Extractive Metallurgy of Titanium

<p>Contents</p> <p>Contributors xi</p> <p>1. Introduction to the development of processes for primary</p> <p>Ti metal production 1</p> <p>Zhigang Zak Fang, Hyrum D. Lefler, F.H. Froes, and Ying Zhang</p> <p>References 8</p> <p>Part 1 Extractive chemical metallurgy processes 11</p> <p>2. A brief introduction to production of titanium dioxide</p> <p>and titanium tetrachloride 13</p> <p>Michael L. Free</p> <p>1. Background 13</p> <p>2. Ore sources 13</p> <p>3. Processing methods 14</p> <p>References 17</p> <p>3. Minerals, slags, and other feedstock for the production</p> <p>of titanium metal 19</p> <p>Dimitrios Filippou and Guillaume Hudon</p> <p>1. Introduction 19</p> <p>2. Ilmenite, rutile, and other natural titanium minerals 21</p> <p>3. Ilmenite smelting to titania slag 26</p> <p>4. Ilmenite conversion to synthetic rutile 32</p> <p>5. Titania slag upgrading to UGS 36</p> <p>6. Production of titanium carbide feedstock 37</p> <p>7. Conclusions 38</p> <p>Acknowledgments 41</p> <p>References 41</p> <p>4. Chemical processes for the production of titanium tetrachloride</p> <p>as precursor of titanium metal 47</p> <p>Guillaume Hudon and Dimitrios Filippou</p> <p>1. Introduction 47</p> <p>2. Titanium tetrachloride 47</p> <p>3. Production of titanium tetrachloride 49</p> <p>4. Titanium tetrachloride purification 55</p> <p>5. Production of pure titanium dioxide 56</p> <p>6. Other precursors 59</p> <p>Acknowledgments 60</p> <p>References 60</p> <p>Part 2 Thermochemical reduction of TiCl4 63</p> <p>5. Fundamentals of thermochemical reduction of TiCl4 65</p> <p>Toru H. Okabe and Osamu Takeda</p> <p>1. Historical developments in titanium metal production 65</p> <p>2. Kroll process 66</p> <p>3. Hunter process 71</p> <p>4. Fundamentals of titanium reduction process 75</p> <p>5. Electrochemical reactions during thermochemical reduction 78</p> <p>6. Reduction mechanism of TiCl4 during the Kroll process 81</p> <p>7. Past research for new titanium production processes 83</p> <p>8. Summary 90</p> <p>References 92</p> <p>6. The Kroll process and production of titanium sponge 97</p> <p>Matthew R. Earlam</p> <p>1. Introduction 97</p> <p>2. Source of ore 99</p> <p>3. Production of TiCl4 100</p> <p>4. Purification of TiCl4 101</p> <p>5. The Hunter process 102</p> <p>6. Armstrong process 103</p> <p>7. Kroll process 103</p> <p>8. Magnesium reduced acid leach (MRAL) (no longer practiced) 104</p> <p>9. Vacuum distillation process TOHO timet 107</p> <p>10. Preparation for melting 110</p> <p>References 111</p> <p>7. A modified Kroll process via production of TiH2 - thermochemical</p> <p>reductions of TiCl4 using hydrogen and Mg 113</p> <p>Mykhailo Matviychuk, Andrey Klevtsov, and Vladimir S. Moxson</p> <p>1. Introduction 113</p> <p>2. Process description 114</p> <p>3. Experimental results 120</p> <p>4. Role of hydrogen for ADMA process 122</p> <p>References 127</p> <p>Further reading 128</p> <p>Part 3 Thermochemical reduction of TiO2 129</p> <p>8. Metallothermic reduction of TiO2 131</p> <p>Toru H. Okabe</p> <p>1. Introduction 131</p> <p>2. Studies on reduction of titanium oxide before 2000 134</p> <p>3. Studies on reduction of titanium oxide after 2000 143</p> <p>4. Future prospects of metallothermic reduction processes for direct</p> <p>production of titanium from oxides 155</p> <p>5. Summary 159</p> <p>References 160</p> <p>9. Hydrogen assisted magnesiothermic reduction (HAMR) of</p> <p>TiO2 to produce titanium metal powder 165</p> <p>Yang Xia, Hyrum D. Lefler, Ying Zhang, Pei Sun, and Zhigang Zak Fang</p> <p>1. Introduction 165</p> <p>2. Fundamentals of the HAMR process 167</p> <p>3. HAMR process description 172</p> <p>4. HAMR product characterization 173</p> <p>5. Summary 176</p> <p>Acknowledgments 176</p> <p>References 177</p> <p>10. Deoxygenation of Ti metal 181</p> <p>Ying Zhang, Zhigang Zak Fang, Pei Sun, Yang Xia, Hyrum D. Lefler,</p> <p>and Shili Zheng</p> <p>1. Introduction 181</p> <p>2. Thermodynamic properties of the TieO solid solutions 182</p> <p>3. Methods of deoxygenation 186</p> <p>4. Concluding remarks 206</p> <p>A. Appendix 207</p> <p>Acknowledgments 220</p> <p>References 220</p> <p>Part 4 Electrochemical reduction of TiO2 and TiOC 225</p> <p>11. Invention and fundamentals of the FFC Cambridge Process 227</p> <p>George Z. Chen and Derek J. Fray</p> <p>1. Background: how the concept of electro-deoxidation came about 227</p> <p>2. Understanding of electro-deoxidation: interactions of the oxide cathode</p> <p>with molten salts 230</p> <p>3. Understanding of electro-deoxidation: metal/insulator/electrolyte 3PI</p> <p>models 235</p> <p>4. Understanding of electro-deoxidation: the metal-to-oxide molar volume</p> <p>ratio 236</p> <p>5. Development of an inert anode for electro-deoxidation in calcium</p> <p>chloride based melts 241</p> <p>6. Electro-deoxidation of other metal oxides 246</p> <p>7. Electro-desulfidation of metal sulfides 257</p> <p>8. Electro-deoxidation of mixed metal oxides 261</p> <p>9. Titanium based medical implant materials 273</p> <p>10. Cathodic protection of titanium 276</p> <p>11. Outlook and Prospective 278</p> <p>12. Conclusions 279</p> <p>References 280</p> <p>12. OS process: calciothermic reduction of TiO2 via CaO electrolysis</p> <p>in molten CaCl2 287</p> <p>Ryosuke O. Suzuki, Shungo Natsui, and Tatsuya Kikuchi</p> <p>1. Introduction 287</p> <p>2. Cell design 296</p> <p>3. Thermodynamics of desired salt 298</p> <p>4. Validity of Ca reduction during electrolysis 303</p> <p>5. Conclusion 308</p> <p>References 309</p> <p>13. Titanium production through electrolysis of titanium oxycarbide</p> <p>consumable anodedthe USTB process 315</p> <p>Hongmin Zhu, Shuqiang Jiao, Jiusan Xiao, and Jun Zhu</p> <p>1. Introduction 315</p> <p>2. Crystalline structure of titanium oxycarbide and titanium</p> <p>oxycarbonitride 316</p> <p>3. Thermodynamic properties and preparation of titanium oxycarbide from</p> <p>TiO2 by carbon thermal reduction 317</p> <p>4. Electrochemical dissolution of consumable anode 320</p> <p>5. Electrochemical deposition on the cathode 325</p> <p>6. Scaling up and practices of USTB process 326</p> <p>References 328</p> <p>14. Electrolysis of carbothermic treated titanium oxides to produce</p> <p>Ti metal 331</p> <p>James C. Withers</p> <p>References 343</p> <p>Further reading 347</p> <p>Part 5 Other processes 349</p> <p>15. Selected processes for Ti production e a cursory review 351</p> <p>Pei Sun, Ying Zhang, and Zhigang Zak Fang</p> <p>1. Introduction 351</p> <p>2. Continuous processes using Mg or Na as the reductant 352</p> <p>3. Processes using low-cost alternatives as reductants 356</p> <p>4. Summary 360</p> <p>Acknowledgments 360</p> <p>References 360</p> <p>16. Recycling of Ti 363</p> <p>Osamu Takeda, Toru H. Okabe</p> <p>1. Introduction 363</p> <p>2. Ti scraps generated in the smelting process 364</p> <p>3. Ti scraps generated in the aircraft industry 367</p> <p>4. Material flow of Ti scraps 373</p> <p>5. Recycling technologies for Ti scraps 374</p> <p>6. Future perspective of recycling technologies 377</p> <p>7. Conclusions and future remarks 382</p> <p>Acknowledgments 383</p> <p>References 383</p> <p>17. Energy consumption of the Kroll and HAMR processes for</p> <p>titanium production 389</p> <p>Yang Xia, Hyrum D. Lefler, Zhigang Zak Fang, Ying Zhang, and Pei Sun</p> <p>1. Introduction 389</p> <p>2. Review of energy consumption in the Kroll process 390</p> <p>3. Modeling and analysis of energy consumption in the HAMR process 398</p> <p>4. Energy consumption in other emerging processes 404</p> <p>5. Summary and comparison of Kroll and HAMR processes 405</p> <p>Acknowledgments 406</p> <p>References 407</p> <p>Index 411</p>