Document Type : Review
Authors
Iran Polymer and Petrochemical Institute, P.O Box 14965-115, Tehran, Iran
Abstract
Titanium (Ti) is the ninth most abundant element on earth. The titanium mineral ores are widely distributed in different parts of the world. The two main ores of titanium include rutile (TiO2) and ilmenite (FeO.TiO2). It is aimed to provide the readers with an insight to the main processes currently employed to extract and recover titanium tetrachloride (TiCl4) from different titanium ores. Due to the crucial importance of TiCl4 catalyst in the synthesis and polymerization of polyolefins, the present work examines the literature and developments made in the processing of ilmenite and rutile ores for the extraction of TiCl4. The attention has been paid to the chlorination processes and the main parameters affecting the recovery of TiCl4. Different approaches developed to date are reviewed. Different processes, reaction mechanisms and conditions as well as the kinetic models developed for extraction and purification of TiCl4 in fluidized bed reactors are also reviewed. A literature survey on the combined fluidized bed reactor systems developed for achieving a high-grade synthetic rutile via selective chlorination of low-grade titanium ores having high metal oxides content such as magnesium oxide (MgO) and calcium oxide (CaO) is also reported. Different strategies adopted to avoid agglomeration process during the extraction process are discussed too.
Keywords
Main Subjects
- Kothari NC, (1974) Recent developments in processing ilmenite for titanium. Int J Min Proc 1: 287-305
- Budinski KG (1988) Surface engineering for wear resistance. Prentice Hall, Englewood Cliffs, 420-460
- Knittel D (1983) Titanium and titanium alloys. In: Grayson M, Ed., Encyclopedia of chemical technology, 3rd Ed., John Wiley and Sons, Hoboken, 98-130
- Rudnick RL, Gao S (2003) Composition of the continental crust. In: Treatise of geochemistry, Rudnick RL, Ed., Vol. 3, Elsevier, Amsterdam, 1-64
- Gambogi J (2009) Titanium, 2007 Minerals Yearbook. US Geological Survey, U.S. Government Printing Office, Washington DC, 195-220
- Stwertka A (1998) Guide to the elements. Revised Edition, Oxford University Press, London, 240- 270
- Williams VA (1990) WIM 150 Detrital heavy mineral deposit. In: Geology of the mineral deposits of Australia and papua New Guinea, Hughes FE, Ed., Monograph 14, Australasian institute of mining and metallurgy, 1609-1614
- Whitehead J (1983) Titanium compounds (Inorganic). In: encyclopedia of chemical technology, Grayson M., Ed., 3rd Ed., John Wiley and Sons, Hoboken, 131-176
- Mandal BM (2013) Fundamentals of polymerization; World scientific: Hackensack, NJ, USA, 46-50
- Albizzati E, Galimberti M (1998) Catalysts for olefins polymerization. Catal Today 41: 415-421
- Fu T, Cheng R, He X, Liu Z, Tian Z, Liu B (2016) Imido-modified SiO2-supported Ti/Mg ziegler- Natta catalysts for ethylene polymerization and ethylene/1-hexene copolymerization. Polyolefins J 3: 103-117
- Shamiri A, Chakrabarti MH, Jahan S, Hussain MZ (2014) The influence of Ziegler-Natta and metallocene catalysts on polyolefin structure, properties, and processing ability. Materials 7: 5069-5108
- Natta G (1959) Kinetic studies of α-olefin polymerization. J Polym Sci 34: 21–48
- Claverie JP, Schaper F (2013) Ziegler-Natta catalysis: 50 years after the Nobel Prize. MRS Bull 38: 213–218
- Gázquez MJ, Bolívar JP, Garcia-Tenorio R, Vaca F (2014) A review of the production cycle of titanium dioxide pigment. Mater Sci Appl 5: 441-458
- Alpert MB, Sullivan WF (1956) Purification of titanium tetrachloride. US Pat 2,712,523
- Anderson WW, Rowe LW (1956) Method for preparing chlorination feed material. US Pat 2,770,529
- Armant DL, Cole SS, (1949) Smelting of titaniferous ores. J Metals 1: 909-913
- Banning LH, Hergert WF, Halter DE (1955) Electric smelting of alluvial ilmenite concentrates from Valley Co., Idaho US Bureau of Mines Rep., 5170: 1-18
- Barksdale J (1966) Titanium, its occurrence, chemistry and technology. Ronald Press, 2nd ed., New York, NY, 1-76
- Barnett CE (1959) Electrowinning of titanium. US Pat 2,908,619
- Becher RG (1963) Improved process for the beneficiation of titanium ores containing iron. Aust Pat 247110
- Becher RG, Canning RG, Goodheart BA, Uusna S (1965) A new process for upgrading ilmenite mineral sands. Proc Aust Min Metall 214: 21- 44
- Belyakova EP (1962) Processing of ilmenite concentrate to obtain titanium. Akad Nauk SSR Inst Met 5:289-294
- Bergholm A (1961) Chlorination of rutile. Trans Metall Soc AIME 221: 1121-127
- Campbell IE, Jaffee RI, Blocher HN, Gurland J, Gosner SW (1948) The preparation and properties of pure titanium. J Electrochem Soc 93: 271-285
- De Boer J, Fast JD (1926) Preparation of pure metals of titanium group by thermal decomposition of iodides. Z Anorg Allg Chem 153: 1-6
- De Boer J, Fast JD (1930) Preparation of pure metals of titanium group by thermal decomposition of iodides. Z Anorg Allg Chem 181: 181-189
- Dean RS, Long JR, Wartman FS, Hayes FT (1946) Ductile titanium – its fabrication and physical properties. Trans Metall Soc AIME 166: 369-389
- Dean RS, Silkes B (1946) Metallic titanium and its alloys. US Bureau Mines IC 7381: 21-39
- Doraiswamy LK, Bijawat HC, Kunte MV (1959) Chlorination of ilmenite in a fluidized bed. Chem Eng Prog 55: 80-88
- Dunn WE (1960) High temperature chlorination of titanium dioxide bearing minerals. Trans Mellat Soc AIME 218: 6-12
- Elger GW, Stickney WA (1971) Production of high purily synthetic rutile from a domestic ilmenite concentrate. US Bureau of Mines 37: 19-28
- Fast JD (1938) Crack-free forming of zirconium and titanium. Metall Wirtschaft 17: 459-462
- Fast JD (1939) Preparation of pure titanium iodides. Rec Tray Chim 58: 174-180
- Frey W (1957) Titanium dioxide pigment with high rutile content. US Pat 2, 779, 662
- Gaskin AJ, Ringwood AE (1959) Production of rutile from ilmenite and selected ores. Aust Pat 222, 517
- Gaskin AJ, Ringwood AE (1960) Production of rutile from ilmenite and selected ores. US Pat 2,954, 278
- Head RB (1951) Reduction of titanium tetrachloride. Aust Pat 209, 985
- Head RB (1960) The thermodynamic properties of the lower chlorides of titanium. Aust J Chem13: 332-340
- Head RB (1961) Electrolytic production of sintered titanium from titanium tetrachloride at a contact cathode. J Electrochem Soc 108: 806- 809
- Henn JJ, Barclay JA (1970) A review of proposed processes for making rutile substitute. US Bureau of Mines IC 8450: 27-37
- Hughes W, Arkless W (1965) Titanium ore beneficiation process. Brit Pat 992, 317
- Jaffee LD (1949) Titanium. J Metals 1: 6-9
- Judd B, Palmer ER (1973) Production of titanium dioxide from ilmenite of the west coast, South Island, New Zealand. Proc Aust Inst Min Metal 247: 23-33
- Kelly KK, Mah AD (1959) Metallurgical thermochemistry of titanium. US Bureau of Mines Rep, 5490: 43-48
- Kroll W (1940) The production of ductile titanium. Trans Electrochem Soc 78: 35-47
- Kroll W (1940a) Methods for manufacturing titanium and alloys. US Pat 2, 205, 854
- Leone OQ, Knudsen H, Couch DJ (1967) High purity titanium electrowon from titanium tetrachloride. J Metals 19: 18-23
- Manocha R (1953) Chlorination of ilmenite. Trans Ind Inst Metals 7: 95-104
- Myhren AJ, Kelton EH, Johnson RL, Snow GE, Grady LD, Andrews EW, Reimert EW, Barnett CE (1968) The New Jersey zinc company electrolytic titanium pilot plant. J Metals 20: 38- 41
- Toshio N (1965) Titanium from slag in Japan. J Mater 17: 25-32
- Opie WR, Svanstrom KA (1959) Electrode position of titanium from fused chloride baths using titanium tetrachloride as feed materials. Trans Mellat Soc AIME 218: 219-225
- Opie WR, Svanstrom KA (1959) Electrolytic production of high purity titanium. US Pat 2,904,479
- Patel CC, Jere GV (1960) Chlorination of ilmenite. Trans Mellat Soc AIME 218: 219-225
- Rabie AA, Saada MY, Ezz SY (1968) Upgrading Egyptian ilmenite by partial chlorination. London, The Inst. of Min. Met., Adv Extra Metall. 516-538
- Rand MJ, Reimert LJ (1954) Electrolytic titanium from titanium tetrachloride. I. Operation of a reliable laboratory cell. II. Influence of impurities in titanium tetrachloride. J Electrochem Soc 111: 429-434
- Reimert LJ (1963) Electrolytic production of titanium in fused salt. US Pat 3, 082,159
- Roberson AH, Banning LH (1955) Preparation and chlorination of titaniferous slag from Idaho ilmenites. Trans Mellat Soc AIME 203: 1334- 1342
- Safiullin NSh, Belyaev EK (1966) Production of high quality titanium dioxide by alkaline decomposition of treated chromium containing ilmenite. Khim Prom UKz 3:5-8
- Safiullin NSh, Belyaev EK (1967) On the preparation of high quality titanium dioxide from chromium containing ilmenite using the method of alkali decomposition. Khim Prom UKz 4: 6-8
- Sankaran C, Misra RN, Bhatnagar PP (1968) Selective chlorination of iron from ilmenite with hydrochloric gas. In: Advances in extractive metallurgy, Inst Min Metall, London, 325-390
- Sehra JC, Snanamoorthy JB, Gadiyar HS, Roa ChS, Jena PK (1966) Chemical beneficiation of quilenilmenite by high temperature hydrochloric acid leaching. Trans Ind Inst Met 19: 114-115
- Stoddard CK, Wyatt JL (1953) Titanium metal. US Pat 2,663,634
- Stoddard CK, Wyatt JL (1955) Retort for reducing titanium tetrachloride with magnesium. US Pat 2,709,078
- Van Arkel A, De Boer J (1925) Darstellungvon reinem titanium-zirkonium-hafnium and thorium metall. Z Anorg Allg Chem 148: 345-350
- Van Arkel A, De Boer, J (1928) Process of precipitating metals on an incandescent body. US Pat 1,671,213
- Walker BV (1967) Titanium dioxide from New Zealand ores. J N Z Sci 10: 1-6
- Walsh RH, Hockin HW, Brandt DR, Dietz PL, Girardot PR (1960) Reduction of iron in ilmenite to metallic iron at less than slagging temperatures. Trans Mellat Soc AIME 218: 994-1003
- Moodley S (2011) A study of the chlorination behaviour of various titania feedstocks. MSc thesis, University of the Witwatersrand, Johannesburg
- Moodley S, Kale A, Bessinger D, Kucukkaragoz C, Erich RH (2012) Fluidization behaviour of various titania feedstocks. J South Afr Ins of Min and Metallurgy, 112, 467–471
- Kale A, Bisaka K (2010) Fluid bed chlorination pilot plant at mintek. The Southern African Institute of Mining and Metallurgy, Advanced Metals Initiative, Light Metals Conference
- Wendell E, Dunn JR (1979) High temperature chlorination of titanium bearing minerals: Part III. Metall Trans B 10: 293-294
- Wendell E, Dunn JR (1979) High temperature chlorination of titanium bearing minerals: Part IV. Metall Trans B 10: 271-277
- Barin I, Schuler W (1980) On the kinetics of the chlorination of titanium dioxide in the presence of solid carbon. Metall Trans B 11: 199-207
- Bonsack JP, Schneider FE (2001) Entrained-flow chlorination of titaniferous slag to produce titanium tetrachloride. Metall Mater Trans B 32: 389-393
- Den Hoed P, Nell J (2002) The carbochlorination of titaniferous oxides in a small scale fluidised bed, IFSA 2002, 133-143
- Burger H, Bessinger D, Moodley S (2009) Technical considerations and viability of higher titania slag feedstock for the chloride process, 7th Heavy mineral conference, 187- 194
- Minkler WW, Baroch EF (1981) The production of titanium, zirconium and hafnium. Metall Treatises, Metall Soc AIME, 171–182
- Stanaway KJ (1994) Overview of titanium dioxide feedstocks. Min Eng 46: 1367-1370
- AthaVale AS, Altekar VA. (1971) Kinetics of selective chlorination of ilmenite using hydrogen chloride in a fluidized bed. Ind Eng Chem Process Des Develop 10: 523-530
- Lakshmanan CM, Hoelscher HE Chennakesavan B (1965) The kinetics of ilmenite benefication in a fluidized chlorinator. Chem Eng Sci 20: 1107- 1113
- Van Deventer JSJ (1988) Kinetics of the selective chlorination of ilmenite. Thermochemica Acta 124: 205-215
- Matsuoka R, Okabe TH (2005) Iron removal from titanium ore using selective chlorination and effective utilization of chloride wastes. EPD Congress, TMS (The Minerals, Metals & Materials Society), 1-10
- Zheng H, Okabe TH (2010) Selective chlorination of titanium ore and production of titanium powder by perform reduction process (PRP), 1-6
- Kang J, Okabe TH (2013) Removal of iron from titanium ore through selective chlorination using magnesium chloride. Mater Trans 54: 1444-1453
- Kang J, Okabe TH (2014) Production of titanium dioxide directly from titanium ore through selective chlorination using titanium tetrachloride. Mater Trans 55: 591-598
- Kang J, Okabe TH (2013) Upgrading titanium ore through selective chlorination using calcium chloride. Metall Mater Trans B 44: 516–527
- Guo Y, He J, Jiang T, Liu S, Zheng F, Wang S (2014) Preparation of synthetic rutile from titanium slag. In: 5th International Symposium on high-temperature metallorganical processing, Schiesinger ME, Yuceio, Padilla R, Mackey PJ, Zhou G, Eds., Wiley, SanDiego, CA, USA
- Yang K, Peng J, Zhang L, Zhu H, Chen G, Zheng X, Tan X, Zhang S (2014) Research on microwave roasting of high titanium slag process. In: 5th International Symposium on high-temperature metallorganical processing, Schiesinger ME, Yucei O, Padilla R, Mackey PJ, Zhou G, Eds., Wiley, SanDiego, CA, USA
- Dmitriev AN, Petukhov RV, Vitkina GYu, Chesnokov YuA, Kornilkov SV, Pelevin AE (2016) The reduction processes of the titanium containing iron ores treatment. Defect and Diffusion Forum 369: 6-11
- Youn IJ, Park KY, (1989) Modeling of fluidized bed chlorination of rutile. Metall Trans B 20: 959-966
- Rhee KI, Sohn HY (1990) The selective chlorination of iron from ilmenite ore by CO-Cl2 mixtures. Part 1: Instrinsic kinetics. Metall Trans B 21: 321- 329
- Jena P, Broccchi EA, Gameiro DH (1998) Kinetics of the chlorination of TiO2 by Cl2 in the presence of graphite powder. Trans Instit Min Metall 107: 139- 145
- Morris, AJ, Jensen, RF (1976) Fluidized-bed chlorination rates of Australian rutile. Metall Trans B 7: 89-93
- Sohn HY, Zhou L, Cho K (1998) Intrinsic kinetics and mechanism of rutile chlorination by CO and Cl2 mixtures. Ind Eng Chem Res 37: 3800-3805
- Sohn HY, Zhou L (1998) The kinetics of carbochlorination of titania slag. Can J Chem Eng 76: 1078-1082
- Sohn HY, Zhou L (1999) The chlorination kinetics of beneficiated ilmenite particles by CO+Cl2 mixtures. Chem Eng J 72: 37– 42
- Le Roux JT (2001), Fluidized bed chlorination of titania slag. MSc thesis. University of Pretoria
- Nell J, den Hoed P (2003) Carbo-chlorination of rutile, titania slag and ilmenite in a bubbling fluidized bed reactor. Int Mineral Process Cong XXII, 1426–1433
- Niu LP, Ni PY, Zhang TA, Lv GZ, Zhou AP, Liang X, Men D (2014) Mechanism of fluidized chlorination reaction of Kenya natural rutile ore. Rare Met 33:485-492
- Maharajh S, Muller J, Zietsman JH (2015) Value-in-use model for chlorination of titania feedstocks, The Southern African Institute of Mining and Metallurgy, Pyrometallurgical Modelling 33-50
- Li B, Yuan ZF, Li WB, Xu C (2004) A new method for deoxidization and chlorination of refined ilmenite with high magnesia and calcia contents. China Particulology 2: 84-88
- Yuan ZF, Xu C, Zheng SH, Zhou JC (2003) Comprehensive utilization of titanium resources in Panzhihua. Modem Chem Ind 23: 1-4
- Perkins EC (1963) Fluidized bed chlorination of titaniferous slag and ores. US Bureau Mines 6317: 1-13
- Yang FL, Hlavacek V (2000) “Effective extraction of titanium from rutile by a low-temperature chloride process”. AIChE J 46: 355- 360
- Yang FL (2000) Recycling titanium from Ti-waste by a low-temperature extraction process. AIChE J 46: 2499-2503
- Luckos A, Mitchell D (2002) The design of a circulating fluidized-bed chlorinator at Mintek. In: IFSA 2002 Industrial Fluidization South Africa, Luckos A, den Hoed P, Eds, Johannesburg, South Africa, 147-160
- Tardos G, Mazzone D, Pfeffer R (1985) Destabilization of fluidized beds due to agglomeration Part I. Can J Chem Eng 63: 377- 383
- Cong X, Zhangfu Y, and Xiaoqiang W(2006) Preparation of TiCl4 with the titanium slag containing magnesia and calcia in a combined fluidized bed. Chinese J Chem Eng 14: 281-288
- Cong X, Zhangfu Y, and Xiaoqiang W, Fan J, Li J, Wang Z (2006) Production TiCi4 using combined fluidized bed by titanium slag containing high-level CaO and MgO. Studies Surf Sci Catal 159: 493-496
- Zhangfu Y , Xiaoqiang W, Cong X, Wenbing L, Mooson K (2006) A new process for comprehensive utilization of complex titania ore. Min Eng 19: 975–978
- Shao-feng X, Zhang-fu Y, Cong X, Liang X (2010) Composition of off-gas produced by combined fluidized bed chlorination for preparation of TiCl4. Trans Nonferrous Met Soc China 20: 128-134
- Zhang-fu Y, Yuan-qing Z, Liang X, Shao-feng X, Bing-sheng X (2013) Preparation of TiCl4 with multistage series combined fluidized bed. Trans Nonferrous Met Soc China 23: 283−288