Extraction of Rare Earth Oxides Using Supercritical Carbon Dioxide ...
Supporting Information
Extraction of Rare Earth Oxides Using Supercritical Carbon Dioxide Modified with Tri-n-Butyl Phosphate - Nitric Acid Adducts Donna L. Baek1, Robert V. Fox1, Mary E. Case1,2, Laura K. Sinclair3, Alex B. Schmidt4, Patrick R. McIlwain5, Bruce J. Mincher1, Chien M. Wai2 1. Idaho National Laboratory, Idaho Falls, Idaho 83415, USA 2. University of Idaho, Moscow, Idaho 83843, USA 3. Cornell University, Ithaca, New York 14853, USA 4. Boise State University, Boise, Idaho 83725, USA 5. Montana State University, Bozeman, Montana 59717, USA
Corresponding author: *Donna L. Baek. Email: [email protected].
1.14
Density, g/mL
1.12 1.10 1.08 1.06 1.04 1.02 1.00 0
1
2
3
4
5
6
7
8
9
10
Starting Aq/Org volume ratio
Figure S1. Plot of the density of adducts prepared against various volume ratios of concentrated HNO3 and Wet TBP.
16 14
Acidity, M
12 10 8 6 4 2 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S2. Acid content in the organic and aqueous phases after contact and centrifugation. Solutions were prepared with concentrated HNO3 and Wet TBP. The solid circles represent the aqueous phase and the open circles represent the organic phase.
1e+6
[H2O], ppm
8e+5
6e+5
4e+5
2e+5
0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S3. Plot of the H2O concentration (ppm) in the aqueous phase after contact and centrifugation as a function of volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Wet TBP.
45000 40000
[H2O], ppm
35000 30000 25000 20000 15000 10000 5000 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S4. Plot of the H2O concentration (ppm) in the organic phase after contact and centrifugation with respect to the volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Wet TBP.
1.14
Density, g/mL
1.12 1.10 1.08 1.06 1.04 1.02 1.00 0
1
2
3
4
5
6
7
8
9
10
Starting Aq/Org volume ratio
Figure S5. Plot of the density of adducts prepared against various volume ratios of concentrated HNO3 and Dry TBP.
16 14
Acidity, M
12 10 8 6 4 2 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S6. Acid content in the organic and aqueous phases after contact and centrifugation. Solutions were prepared with concentrated HNO3 and Dry TBP. The solid circles represent the aqueous phase and the open circles represent the organic phase.
1e+6
[H2O], ppm
8e+5
6e+5
4e+5
2e+5
0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S7. Plot of the H2O concentration (ppm) in the aqueous phase after contact and centrifugation as a function of volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Dry TBP.
45000 40000
[H2O], ppm
35000 30000 25000 20000 15000 10000 5000 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S8. Plot of the H2O concentration (ppm) in the organic phase after contact and centrifugation with respect to the volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Dry TBP.
1.3
Density, g/mL
1.2
1.1
1.0
0.9 0.0
0.2
0.4
0.6
0.8
1.0
1.2
Starting Aq/Org volume ratio
Figure S9. Plot of the density of adducts prepared against various volume ratios of fuming HNO3 and Wet TBP.
12
Acidity, M
10 8 6 4 2 0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
Starting Aq/Org volume ratio
Figure S10. Acid content in the organic phase after contact and centrifugation. Solutions were prepared with fuming HNO3 and Wet TBP.
60000
[H2O], ppm
50000 40000 30000 20000 10000 0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
Starting Aq/Org volume ratio
Figure S11. Plot of the H2O concentration (ppm) in the organic phase after contact and centrifugation with respect to the volume ratio of the aqueous and organic phase. Solutions were prepared with fuming HNO3 and Wet TBP.
Pressure, MPa (psi)
(3626) 25
20 85 C 15
10
65 C
45 C
(725) 5 0.001
0.01
0.1
1
Mole fraction of TBP(HNO3)1.9(H2O)0.7
Figure S12. Phase Diagram of TBP(HNO3)1.9(H2O)0.7 in sc-CO2. The lines are used as a guide for the eye.
Pressure, MPa (psi)
(3626) 25
20 85 C 15
65 C
10
45 C
(725) 5 0.001
0.01
0.1
1
Mole fraction of TBP(HNO3)1.2(H2O)0.4
Figure S13. Phase Diagram of TBP(HNO3)1.2(H2O)0.4 in sc-CO2. The lines are used as a guide for the eye.
Extraction of Rare Earth Oxides Using Supercritical Carbon Dioxide Modified with Tri-n-Butyl Phosphate - Nitric Acid Adducts Donna L. Baek1, Robert V. Fox1, Mary E. Case1,2, Laura K. Sinclair3, Alex B. Schmidt4, Patrick R. McIlwain5, Bruce J. Mincher1, Chien M. Wai2 1. Idaho National Laboratory, Idaho Falls, Idaho 83415, USA 2. University of Idaho, Moscow, Idaho 83843, USA 3. Cornell University, Ithaca, New York 14853, USA 4. Boise State University, Boise, Idaho 83725, USA 5. Montana State University, Bozeman, Montana 59717, USA
Corresponding author: *Donna L. Baek. Email: [email protected].
1.14
Density, g/mL
1.12 1.10 1.08 1.06 1.04 1.02 1.00 0
1
2
3
4
5
6
7
8
9
10
Starting Aq/Org volume ratio
Figure S1. Plot of the density of adducts prepared against various volume ratios of concentrated HNO3 and Wet TBP.
16 14
Acidity, M
12 10 8 6 4 2 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S2. Acid content in the organic and aqueous phases after contact and centrifugation. Solutions were prepared with concentrated HNO3 and Wet TBP. The solid circles represent the aqueous phase and the open circles represent the organic phase.
1e+6
[H2O], ppm
8e+5
6e+5
4e+5
2e+5
0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S3. Plot of the H2O concentration (ppm) in the aqueous phase after contact and centrifugation as a function of volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Wet TBP.
45000 40000
[H2O], ppm
35000 30000 25000 20000 15000 10000 5000 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S4. Plot of the H2O concentration (ppm) in the organic phase after contact and centrifugation with respect to the volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Wet TBP.
1.14
Density, g/mL
1.12 1.10 1.08 1.06 1.04 1.02 1.00 0
1
2
3
4
5
6
7
8
9
10
Starting Aq/Org volume ratio
Figure S5. Plot of the density of adducts prepared against various volume ratios of concentrated HNO3 and Dry TBP.
16 14
Acidity, M
12 10 8 6 4 2 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S6. Acid content in the organic and aqueous phases after contact and centrifugation. Solutions were prepared with concentrated HNO3 and Dry TBP. The solid circles represent the aqueous phase and the open circles represent the organic phase.
1e+6
[H2O], ppm
8e+5
6e+5
4e+5
2e+5
0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S7. Plot of the H2O concentration (ppm) in the aqueous phase after contact and centrifugation as a function of volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Dry TBP.
45000 40000
[H2O], ppm
35000 30000 25000 20000 15000 10000 5000 0 0
1
2
3
4
5
6
7
8
9
Starting Aq/Org volume ratio
Figure S8. Plot of the H2O concentration (ppm) in the organic phase after contact and centrifugation with respect to the volume ratio of the aqueous and organic phase. Solutions were prepared with concentrated HNO3 and Dry TBP.
1.3
Density, g/mL
1.2
1.1
1.0
0.9 0.0
0.2
0.4
0.6
0.8
1.0
1.2
Starting Aq/Org volume ratio
Figure S9. Plot of the density of adducts prepared against various volume ratios of fuming HNO3 and Wet TBP.
12
Acidity, M
10 8 6 4 2 0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
Starting Aq/Org volume ratio
Figure S10. Acid content in the organic phase after contact and centrifugation. Solutions were prepared with fuming HNO3 and Wet TBP.
60000
[H2O], ppm
50000 40000 30000 20000 10000 0 0.0
0.2
0.4
0.6
0.8
1.0
1.2
Starting Aq/Org volume ratio
Figure S11. Plot of the H2O concentration (ppm) in the organic phase after contact and centrifugation with respect to the volume ratio of the aqueous and organic phase. Solutions were prepared with fuming HNO3 and Wet TBP.
Pressure, MPa (psi)
(3626) 25
20 85 C 15
10
65 C
45 C
(725) 5 0.001
0.01
0.1
1
Mole fraction of TBP(HNO3)1.9(H2O)0.7
Figure S12. Phase Diagram of TBP(HNO3)1.9(H2O)0.7 in sc-CO2. The lines are used as a guide for the eye.
Pressure, MPa (psi)
(3626) 25
20 85 C 15
65 C
10
45 C
(725) 5 0.001
0.01
0.1
1
Mole fraction of TBP(HNO3)1.2(H2O)0.4
Figure S13. Phase Diagram of TBP(HNO3)1.2(H2O)0.4 in sc-CO2. The lines are used as a guide for the eye.
