ELECTRO-ASSISTED EXTRACTION OF CRITICAL RAW MATERIALS...
Transcript of ELECTRO-ASSISTED EXTRACTION OF CRITICAL RAW MATERIALS...
V. LOPES1, N. COUTO1, A.R. FERREIRA1, E.P. MATEUS1, S. PAMUKCU2, ALEXANDRA B. RIBEIRO1
ELECTRO-ASSISTED EXTRACTION OF CRITICAL RAW MATERIALS FROM COAL ASH
1 CENSE, Departamento de Ciências e Engenharia do Ambiente, Faculdade de Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal2 Department of Civil and Environmental Engineering, Lehigh University, Bethlehem, PA 18015, USA
HERAKLION 2019 - 7th International Conference on Sustainable Solid Waste Management, 29th June 2019, Crete Island, Greece
Rare Earth Elements (REEs)
59
PrPraseodymium
140.908
60
Nd
Neodymium144.243
62
Sm
Samarium150.36
63
EuEuropium151.964
64
Gd
Gadolinium157.25
65
TbTerbium158.925
66
Dy
Dysprosium162.500
67
Ho
Holmium164.930
68
ErErbium167.259
69
Tm
Thulium168.934
70
YbYtterbium
173.055
71
LuLutetium174.967
57
LaLanthanum
138.905
58
CeCerium140.116
21
ScScandium
44.956
39
YYttrium88.906
61
Pm
Promethium144.913
‘Rare’ because they mix diffusely with other minerals underground therefore difficult and costly to extract‘Rare’ because they mix diffusely with other minerals underground therefore difficult and costly to extract
La57- 71
REEs applications
Chart by netl.doe.gov
ProblemEU overview
** 0 - 1: 1 means non-substitutable EU, 2017 Source: Geology.com using data from the United States Geological Survey
o EU is almost entirely dependent upon imports from China
o The 2011 REE-price crisis pointed to the need to reduce the dependence on China’s
imports
o Substitution Index**: 0.96 (HREE) & 0.90 (LREE)
o End of life recycling rate: 8% (HREE) & 3% (LREE) REE Production
1
1
1
Geopolitical strategy
Final List of 35 Minerals deemed critical to U.S. National Security and Economy
2018 May (Dep. of Interior)
List of Critical Raw Materials for the EU – 27 CRMs
2017 September (European Commission)Y
DyEuTb
Nd
CeLaTm
Sm
Pr
Supply Risk
1
2
3
4
21 43
Imp
ort
ance
to C
lean E
nerg
y
Criticality matrix (2015 – 2025)
(Based on the US Dept. of Energy, 2011)
2011 Critical Materials Strategy - by the U.S. Department of Energy - includes criticality assessments:
• Supply challenges for 5 REE may affect clean energy technology deployment in the years ahead.
Aim
In progress:• Assessment and analysis of the feasibility of electrodialytic recover of REEs
from anthracite ash• Proof of concept
Recovery of REEs from a secondary resource (e.g. coal by-product) through electro-based technologies
Recovery of REEs from a secondary resource (e.g. coal by-product) through electro-based technologies
Recover of REEs from fine anthracite coal ash under the influence of an applied low level direct current
Electrodialytic Process
Matrix compartment: anode
Efficient & environmentally-friendly separation and processing technology Efficient & environmentally-friendly separation and processing technology
• Blaschak Coal Corporation, Centralia,
PA, USA
• Northern Pennsylvania
• Lat. 40.8° N, Long. 76.36° W
• Mammoth Vein
Anthracite origin
Imagery ©2019 Google, Map data ©2019
Imagery ©2019 Landsat/Copernicus, Data SIO, NOAA, U.S. Navy, NGA, GEBCO, NOAA, Map data ©2019 Google
Methodology
Anthracite
Anthracite ashASTM (D3174-12)
Electrodialytic cell
Fluxing
ICPEDXSEM-EDS
CutCrush
GrindingAshing pH desorption
testED experiments
FluxingICP
Processing
Characterization
Extraction/Analysis
REE recover
CharacterizationRelative REE content in anthracite ash
Critical
Near Critical
Not CriticalOther REE
Sc Y La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
3,71%
10,09%
19,35%
38,07%
4,04%
14,61%
2,39%0,44%
2,10%0,28%
1,90%0,34%1,21%0,10%
1,28%0,09%
59
PrPraseodymium
140.908
60
Nd
Neodymium144.243
62
Sm
Samarium150.36
63
EuEuropium151.964
64
Gd
Gadolinium157.25
65
TbTerbium158.925
66
Dy
Dysprosium162.500
67
Ho
Holmium164.930
68
ErErbium167.259
69
Tm
Thulium168.934
70
YbYtterbium
173.055
71
LuLutetium174.967
21
ScScandium
44.956
39
YYttrium88.906
57
LaLanthanum
138.905
58
CeCerium140.116
LREE
HREE
REE
SEM microphotograph of anthracite ash
CharacterizationParticle morphology of anthracite ash
• Disperse
• Angular
• Size range: 1 to 10 um
CharacterizationParticle morphology of anthracite ash
Trace elements• Carbon• Oxygen• Aluminum• Silicone• Phosphorus• Titanium• Iron
REEs • Lanthanum• Neodymium• Cerium
SEM microphotographs and respective EDS spectra of a) REE particle; b) agglutination of minerals
b)
a)
pH desorption from anthracite ash
0 1 2 3 4 5 6 7 8 9 10 11 12 13 140%
20%
40%
60%
80%
100%
120%
Sc Y La Ce Pr Nd Sm EuGd Tb Dy Ho Er Tm Yb Lu
pH
LREE
HREE
Outlier
%
ED experiments
Ferreira et al. 2019, Water Air & Soil Pollution, 230(4): 78-88. 1
• 2C-ED cell
• L/S = 15
• CEM = cation exchange membrane
• MMO coated titanium bar
• Time: 3 days
• Current intensity: 10 mA
• pH: no adjustment
1
1
1 +
ResultsDesorped REEs after ED
Critical
Near Critical
Not CriticalOther REE
59
PrPraseodymium
140.908
60
Nd
Neodymium144.243
62
Sm
Samarium150.36
63
EuEuropium151.964
64
Gd
Gadolinium157.25
65
TbTerbium158.925
66
Dy
Dysprosium162.500
67
Ho
Holmium164.930
68
ErErbium167.259
69
Tm
Thulium168.934
70
YbYtterbium
173.055
71
LuLutetium174.967
21
ScScandium
44.956
39
YYttrium88.906
57
LaLanthanum
138.905
58
CeCerium140.116
LREE
HREE
REE
1,1%
4,9%
15,5%
12,7%13,0%12,0%
10,8%
13,5%
8,9%
14,4%
5,4%
10,5%
4,9%
14,4%
3,1%
23,4%
ResultsREEs criticality analysis of relative content after ED
Catholyte Anolyte Membrane Ash0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
33,5821,15 23,56 29,34
29,34 66,29 65,60 52,42
37,07
12,56 10,83 18,24
%
Conclusions
REE desorption improved with the ED process
LREE show higher desorption rates
HREE show promising capabilities of passing through the CEM
Critical REEs
Relative % of REEs desorped by ED
Tb 14.4
Eu 13.5
Nd 12.0
Dy 5.4
Y 4.9
ED process is a promising extraction technique for rare earth elements recover from coal ash
• Blaschak Coal Corporation, 2019. Representative analysis Lattimer mammoth vein. Accessed in June 2019 http://www.blaschakcoal.com/wp-content/uploads/Lattimer-Mammoth-Vein-Rep-Analysis.pdf
• European Commission, 2017. (COM(2017) 490) ‘on the 2017 list of Critical Raw Materials for the EU’ 2017.
• Ferreira, A.R.; Couto, N.; Ribeiro, A.B.; Ottosen, L.M. 2019. Electrodialytic arsenic removal from bulk and pre-treated soil. 2019, Electrodialytic arsenic removal from bulk and pre-treated soil. Water Air & Soil Pollution, 230(4):78-88.
• NETL - National Energy Technology Laboratory. REE Program. Accessed in June 2019, https://netl.doe.gov/coal/rare-earth-elements/program-overview/background
• REE - Rare Earth Elements and their Uses. Accessed in June 2019, https://geology.com/articles/rare-earth-elements/
• US DoE, 2011. Critical Materials Strategy report. US Department of Energy
References
This work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 778045, and from FCT/MEC through grant UID/AMB/04085/2019 to the Research unit CENSE – Center for Environmental and Sustainability Research. N. Couto also acknowledges FCT Investigator Contract CEECIND/04210/2017.
Acknowledgements
pH desorption LREE
0 1 2 3 4 50%20
%40
%60
%80
%10
0%
REE desorption at acidic pH
pH
Deso
rpti
on (
%)
59
PrPraseodymium
140.908
60
Nd
Neodymium144.243
62
Sm
Samarium150.36
63
EuEuropium151.964
57
LaLanthanum
138.905
58
CeCerium140.116
21
ScScandium
44.956
LREE - Stable complexes are the first to desorp- Higher desorption rates compared
to HREE
LREE - Stable complexes are the first to desorp- Higher desorption rates compared
to HREE
Tendency- Desorption starts from lower to
higher atomic number (i.e. inversely related with ionic
radius)
Tendency- Desorption starts from lower to
higher atomic number (i.e. inversely related with ionic
radius)
Scandium- Different electronic and
magnetic properties
Scandium- Different electronic and
magnetic properties
ResultsRelative distribution of REEs in the ash
Before ED
31,57%
17,50%
50,93%
27,31%
57,53%
15,16%
After ED
ResultsREE distribution within the cell
59
PrPraseodymium
140.908
60
Nd
Neodymium144.243
62
Sm
Samarium150.36
63
EuEuropium151.964
64
Gd
Gadolinium157.25
65
TbTerbium158.925
66
Dy
Dysprosium162.500
67
Ho
Holmium164.930
68
ErErbium167.259
69
Tm
Thulium168.934
70
YbYtterbium
173.055
71
LuLutetium174.967
21
ScScandium
44.956
39
YYttrium88.906
57
LaLanthanum
138.905
58
CeCerium140.116
%
ResultsRelative distribution of REEs in the liquid phase after ED
Anolyte Catholyte
11
14
20
5
7
11
ResultsREE in the catholyte after ED
Critical
Near Critical
Not CriticalOther REE
59
PrPraseodymium
140.908
60
Nd
Neodymium144.243
62
Sm
Samarium150.36
63
EuEuropium151.964
64
Gd
Gadolinium157.25
65
TbTerbium158.925
66
Dy
Dysprosium162.500
67
Ho
Holmium164.930
68
ErErbium167.259
69
Tm
Thulium168.934
70
YbYtterbium
173.055
71
LuLutetium174.967
21
ScScandium
44.956
39
YYttrium88.906
57
LaLanthanum
138.905
58
CeCerium140.116
LREE
HREE
REE
2,8%4,7%
0,7%0,5%2,5%
0,6%2,2%
12,3%
2,9%
24,0%
4,7%
24,4%
12,3%
32,6%
5,3%
33,5%
Future Work
• 7 days
Higher desorption rates
TT
pH adjustment
Increase current intensity
Experiment duration
• 50 mA Higher desorption rate
Higher migration speed of the REE from the anolyte to the catholyte
• In the catholyte (pH ~2)
Prevention of ion element precipitation
Prevention of the formation of aggregated elements around the electrodes and the membrane
Prevent membrane obstruction