Selective Chlorination of Titanium Ore by Electrochemical Method

電気化学的手法によるチタン鉱石の選択塩化
Isao Obana* and Toru H. Okabe**
*Graduate School of Engineering, The University of Tokyo **Institute of Industrial Science, The University of Tokyo

Introduction The Kroll process New Ti reduction process (EMR / MSE process)
Features of titanium Applications Titanium production process Reduction: Features of the EMR process:
e- A Titanium reduction
Lightweight and high Aircraft ◎Resistant to iron and carbon
Cathode:
strength Spacecraft Mg & TiCl4 e- TiO + 4 e - → Ti + 2 O2- contamination
Corrosion resistant Chemical plant Carbon 2
○Semi-continuous process
feed port Anode:
Biocompatibility Implant electrode
Ca → Ca2+ + 2 e- ○Reduction and electrolysis
Some titanium alloys: Artificial bone
e- O2- Electrolysis:
operations can be carried
shape-memory effect etc. Sponge Molten out independently.
superelasticity titanium CaCl2-CaO Reductant production ×Difficult metal / salt separation
TiO2 Ti Cathode: with oxide system
Comparison between titanium and common metals Ti crucible Ca2+ + 2 e- → Ca ×Complicated cell structure
Ti Al Fe （Cathode） Anode: △Complicated process
Chlorination
Melting point (℃) 1660 660 1,540 Ti ore + C + 2 Cl2 → TiCl4 (+ FeClx) + CO2 C + x O2- → COx + 2x e-
Reduction Ca-X alloy
Price (\ / kg) 3,000 600 50 Overall reaction
TiCl4 + 2 Mg → Ti + 2 MgCl2
Production vol. < 50,000 20,000,000 800,000,000 Electrolysis Ti reduction Reduction production TiO2 + C → Ti + CO2
(t / year・world) MgCl2 → Mg + Cl2
< 1/400 < 1/16,000
Features of the Kroll process: Wastes from the Kroll process
◎ High-purity Ti can be obtained. Issues related to chloride wastes:
$ 0.1 ～ 0.2 / kg Ti
Ilmenite (Ti ore) ◎ Metal / salt separation is easy. FeOx Others 1. Disposal cost and environmental burden
Others
×50 ～ 100 ○ Chlorine circulation is established. Upgrade 2. Additional chlorine gas has to be purchased.
Sponge titanium $ 10 / kg Ti ○ Efficient Mg electrolysis can be utilized. Chloride
○ Reduction and electrolysis can be FeOx TiOx 3. Effective utilization has not been established.
×2 ～ 5 carried out independently.
TiOx wastes
Bulk metal $ 18 ～ 20 / kg Ti × Process is complicated.
× Batch-type reduction process is used. Ti ore (Ilmenite) Upgraded Ilmenite (UGI) Upgrading Ti ore for minimizing
Bars & rods $ 30 ～ 50 / kg Ti chloride wastes
× Production speed is low. Discarded
× Chloride wastes cannot be utilized.

New process
This study (electrochemical method)
Ti smelting process using low-grade Ti ore Thermodynamic analysis Experiment
This study Selective chlorination・Iron removal process
Ti ore: mixture of FeOx and TiOx Cathode： Fen+ + n e- → Fe
Ca2+ + 2 e- → Ca
Low-grade Ti ore MClx FeClx Ti scrap Fe-Cl-O and Ti-Cl-O systems, T = 1100 K Anode ： 2 Cl- → Cl2 + 2 e-
(FeTiOX) (CaCl2) 0
Potential region for
FeO x + C + Cl 2 → FeClｘ (l, g) + CO x
Selective chlorination Chlorine recovery -10 selective chlorination
of iron V1 V2
CO / CO2 eq.
log pO (atm)

-20 A1 A2 Potential lead (Ni wire)

Upgraded Ti ore FeClx Fe TiCl4 C / CO eq. Stainless steel tube
(TiO2) (+AlCl3) -30 Ar inlet
2

MgO (g) / MgCl2 (l) eq. Rubber plug

-40 Wheel flange
Ti smelting Advantages: H2O (g) / HCl (g) eq. Reaction chamber
Thermocouple
1. Material cost can be reduced by using low-grade ore. -50
2. Chlorine circulation in the Kroll process can be improved. CaO (s) / CaCl2 (l) eq. Heater
aCaO = 0.1
Ti metal 3. This process can also be applied to the new Ti production -60
Mild steel crucible (Cathode)
Nickel electrode
processes by the direct reduction of TiO2. -40
-–
40 -30 -20 -10 0
log pCl (atm) Carbon crucible (Anode)
2 Ti ore
Fig. Chemical potential diagram for Fe-Cl-O and Molten salt (CaCl2)
Ti-Cl-O systems at 1100 K. Ceramic insulator
Earlier studies (pyrometallurgical methods) Iron removal from Ti ore by
Results selective chlorination using MgCl2 Fig. Schematic illustration of experimental apparatus
Experiment in this experiment.
is thermodynamically feasible.
FeOx (s) + MgCl2 (l) = FeClx (l) + MgO (s) XRF analysis Experimental condition:
Vacuum pump T = 1100 K; t’ = 9 h; Atmosphere: Ar;
Glass flange Residue after selective chlorination
Results Voltage, E = 1.5 V
Glass beads → Fe was selectively chlorinated.
Stainless-steel net Potentiostatic electrolysis XRF analysis
Chloride Deposit Table Analytical results of titanium ore, the sample
Condenser 5 After the electrochemical treatment, Fe was
Stainless-steel obtained after selective chlorination, Voltage of 1.5 V was imposed.
Current, i / A

4 selectively chlorinated and removed.

susceptor and the sample after reduction.
Carbon crucible 3
Concentration of element i, Ci (mass %)a Table Analytical results of titanium ore (starting sample)
Chlorination Residue 2
Ti Fe Si Al V and the sample obtained after electrochemical
Reactor Mixture of 1 selective chlorination.
Ti ore and MgCl2 Ti ore (UGI from Ind.) 95.10 2.29 0.41 0.12 0.75
0
Concentration of element i, Ci (mass %)a
RF coil After exp. 96.45 0.43 0.44 0.37 1.50 0 15 5
20 10
25 30 35
Quartz flange After reductionb 98.30 0.05 0.38 0.12 0.52 Time, t / ks Ti Fe Si Al V Fe / Ti (%)
Ceramic tube Fig. Experimental result of potentiostatic electrolysis Ti ore 42.62 48.72 2.19 2.23 0.64 114
a: Value determined by XRF analysis
(Voltage, E = 1.5 V; Time, t’ = 9 h ≒ 32 ks)
N2 gas b: Dechlorinated Ti ore was reduced by calciothermic reduction. After exp. 78.38 16.22 0.97 0.88 1.76 20.7
Fig. Experimental apparatus for selective chlorination Average current at approximately 3 A
of titanium ore using MgCl2 as a chlorine source. 82% of Fe was successfully removed.
Iron was removed from Ti ore passed for 9 h.
Experimental condition:
T = 1100 K; t ’ = 1 h; Atmosphere: N2; by chemical methods. Iron was removed from Ti ore by the electrochemical method.
Ti ore (UGI): 4 g, MgCl2: 2 g

Conclusions Future works Ultimate goals: Ti ore (TiO2 + FeOｘ) Low-value ore
Selective chlorination of Ti ore ・A more efficient process Low-cost Ti production Selective chlorination FeClx
by the electrochemical method for producing Fe-free Ti ore directly from low-grade
was investigated, and 80 mass% Fe by the electrochemical method Ti ore will be established. Fe-free TiO2 Direct
was successfully removed from will be investigated. reduction of
low-grade Ti ore. ・Behavior of chlorine in selective Ti smelting ・・・・・・ oxides
chlorination will be investigated. Ti metal Metal