesia
*E-mail: [email protected]/ [email protected]/ [email protected]
Abstract. Ilmenite is found in the form of iron sand with reserves of 927,315,827 tons spread across several regions in Indonesia, including Banten which has seven million tons of iron sand. This mineral can be used as a raw material for making TiO2 pigments. The problem faced in the use of Ilmenite is its complex mineral structure which causes difficulties at the processing stage. The synthesis of TiO2 from ilmenite ore commonly used the sulfate process and the chloride process. The sulfate process is less environmentally friendly, has excessive costs, and produces a lot of liquid waste. While the chloride process requires high-grade raw materials and requires chlorine gas. Therefore, in this study, the synthesis of TiO2 from ilmenite Banten using caustic fusion, acid leaching using hydrochloric acid, and the use of citric acid were conducted. Caustic fusion is conducted with ratio between ilmenite and NaOH is 1:2, with a fusion temperature of 850°C and a fusion time of 60 minutes. Then next process is water leaching and acid leaching. The result of this study is that the TiO2 obtained from each acid leaching is hydrochloric acid leaching producing powder pigment with 94.189% TiO2, acetic acid leaching producing 37.099%
TiO2, citric acid leaching producing 41.480% and hydrochloric acid leaching without fusion process producing 43.991% TiO2.
Keywords: alkaline fusion, chloride process, ilmenite, titanium dioxide.
1. Introduction
Indonesia is one of the countries that has abundant mineral reserves of ilmenite (FeTiO3) in the form of iron sand, which is around 638 million tons. Based on data in the Foreign Trade Statistics Bulletin by the Central Statistics Agency (BPS), during 2019 Indonesia imported 3,690,304 kilograms of titanium oxide (TiO2). Because of this, the amount of TiO2 imports must be reduced by producing TiO2 through ilmenite sand processing in Indonesia [1–4]. Recent research has focused on developing innovative technologies for processing iron sands into products that are chemically equivalent to rutile [5]. The ilmenite mineral used in this study is in the form of iron sand originating from Rancecet, Pandeglang, Banten. Banten iron sand is used because Banten has a large estimated reserves of iron sand (7,118,890 tons). TiO2 levels in Banten ilmenite are 29 - 30% [6]. In addition, based on information obtained from residents of Rancecet, there is a lot of iron sand mining in the area that has not been further used because the iron sand processing plant in the area has stopped operating. The abundance of iron sand reserves and the lack of use of Banten iron sands, the high number of TiO2 imports in Indonesia and the ESDM Ministerial Regulation No. 25 encourage research on the processing and refining of Banten iron sands to meet the needs of TiO2 in Indonesia and increase the added value of natural resources in Indonesia.
The content of TiO2 in ilmenite varies between 45% - 60% depending on where the ilmenite comes from. Processing of ilmenite ore through the hydrometallurgical route can produce TiO2 as a bleaching pigment material, a superior color pigment (white color), the main material for the manufacture of TiO2
2
polymeric precursor, for the manufacture of modern ceramic materials, such as optical coatings (optic films), electro-optic materials. optical and ceramic polymer composite materials [7–10].
To increase the levels of TiO2 present in ilmenite minerals, an extraction process needs to be conducted to separate the element Titanium (Ti) with other impurities such as Iron (Fe), Silicon (Si) and Aluminum (Al). Ilmenite can be decomposed using sodium hydroxide (NaOH) or potassium hydroxide (KOH) [11,12]. The choice of using NaOH is because the price is more economical, where the price of NaOH is around $ 5.99 / pound while the price of KOH is around $ 9.99 / pound [13]. In addition, compared to KOH, NaOH is more soluble in water [14].
The titanium extraction process from ilmenite uses the caustic fusion method followed by water leaching and acid leaching because it has the advantage of being able to produce high levels of TiO2. The results of [15–19] research showed that by conducting caustic fusion, 92% of titanium could be synthesized with hydrochloric acid and 89% could be synthesized with sulfuric acid. The existence of the caustic fusion method before the acid leaching process can remove impurities in the form of Si and Al and is able to break the bonds of Ti and Fe elements in ilmenite to increase the Ti content in the final product. In addition, the caustic fusion method can maximize the recovery of TiO2 during acid leaching by converting ilmenite minerals into Na2TiO3 intermediate [20]. The existence of this caustic fusion process makes the titanium dioxide extraction process faster in terms of time and requires less acid solution. In addition to adding the caustic fusion process, the use of inorganic acid solutions that are not environmentally friendly can be replaced by using organic acid solutions that are more environmentally friendly.
Therefore, in this research, TiO2 synthesis will be conducted from low-grade ilmenite ore using alkaline fusion, acid leaching using hydrochloric acid, citric acid, and acetic acid.
2. Research Methods 2.1. Materials
Ilmenite was obtained from Rancecet, Pandeglang, Banten. The chemicals used are NaOH P.A (≥99%, Merck, Darmstadt-Germany), HCl 37% (SMART-LAB, Tangerang-Indonesia), Acetic acid (glacial) (100%, Merck, Darmstadt-Germany) and Citric acid (Merck, Darmstadt-Germany).
2.2. Methods
Caustic fusion is one of several methods used to increase the titanium content of ilmenite. Caustic fusion process is conducted to thermally decompose ilmenite. The ratio between ilmenite and NaOH is 1:2, with a fusion temperature of 850 °C and a fusion time of 60 minutes. Furthermore, the fused frit was leached by using water in a ratio of 1:5 (w/v), after which it was dried. Then the acid leaching process was conducted using hydrochloric acid, acetic acid, and citric acid with a concentration of 6.5M with leaching temperature of 90°C and a leaching time of 240 minutes [2,6,13].
2.3. Sample Code
Ilmenite Banten with a particle size of -100+150 mesh is coded MS 31. Frit resulting from the caustic fusion process is coded FUSI, for samples resulting from the water leaching process are coded WL. For sampel resulting from water leaching process that did not go through a caustic fusion process coded R1- 2C. The acid leached product using hydrochloric acid is coded R2-5, for the acid leached product using acetic acid the code is A100 and the acid leached product using citric acid is coded S100. The product resulting from acid leaching using hydrochloric acid without any caustic fusion process is coded R2-2C.
2.4. Characterization Test
The characterization tests conducted in this study were X-Ray Fluorescence (XRF) and X- Ray Diffraction (XRD). X-Ray Fluorescence characterization was conducted to figure out the composition of the sample. X-Ray Diffraction characterization was conducted to figure out the phase formed in the sample.
3. Results and Discussion
3.1 Characterization of Banten ilmenite
Characterization of Banten ilmenite was conducted by testing XRF and XRD. The composition of the Banten ilmenite concentrate with a particle size of -100+150 mesh (MS 31) can be seen in table 1. From table 1, the elemental composition in Banten ilmenite with a particle size of -100+150 mesh is iron with a content of 56.048%, titanium with a content of 37.120% and the rest are impurities such as magnesium, aluminum, silicon, vanadium, and others in their oxide form for the phase contained in Banten ilmenite with a particle size of -100+150 mesh is ilmenite (FeTiO3). It is proven by the results of the XRD analysis which can be seen in Figure 1 with the sample code MS 31 and the result can be compared with the result of research from Aristanti [6].
Table 1. Composition of Ilmenite Banten -100+150 mesh (MS 31)
Sample ELEMENT (%)
MgO Al2O3 SiO2 P2O5 CaO TiO2 V2O5 Cr2O3 MnO Fe2O3
MS 31 0.732 1.006 2.069 0.482 0.664 37.120 0.421 0.027 0.854 56.048
Figure 1. Ilmenite Banten XRD Analysis -100+150 mesh (MS 31) 3.2. Characterization of Caustic Fusion and Acid Leach TiO2
The extraction process of titanium dioxide (TiO2) in this study was conducted by the steps of the Banten ilmenite sieving process using a sieve with a mesh size of 100 and a mesh of 150. For sodium hydroxide, the preparation is pulverizing sodium hydroxide until it passes through a 60-mesh sieve. Then the next process is the caustic fusion process. The caustic fusion was conducted by mixing Banten ilmenite with sodium hydroxide (NaOH) in a ratio 1:2 at temperature 850°C for 60 minutes, where the results obtained from the caustic fusion process were in the form of frit, which would then be leached by using water.
The caustic fusion process with alkali is carried out to decompose ilmenite thermally. In this decomposition process there is a chemical separation between titanium dioxide (TiO2) from iron oxide, silica, and other impurities as well form metal-sodium compounds which are soluble in water or acids so that it can be separated in the next step. In the caustic fusion process, NaOH will react with ilmenite according to reaction 1. With the reaction of NaOH with ilmenite, the ilmenite bond (FeTiO3) will split into Na2TiO3 and NaFeO2, so that during the water leaching process, the bonded NaOH with impurities such as iron, magnesium, aluminum, silicon will easily dissolve. while the NaTiO3 will not dissolve
4
because titanium has non-polar properties (not easily dissolved in water).
The water leaching process is conducted to dissolve the sodium hydroxide which has been bound to the impurity elements present in ilmenite. After the water leaching process is complete, a filtering process is conducted, from this filtering process the residue is obtained which is then dried and then the acid leaching process is conducted. In table 2, it can be seen the results of the XRF analysis of water leaching residue that through caustic fusion (WL) and water leaching residue that did not through caustic fusion (R1-2C). When compared with table 1, after the water leaching process is conducted there are several impurities such as magnesium, aluminum, silicon, and others which are reduced in levels.
Between the WL and R1-2C samples the WL samples had more reduced impurities. This happens because the impurities bind to NaOH in the fusion process and dissolve during the water leaching process. The chemical reactions that occur in the caustic fusion and water leaching process can be seen in reactions 1 and [21] 2.
4FeTiO3(s) + 12NaOH(s) + O2 → 4Na2TiO3(s) + 4NaFeO2(s) + 6H2O(g) (1) Na2TiO3 + NaFeO2 + H2O → Na2Ti3O7 + FeO + NaOH (2)
Na2Ti3O7 + 8HCl→ 3TiOCl2 + 2NaCl+ 4H2O (3)
Table 2. Results of XRF Analysis of Water Leaching Residue (WL)
Sample ELEMENT (%)
MgO Al2O3 SiO2 P2O5 CaO TiO2 V2O5 Cr2O3 MnO Fe2O3
WL 0.600 0.464 0.988 0.467 0.517 32.215 0.257 0.414 1.274 61.867 R1-2C 0.579 1.014 2.624 0.488 2.623 32.086 0.464 0.561 0.788 57.851 The solids from the water leaching process have been dried, followed by the acid leaching process. WL samples are used for acid leaching of A100, S100 and R2-5 and R1-2C sample is used for acid leaching of R2-2C sample. Acid leaching is conducted using three types of acids, hydrochloric acid, acetic acid, and citric acid. After the acid leaching was carried out, then a filtering process was carried out and then the washing process with water on the acid leaching residue was carried out until it reached a pH of 1.4- 1.55, then dried at a temperature of 60°C. Table 3 shows the results of the XRF analysis on the acid leaching products that have been carried out. From table 3, the product that has the highest TiO2
content is the sample with the code R2-5, which is the product of caustic fusion and acid leaching using hydrochloric acid. When compared with the sample code R2-2C which is the product of acid leaching using hydrochloric acid, but not through the caustic fusion process, there are differences in the levels of TiO2 produced. This is because impurity elements in sample R2-5 already decrease after water leaching process. It can be seen in Table 2. The results of this acid leaching are influenced by the level of acidity of the acid solution used. This is also influenced by the number of H+ ions in an acidic solution, the fewer the number of H+ ions, the stronger the acid, so it is easy to dissolve Fe. Because element Fe or Iron has the property of easily corroded, so that when it meets with acid it can be dissolved to acid liquid.
The chemical reactions that occur in the acid leaching process can be seen in reactions 3 [21].
Table 3. XRF Analysis Results of Acid Leaching Products
Sample ELEMENT (%)
MgO Al2O3 SiO2 P2O5 CaO TiO2 V2O5 Cr2O3 MnO Fe2O3
R2-2C 0.569 0.523 2.190 0.405 0.216 43.991 0.493 0.115 0.821 49.999 A100 0.0 0.186 0.671 0.324 0.304 37.099 0.267 0.411 1.121 58.762 S100 0.0 0.0 0.248 0.0 0.351 41.480 0.294 0.400 0.788 55.714 R2-5 0.0 0.020 0.144 0.0 0.225 94.189 0.0 0.0 0.008 4.527
Characterization by XRD testing was conducted on the acid leached product to figure out the final phase formed in the sample. The results of XRD characterization of acid leaching products can be seen in Figure 2 and Figure 3. Figure 2 is the result of XRD analysis of sample R2-2C which is an acid leaching process that does not go through a caustic fusion process. From Figure 2 the phases formed in the sample R2-2C are pseudo brookite (Fe2TiO5) and rutile (TiO2).
Figure 2. Result of XRD Analysis of Sample R2-2C
In Figure 3 it can be seen the results of XRD analysis for samples with codes A100, S100 and R2-5 which are the product of the acid leaching process through the caustic fusion process. From Figure 3, the phases formed in sample A100 which are the product of acid leaching using acetic acid solution are magnesioferrite (MgFe2O4) and periclase (MgO). The phases formed in the acid leaching product using citric acid (S100) are magnesioferrite (MgFe2O4) and perovskite (CaTiO3) and the phase formed in sample R2-5 is rutile (TiO2).
Figure 3. Result of XRD Analysis of Acid Leaching Products
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4. Conclusion
The first characterization conducted on Banten ilmenite showed that Banten ilmenite consisted of 56.048% Fe elements, 37.120% Ti elements and the rest were impurities. From the results of the first XRD analysis, the phase contained in Banten ilmenite is ilmenite (FeTiO3). The highest concentration of titanium dioxide (94.189%) was obtained in sample R2-5 which was a sample that had undergone a caustic fusion process and acid leaching using hydrochloric acid. Of the three acid solutions used in acid leaching: acetic acid, citric acid, and hydrochloric acid with the same concentration, it was found that the hydrochloric acid solution produced high levels of titanium dioxide. Further research is needed to optimize the acid leaching process by combining the organic acids and inorganic acid to reduce the use of inorganic acids. Research can also be conducted using monosodium glutamate to replace sodium hydroxide in the fusion process.
Acknowledgments
The authors gratefully acknowledge the support of Materials Science University of Indonesia and the Research Center of Mining Technology-National Research and Innovation Agency of Indonesia (PRTPB-BRIN) for the research facility and financial support. We are also thankful for financial support provided by the Ministry of Education, Culture, Research, and Technology-Directorate of Higher Education, Research and Technology under research project PDD 2022 and contract no. NKB- 968/UN2.RST/HKP.05.00/2022.
References
[1] Mohar M T, Fatmawati D and Sasongko S B 2013 Production of Titanium Dioxide Pigments from Ilmenite Remaining Zircon Sand Processing with the Becher Process Journal of Chemical and Industrial Technology 2 110–6
[2] Aristanti Y, Supriyatna Y I, Masduki N P and Soepriyanto S 2019 Effect of calcination temperature on the characteristics of TiO2 synthesized from ilmenite and its applications for photocatalysis IOP Conference Series: Materials Science and Engineering vol 478 (Institute of Physics Publishing) [3] Supriyatna Y I, Sumardi S, Astuti W, Nainggolan A N, Ismail A W, Petrus H T B M and Prasetya A
2020 Characterization and A Preliminary Study of TiO2 Synthesis from Lampung Iron Sand Key Engineering Materials vol 849 KEM (Trans Tech Publications Ltd) pp 113–8
[4] Ahmad A, Awan H and Aziz S 2013 Synthesis and Applications of TiO2 Nanoparticles In :70th Annual Session Proceedings of Engineering Congress Pakistan pp. 405-412
[5] Jabit N A 2017 Chemical and Electrochemical Leaching Studies of Synthetic and Natural Ilmenite In Hydrochloric Acid Solutions Dissertation of Mineral Resources Engineering Murdoch University pp. 1-303
[6] Aristanti Y, Supriyatna Y I, Masduki N P and Soepriyanto S 2018 Decomposition of banten ilmenite by caustic fusion process for TiO2 photocatalytic applications IOP Conference Series: Materials Science and Engineering vol 285 (Institute of Physics Publishing)
[7] Zhu Z, Zhang W and Cheng C Y 2011 A literature review of titanium solvent extraction in chloride media Hydrometallurgy Volume 105(3-4) pp. 304–13
[8] Setiawan B 2012 Extraction of Titanium Dioxide Anatase from Ilmenite Bangka through Ammonium Peroxo Titanate Compounds and Initial Photo Reactivity Test Library University of Indonesia
[9] Middlemas S, Fang Z Z and Fan P 2013 A new method for production of titanium dioxide pigment Hydrometallurgy 131–132 pp.107–13
[10] Middlemas S, Fang Z Z and Fan P 2015 Life cycle assessment comparison of emerging and traditional Titanium dioxide manufacturing processes J Clean Prod 89 137–47
[11] Schultz H, Bauer G, Schachl E, Hagedorn F and Schmittinger P 2000 Potassium Compounds Ullmann’s Encyclopedia of Industrial Chemistry (Weinheim, Germany: Wiley-VCH Verlag GmbH
& Co. KGaA)
[12] Whitfield R and Brown F 2017 The Economic Benefits of Sodium Hydroxide Chemistry in the Production of Pulp and Paper in the United States and Canada Lisa Wood Prepared for the American Chemical Council
[13] Supriyatna Y I, Astuti W, Sumardi S, Sudibyo, Prasetya A, Ginting L I B, Irmawati Y, Asri N S and Petrus H T B M 2021 Correlation of Nano Titanium Dioxide Synthesis and the Mineralogical Characterization of Ilmenite Ore as Raw Material International Journal of Technology 12 749–59 [14] Sukmara S, Suyanti, Adi W A and Manaf A 2022 Mineral analysis and its extraction process of
ilmenite rocks in titanium-rich cumulates from Pandeglang Banten Indonesia Journal of Materials Research and Technology 17 3384–93
[15] Hanum Lalasari L, Firdiyono F, Herman Yuwono A, Harjanto S and Suharno B 2012 Preparation, Decomposition and Characterizations of Bangka - Indonesia Ilmenite (FeTiO<sub>3</sub>) Derived by Hydrothermal Method Using Concentrated NaOH Solution Adv Mat Res 535–537 750–6
[16] Jabit N A and Senanayake G 2018 Characterization and Leaching Kinetics of Ilmenite in Hydrochloric Acid solution for Titanium Dioxide Production Journal of Physics: Conference Series vol 1082 (Institute of Physics Publishing)
[17] Manhique A J, Focke W W and Madivate C TITANIA RECOVERY FROM LOW-GRADE TITANOFERROUS MINERALS
[18] Zhang L, Hu H, Liao Z, Chen Q and Tan J 2011 Hydrochloric acid leaching behavior of different treated Panxi ilmenite concentrations Hydrometallurgy 107 40–7
[19] Parirenyatwa S, Escudero-Castejon L, Sanchez-Segado S, Hara Y and Jha A 2016 Comparative study of alkali roasting and leaching of chromite ores and titaniferous minerals Hydrometallurgy 165 213–26
[20] Subagja R 2016 Extraction of Titanium from Bangka Ilmenite through Decomposition with KOH and Dissolution with Sulfuric Acid National Seminar on Science and Technology, Faculty of Engineering, University of Muhammadiyah Jakarta
[21] Sanchez-Segado S, Lahiri A and Jha A 2015 Alkali Roasting of Bomar Ilmenite: Rare Earths Recovery and Physics- Chemical Changes Open Chemistry volume 13(1) pp. 270–8
