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RMW3 20 Harata T
RMW3 20 Harata T
1
Production of Scandium and Al-Sc Alloy
1. Introduction
2. Metallothermic reduction
4. Summary
2
Scandium?
MIG29
Bicycle frame
3
Crustal abundance of scandium
Rank. Atomic Element Content of Rank Atomic Element Content of Rank. Atomic Element Content of
number, earth crust number, earth crust number, earth crust
Z (%) Z (%) Z (%)
-3
01 08 O 46.60 24 30 Zn 07.010
-3 -4
02 14 Si 27.72 25 58 Ce 06.010 46 68 Er 02.810
-3 -4
03 13 Al 08.13 26 29 Cu 05.510 49 50 Sn 02.010
-3 -4
04 26 Fe 05.00 27 39 Y 03.310 50 73 Ta 02.010
-3 -4
05 20 Ca 03.63 28 57 La 03.010 51 92 U 01.810
st abundant
-3
06 11 Na 02.83 29 60 Nd 02.810
-3
31
-4
07 19 K 02.59 30 27 Co 02.510 55 74 W 01.510
-3 -4
08 12 Mg 02.09 31 21 Sc 02.210 56 63 Eu 01.210
-4
09 22 Ti 00.44 57 67 Ho 01.210
-3 -5
10 01 H 00.14 33 07 N 02.010 58 65 Tb 0810
-3 -5
11 15 P 00.105 34 41 Nb 02.010 59 53 I 0510
-3 -5
12 25 Mn 00.095 35 31 Ga 01.510 60 69 Tm 0510
-3 -5
13 09 F 00.0625 36 82 Pb 01.310 61 71 Lu 0510
-3
37 05 B 01.010
-4 -6
16 16 S 00.026 38 59 Pr 08.210 67 80 Hg 0810
-6
17 06 C 00.020 68 47 Ag 0710
-4
40 62 Sm 06.010
-4 -6
20 17 Cl 00.013 41 64 Gd 05.410 73 78 Pt 0110
-4 -7
42 66 Dy 04.810 74 45 Rh 0510
-3 -4 -7
23 28 Ni 07.510 43 70 Yb 03.010 75 79 Au 0410
Content of
Form Mineral name
Sc2O3 (mass%) Thortveitite ore [(Sc, Y)2Si2O7]
Thortveitite 25.0~48.3
Zircon 0.005~0.3
Beryl 0.0005~1.2
Silicates
Garnet 0.02~0.4
Olivine 0.0003~0.02
Pyroxene ~0.04 ~48.3 mass%Sc2O3
Xenotime 0.0015~1.5
Phosphates Monazite 0.002~0.5
Apatite 0.0003~0.08
Currently, Sc is recovered from rare
Davidite 0.02 earth ores or as a by-product from
Columbite 0.01~0.8 uranium mill tailings.
Uraninite 0.15~0.2
Wolframite 0.005~1.3
Magnetite 0.001~0.04 Sc is distributed very widely among
Oxides 800 different earthly species of minerals.
Hematite ~0.15
Titanomagnetit 0.0002~0.02
Ilmenite 0.0015~0.15
Rutile 0.005~0.16
Recently, possibility of recovering
Laterite 0.003~0.03
Sc from Ni laterite ore is focused.
5
Possibility of recovering scandium from nickel ore
Pyrometallurgy Hydrometallurgy
Ni ore containing Sc Ni ore containing Sc
Hydrometallurgical process
Pyrometallurgical process
Leachant
Ni and Co Leachant
Ni Containing Sc2O3 Sc2O3
6
Purpose of this study
Ellingham diagram
Standard Gibbs energy of formation, Gf / kJ mol-1
3 La+ O 2
= Disadvantage
4/ a+
-1100 2C The production cost is high because an
c 2O
3
a F2 S
=C 2/3 expensive reaction apparatus is required
+ F2 =
Ca + O2 for handling fluorides.
Sc
-1200 4/3
Contamination from the crucible can not be
prevented due to the high temperature reaction.
-1300
300 500 700 900 1100 1300
Temperature, T / K
Purpose of this study
Development of a new process which can produce Sc metal
or Al-Sc alloy directly from Sc2O3 at low temperatures (~1273 K).
7
Production of Scandium and Al-Sc Alloy
1. Introduction
2. Metallothermic reduction
4. Summary
8
The concept of metallothermic reduction
Metallothermic reduction
Reduction:
4 Sc2O3 (s) + 3 Ca (g) 2 Sc (s) + 3 CaSc2O4 (s)
Reduction and alloying:
Sc2O3 (s) + Al (l) + 3 Ca (g) Al-Sc alloy (l) + 3 CaO (s)
Sc2O3 (+ Al + CaCl2)
Temperature, Tred = 1273 K
Ta crucible
Time: tred = 6 h
Ca vapor
Ca shots
Ti sponge
9
Result (1) Sc2O3 (+ Al) + Ca
Reduction experiment in the absence of a collector metal
Exp. A: Sc2O3 (0.005 mol) + Ca (0.030 mol, vapor)
Obtained sample Sc JCPDS # 17-0714
Intensity, I (a.u.)
CaSc2O4 JCPDS # 05-0629
Sc2O3 JCPDS # 20-0234
10 20 30 40 50 60 70 80 90 100
Angle, 2 / degree
A complex oxide (CaSc2O4) was formed and reduction was incomplete.
10 20 30 40 50 60 70 80 90 100
Angle, 2(degree)
Sc2O3 was successfully reduced to metallic Sc and alloyed in situ
to form liquid Al-Sc alloy without forming CaSc2O4.
10
Result (2) Sc2O3 + Al + Ca +CaCl2
Reduction experiment using a collector metal and flux
Exp. C: Sc2O3 (0.0011 mol), Ca (0.0065 mol), Al (0.036 mol), CaCl2 (0.0095 mol)
Obtained Al-Sc alloy
Al JCPDS # 04-0787
Intensity, I (a.u.)
Al3Sc JCPDS # 17-0412
Al4Ca JCPDS # 14-0428
10 20 30 40 50 60 70 80 90 100
Angle, 2 / degree
Metallic phase was easily separated from slag phase.
EPMA analysis
(a) Aluminum (b) Scandium (c) Calcium
Al3Sc
Al4Ca
11
Production of Scandium and Al-Sc Alloy
1. Introduction
2. Metallothermic reduction
4. Summary
12
The concept of molten salt electrolysis
Electrolysis
Cathodic reaction : Sc3+ (in salt) + 3 e- Sc (l, in Al)
Anodic reaction : C (s) + x O2- (in salt) COx (g) + 2x e-
Overall reaction : Sc2O3 (in salt) + C (s) 2 Sc (in Al)+ COx (g)
T = 1173 K
e-
Carbon electrode (anode)
Sc2O3
Molten salt
Solid Sc2O3
particle
CaCl2 + Sc2O3 O O2-
molten salt
e- e-
Al liquid electrode (cathode) Al liquid electrode
13
Molten salt electrolysis (XRD, EPMA)
Sectioned sample XRD analysis
Al JCPDS # 17-0412
Intensity, I (a.u.)
Al3Sc JCPDS # 04-0787
Analysis area
5 mm
10 20 30 40 50 60 70 80 90 100
Angle 2/ degree
EPMA analysis
(a) Aluminum (b) Scandium (c) Calcium
Al3Sc
Al-Sc alloy with low Ca contamination (<0.65 mass%) was successfully produced
by electrolysis of CaCl2-Sc2O3 molten salt. 15
Evaluation of current efficiency
(a) CaCl2-2mol%Sc2O3 molten salt (b) CaCl2-4mol%Sc2O3 molten salt
0.6 0.6
0.25 A 0.25 A
Calculated mass of Sc
in the sample, wSc / g
1A 0.5 A
Calculated mass of Sc
in the sample, wSc / g
Theoretical maximum 1A
0.4 Theoretical maximum
0.4
0 0%
0 0% 1
0.2 1 0.2 =
=
0 0
0 1000 2000 3000 4000 0 1000 2000 3000 4000
Electrical charge Q / C Electrical charge Q / C
(c) CaCl2-8mol%Sc2O3 molten salt
0.6
0.25 A
wSc = wAl-Sc CSc
Calculated mass of Sc
in the sample, wSc / g
Metallothermic reduction
When Al was used as a collector metal for the reduction of Sc2O3,
metallic Sc was successfully obtained directly from Sc2O3 and alloyed
in situ to form liquid Al-Sc alloy.
CaCl2 + Sc2O3
molten salt
Al-Sc
Al-Scliquid
liquidalloy
alloy
with low Ca 18