Production of Scandium and Al-Sc Alloy

Masanori Harataa, Takao Nakamurab

Hiromasa Yakushijic, Toru H. Okabea

aThe University of Tokyo

bChiba Institute of Technology
cPacific Metals Co., Ltd.

1
Production of Scandium and Al-Sc Alloy

1. Introduction

2. Metallothermic reduction

3. Molten salt electrolysis

4. Summary

2
 Scandium?

One of the rare earth elements Sc metal

Low density (2.99 g / cm3)
High chemical reactivity
High price (10,000~ yen / g)

Al-Sc alloy Al-Sc alloy Halide lamp

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

Scandium is the 31st most abundant element in the earth crust.

4
 Scandium-containing minerals

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

Matte/Metal Slag Ni and Co recovery

Ni and Co Leachant
Ni Containing Sc2O3 Sc2O3

Sc2O3 in a slag can not Sc2O3 in leachant can be

be recovered. recovered at a low cost.

6
 Purpose of this study
Ellingham diagram
Standard Gibbs energy of formation, Gf / kJ mol-1

-800 Conventional process

= TiO 2 l 2O 3 Fluorination:
3 A 973 K
Ti +O 2
=2
/
Sc2O3 (s) + 6 HF (g) 2 ScF3 (s) + 3 H2O (g)
O2
-900 l+
4/ 3A
Reduction: ~1873 K
cF 3
=2 /3 S 2 ScF3 (l) + 3 Ca (g) 2 Sc (l) + 3 CaF2 (l)
F2
-1000 S c+
2 /3 a 2O 3
/ 3 L O
= 2 2 Ca
O 2

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

3. Molten salt electrolysis

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)

Stainless steel reaction

chamber

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.

Reduction experiment using a collector metal

Exp. B: Sc2O3 (0.0011 mol), Ca (0.0065 mol), Al (0.036 mol)
Intensity, I (a. u.)

Obtained Al-Sc alloy Al3Sc JCPDS # 17-0412

Al JCPDS # 04-0787
Al4Ca JCPDS # 14-0428

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

3. Molten salt electrolysis

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

Sc segregated at the surface of the sample.

14
 Molten salt electrolysis (XRF)

XRF results of the samples obtained after the electrolysis.

Exp. # Molten salt system Current, i /A Time, t /s Al Sc Ca Fe
1
d-1 CaCl2-1.37mol%Sc2O3 1.00 1800 88.3 11.5 0.14 <0.01
2
d-1 CaCl2-1.37mol%Sc2O3 1.00 1800 96.9 3.1 <0.01 <0.01
1
d-2 CaCl2-2mol%Sc2O3 0.25 7200 97.4 2.2 0.21 0.26
1
d-3 CaCl2-2mol%Sc2O3 1.00 1800 83.3 16.3 0.28 0.19
1
d-4 CaCl2-2mol%Sc2O3 1.00 3600 95.6 3.9 0.46 <0.01
1
d-5 CaCl2-4mol%Sc2O3 0.25 3600 98.9 0.8 0.08 0.21
1
d-6 CaCl2-4mol%Sc2O3 0.50 3600 92.4 6.7 0.45 0.47
1
d-7 CaCl2-4mol%Sc2O3 1.00 1800 93.2 6.2 0.35 0.25
1
d-8 CaCl2-4mol%Sc2O3 1.00 3600 85.7 13.8 0.39 0.09
1
d-9 CaCl2-8mol%Sc2O3 0.25 3600 67.0 32.3 0.65 <0.01
2
d-9 CaCl2-8mol%Sc2O3 0.25 3600 83.1 16.5 0.10 0.27
1
d-10 CaCl2-8mol%Sc2O3 0.25 7200 89.4 9.6 0.39 0.60
1 Surface of the sample was analyzed.
2 Section of the sample was analyzed.

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

Theoretical maximum wSc : Mass of Sc in the sample.

0.4
wAl-Sc: Mass of the sample obtained
after electrolysis.
0%
CSc : Concentration of Sc in the
0
0.2 1 sample determined by XRF.
=

Current efficiency of each sample varied widely.

0
0 1000 2000 3000 4000
In some experiment, current efficiency
Electrical charge Q / C was more than 100%.
16
 Summary
For producing Sc and Al-Sc alloy directly from Sc2O3 at low temperatures,
metallothermic reduction and molten salt electrolysis were conducted.

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.

When aluminum was used as a collector metal, excess calcium

remained in the alloy sample in the form of Al4Ca.

Molten salt electrolysis

It was difficult to evaluate the current efficiency of electrolysis because

Sc segregated around the surface of the Al-Sc alloy sample.

Al-Sc alloy0.81~32.31 mass%) with low calcium impurity(~0.69 mass%)

was successfully produced by the electrolysis of CaCl2-Sc2O3 molten salt.
17
Future Process of high performance Al alloy production

Carbon electrode (anode)

e- A
V Cathodic reaction:
Sc2O3 Al Sc3+ (in salt) + 3 e- Sc (l, in Al)
Anodic reaction:
COx (g) C (s) + x O2- (in salt) COx (g) + 2x e-
Overall reaction:
Sc2O3 (in salt) + C (s)
2 Sc (in Al)+ COx (g)

CaCl2 + Sc2O3
molten salt

Al-Sc liquid alloy

Al-Sc
Al-Scliquid
liquidalloy
alloy
with low Ca 18