The document discusses the synthesis, characterization, and testing of novel silica polyamine composites aimed at recovering rare earth elements and treating hazardous mining wastewater. It highlights the advantages of these composites over existing technologies, including faster capture kinetics and increased stability. Additionally, it details various chemical processes and analyses performed to evaluate the performance of these composites in metal recovery applications.

1. Synthetic Development of Novel Silica Polyamine Composites
and Reclamation of Hazardous Mining Wastewater

2. Acknowledgments

3. Acknowledgments
Dr. Ed Rosenberg
Dr. Bob Fischer Joel Clancey
Carolyn Hart Jeff McKenzie
Rosenberg Research Group
Pacific Northwest National Laboratory
Purity Systems, Inc.
Montana Board of Research &
Commercialization Technology
Department of Energy

4. Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery

5. Advantages Over Competing Technologies
• Faster capture kinetics
• Lower back-pressures
Crosslinked Polystyrene
• No shrink/swell upon load/strip cycles
• Longer material lifetimes
• Higher metal capacities
• More stable to radiolytic decomposition
Self-Assembled Monolayers
on Mesoporous Supports
Crick, D.W.; Alexandratos, S.D. Magn. Reson. Chem. 1994, 32, S40-S44.
Fryxell, G.E.; Lin, Y.; Fiskum, S.; Birnbaum, J.C.; Wu, H. Environ. Sci. Technol. 2005, 39, 1324-1331.

6. Silica Gels
Supplier Diameter Pore Diameter Pore Volume Porosity Surface Area
µm Å mL/g % m2/g
Crosfield 90 - 105 267 2.82 84.7 422
Qingdao Haiyang 150 - 250 194 2.39 85.0 493
Qingdao Meigao 180 - 250 378 2.86 85.3 303
Nanjing 180 - 250 164 2.30 85.8 561
Nanjing Tianyi 80 - 250 150 2.28 85.6 526

7. Synthesis of Silica Polyamine Composite
O
H H
- +
O Na OH OH
H
OH OH O
1. Acid Wash OH
2. Dry Humidify H
- +
O Na OH OH
H
O
- + H
O Na OH OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
Hydration of Crosfield Silica Gel
7 1.4
6 1.2
5 1.0
H2O : Si-OH
% H2O (m/m)
4 % H2O 0.8
H2O : Si-OH
3 0.6
3 Foot Column:
2 Top Foot: 6.1% 0.4
Middle Foot: 6.3%
1 Bottom Foot: 6.1% 0.2
0 0.0
0 40 80 120 160 200
Hydration Time (hr)

8. Synthesis of Silica Polyamine Composite
O
H H
- +
O Na OH OH
H
OH OH O
1. Acid Wash OH
2. Dry Humidify H Cl3Si(CH2)3Cl
- +
O Na OH OH
H
O
- + H
O Na OH OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
O
Si Cl
O
O
Si Cl
O
O
Si Cl
O
O
Si Cl
O
O
(d) Lateral Polymerization

9. Synthesis of Silica Polyamine Composite
O
H H
- +
O Na OH OH
H
OH OH O
1. Acid Wash OH
2. Dry Humidify H Cl3Si(CH2)3Cl
- +
O Na OH OH
H
O
- + H
O Na OH OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
P N
O O
Si N N Si Cl
O O
O O
Si N Poly(allylamine) Si Cl
O O
O O
Si N Si Cl
O N O
O O
N N
Si N Si Cl
O O
O O
P
(e) Silica-Polyamine Composite (d) Lateral Polymerization

10. Synthesis of Silica Polyamine Composite
O
H H
- +
O Na OH OH
H
OH OH O
1. Acid Wash OH
2. Dry Humidify H Cl3Si(CH2)3Cl
- +
O Na OH OH
H
O
H
O- Na+ OH OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
H H
P
N H
N
O O
Si Si Cl
O N O
O N O
Si H Si Cl
Poly(ethyleneimine) O
O N
O N O
Si Si Cl
O N O
O H O
N
Si N Si Cl
O N H O
O O
P

11. Ligand Modification
HO
HO O O
HO N
O O
HO
O N
H N
N O H
N HO
O
O O
O OMe
O OMe P
O OH OH P
P P OR OMe
H OH H
H H
N N N R = H/Me (1.2:1) H
(2.5:1) N

12. Anhydride Synthesis
OH
O O O N
NH2 HO O
O O HO HO
DMSO, 75 C, 24 hr. O N
+ N N
O N N O H
Triethylamine N HO
n O excess O O
n
HO
O
NH2 O
O O THF, reflux, 24 hr.
+ H
N O
excess
n
n

13. Composite Characterization
• Mass/density gains
• Elemental analysis (Schwartzkopf Microanalytical Laboratory)
• Solid state NMR (Pacific Northwest National Laboratory)

14. Variable Amplitude - Cross Polarization Magic Angle Spinning
Variable Amplitude of Contact Time – Used to accommodate for the
variable spin temperatures of each carbon type (& orientation).
Cross Polarization – Enhances the sensitivity by using the large
proton magnetization to polarize 13C.
Magic Angle Spinning (54.7 1º) – Eliminates the peak broadening
caused by chemical shift anisotropy (CSA).
Proton Decoupling – Removes the proton dipolar broadening.
Schafer and Stejskal (1976)

15. Composite Performance Testing
• Batch Capacity pH Profile
• Breakthrough Performance

16. Composite Performance Testing
• Batch Capacity pH Profile
BPAP-CF 041504-DN
80
70 Fe(III)
60 Eu(III)
v ( [c] - [e] )
Metal Capacity (mg/g)
C =
m 50
40
C = composite metal capacity (mg/g)
30
v = volume challenge solution (L)
c = conc. challenge solution (mg/L) 20
e = conc. extraction solution (mg/L)
m = mass of composite (g) 10
0
-2 -1 0 1 2 3 4 5 6
pH (H2SO4)

17. Composite Performance Testing
• Batch Capacity pH Profile
BPAP-CF 041504-DN
1.40
1.20 Fe(III)
Metal Capacity (mmol/g)
v ( [c] - [e] ) 1.00 Eu(III)
C =
m
0.80
C = composite metal capacity (mg/g) 0.60
v = volume challenge solution (L)
c = conc. challenge solution (mg/L) 0.40
e = conc. extraction solution (mg/L)
m = mass of composite (g) 0.20
0.00
-2 -1 0 1 2 3 4 5 6
pH (H2SO4)

18. Composite Performance Testing
• Breakthrough Performance
BPAP-CF 041504-DN Precision Study
0.50 CV/min., Feed pH 1.0, Eu(III) FT Capacity 50 ± 2 mg/g
3000
10
2500
Ave.
2000
Eu(III) mg/L
1500
5
Pump
1000
500
0
100
0 5 10 15 20
Column Volume (CV = 5.0 mL)

19. Composite Performance Testing
• Breakthrough Performance
BPAP-CF 041504-DN Precision Study
0.50 CV/min., Feed pH 1.0, Eu(III) FT Capacity 50 ± 2 mg/g
3000
10
2500 BT#1
BT#2
2000 BT#3
Eu(III) mg/L
1500
5
Pump
1000
500
0
100
0 5 10 15 20
Column Volume (CV = 5.0 mL)

20. Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery

21. Mixed Silane Gels
H A B C D
O
H O O O
O
OH Si Cl Si Cl Si Si
H O O O O
O O O O
Cl3SiCH3
O Si
OH + Si Cl Si Si Cl
H O O O O
O O O O
Cl3Si(CH2)3Cl
OH Si Cl Si Cl Si Si
H O O O O
O O O O O
H
OH Si Cl Si Si Si
O O O O
O O O O
OH H Si Cl Si Cl Si Cl Si
O O O O O
O O O O
H
CPTCS (66:33) 58:42 (33:66) 28:72 MTCS

22. Mixed Silane Gels
H A B C D
O
H O O O
O
OH Si Cl Si Cl Si Si
H O O O O
O O O O
Cl3SiCH3
O Si
OH + Si Cl Si Si Cl
H O O O O
O O O O
Cl3Si(CH2)3Cl
OH Si Cl Si Cl Si Si
H O O O O
O O O O O
H
OH Si Cl Si Si Si
O O O O
O O O O
OH H Si Cl Si Cl Si Cl Si
O O O O O
O O O O
H
CPTCS (66:33) 58:42 (33:66) 28:72 MTCS
O
Si Cl
O
O Gel Silane O3SiR O2Si(OH)R OSi(OH)2R
Si Cl Coverage
O (umol/m2) (%) (%) (%)
OH
A 4.6 28 59 13
OH B 5.3 30 56 14
OH
C 5.8 - - -
Si Cl
O D 6.6 48 44 7.3
OH
OH
OH

23. Mixed Silane Gels
H A B C D
O
H O O O
O
OH Si Cl Si Cl Si Si
H O O O O
O O O O
Cl3SiCH3
O Si
OH + Si Cl Si Si Cl
H O O O O
O O O O
Cl3Si(CH2)3Cl
OH Si Cl Si Cl Si Si
H O O O O
O O O O O
H
OH Si Cl Si Si Si
O O O O
O O O O
OH H Si Cl Si Cl Si Cl Si
O O O O O
O O O O
H
BPAP-QH (Mixed Anchor Study)
CPTCS BPAP-QH (Mixed Anchor Study)
(66:33) 58:42 (33:66) 28:72 MTCS
3000 4500
BPAP-QH 041104-DN A 4000
2500 BPAP-QH 041404-DN B BPAP-QH 041104-DN A
BPAP-QH 042004-DN C 3500 BPAP-QH 041404-DN B
BPAP-QH 042004-DN C
2000 3000
Fe(III) mg/L
Fe(III) mg/L
2500
1500
2000
1000 1500
1000
500
500
0 0
0 2 4 6 8 10 12 14 16 18 20 0 1 2 3 4 5 6 7 8 9 10
Column Volume (CV = 5.0 mL) Column Volume (CV = 5.0 mL)

24. Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery

25. Chloromethylphosphonic Dichloride Pathway
O 4 hrs. neat O
O NH2
Cl ambient
Cl P + HO Cl P +
Cl O
n
O O THF
P OH 6 M HCl (0.5% DMSO)
P O
6 hrs. reflux, 24 hrs.
H OH H O
N N
n n
Elemental analysis: N*/P = 10
Boduszek, B. Phosphorus, Sulfur, and Silicon 1996, 113, 209-218.

26. Chloromethylphosphonic Dichloride Pathway
P N
O
Si N N
O
O
Si N
O
O
Si N N
O
O
N N
Si N
O
O
P
Elemental analysis: N*/P = 10

27. Michaelis-Arbuzov Rearrangement
O ice bath O NH2
P 1 hr. OMe
MeO OMe + Cl P
Cl +
OMe Cl OMe
O
n
O O
O OH O OMe
P Br P CH3OH
OH Si OMe pH 9 (NaOH)
Me
Me Me 80 C, 24 hrs.
H H
N N
dry C2H3N
n n
Elemental analysis: N*/P = 5.9
Bhattacharya, A.K.; Thyagarajan, G. Chemical Reviews, 1981, 81, 415-430.

28. Michaelis-Arbuzov Rearrangement
o
150 C
O
P 45 min.
Br Br + MeO OMe Br P OMe
OMe 15 mmHg
o OMe
4 eq. eq. 65 C
Dimethyl(3-bromopropyl)phosphonate
Maguire, A.R. et al. Bioorg. Med. Chem. 2001, 9, 745-762.

29. Michaelis-Arbuzov Rearrangement
1H e/f
1H a c
O
Br dP OMe
b
OMe f
e
a
b/c b/c
ppm (t1) 3.50 3.00 2.50 2.00 1.50
b a d
e/f c
13C 31P
ppm (t1) 50 40 30 20 10 ppm (t1) 35.0 30.0
Maguire, A.R. et al. Bioorg. Med. Chem. 2001, 9, 745-762.

30. Phosphonate Composite (BP-6)
o
O
O NH2 60 C H P
pH 9 (NaOH) N OMe
Br P OMe +
24 hrs. OR
OMe
n R = H/Me (1.9:1)
n
Elemental analysis: N*/P = 1.5

31. Phosphonate Composite (BP-7)
O
O NH2 o
60 C H P OMe
TEA, EtOH N
Br P OMe + OR
22 hrs.
OMe
R = H/Me (1:1.5)
n
n
Elemental analysis: N*/P = 1.7

32. The Mannich Reaction (Acid Catalyzed)
HCl Activated BP-1
H H
N
P H
H O OH
.. + H+
..
N + C N
P H H H P H - H2O
O ..
+
P OH -H + P OH H  H
OH HO + N C
N OH P H
P H
O
BPAP
P
HO H
HO
Smith, M.B. and March, J., March’s Advanced Organic Chemistry, 5th ed. 2001, 1189-1190.
Blicke, F.F., The Mannich Reaction, Organic Reactions, Chapter 10, 1942, 303-341.

33. Phosphonic Acid Composite (BPAP)
HCl Activated BP-1
H H
N
OH H P P H
HO
P N O OH
O P
OH
O H O OH
OH .. + H+
O
..
Si N N N + C N
P OH P H
H H H P H - H2O
O H O
O
Si N O
O ..
OH +
 H
O P OH -H + P OH H
P OH HO + N C
N OH OH
P N P H
H P H
O
BPAP
P
HO H
HO
Elemental analysis: N*/P = 0.75
Smith, M.B. and March, J., March’s Advanced Organic Chemistry, 5th ed. 2001, 1189-1190.
Blicke, F.F., The Mannich Reaction, Organic Reactions, Chapter 10, 1942, 303-341.

34. BPAP 1H - 31P HETCOR NMR
OH H P
HO
P N
HO OH
O
P O
O HO O
O
Si N N P OH
H
O
O H NH(CH2P(O)(OH)2)
Si N
O OH
O
P OH
N
P
H
N((CH2P(O)(OH)2)2
1H
(ppm)
31P
CH2
NH
31P
Crick, D.W.; Alexandratos, S.D. Magn. Reson. Chem. 1994, 32, S40-S44.

35. Phosphinic Acid Composite (BP-5)
O OH
NH2 P
2.0 N HCl, reflux, 20 hr. H
+ CH2O + H3PO2 H
N
excess excess
n
n
Elemental analysis: N*/P = 0.58
Varga, T.R. Synthetic Communications 1997, 27, 2899-2903.

37. BPAP-QH 121403-DN BT#'s 1, 2, 10, 20 & 30 BPAP-QH 121403-DN Strip Profile of BT#'s 1, 2, 10, 20 & 30
3.1 g/L Fe(III), pH 1.5, 0.32 CV/min. at 33 psi (2.2 bar) 9 N H2SO4 (25%), 0.42 slowing to 0.27 CV/min. at 70 psi (4.7 bar)
4000 4000
BT#1
3500 3500
BT#2
SP#1
3000 BT#10 3000
SP#2
BT#20
2500 2500 SP#10
Fe(III) mg/L
Fe(III) mg/L
BT#30 SP#20
2000 2000
SP#30
1500 1500
1000 1000
500 500
0 0
0 2 4 6 8 10 12 14 16 0 1 2 3 4 5 6
Column Volume (CV = 490 mL) Column Volume (CV = 490 mL)
BPAP-QH 121403-DN Pilot Scale Cycle Testing Results
50
45
40 Flowthrough Capacity
35 Strip Capacity
Capcity (g/kg)
30
25
20
15
10
5
0
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Cycle Number

38. Fe3+ Removal – Copper Electrowinning Solutions
BPAP-CF 041504-DN
0.050 CV/min., 1.5 M EDTA (pH 10.6), 5.0 M H3PO3, 5.0 M H3PO4
7000
6000 1.5 M EDTA (99% stripped)
5.0 M H3PO3 (94% stripped)
5000
5.0 M H3PO4 (78% stripped)
Fe(III) mg/L
4000
3000
2000
1000
0
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10

39. Fe3+ Removal – Copper Electrowinning Solutions
BPAP-CF 041504-DN
0.50 CV/min., Feed Solution = 4 N H2SO4, 30 mg/g Fe(III) Capacity
600 12000
500 10000
400 8000
Cu(II) mg/L
Fe(III) mg/L
300 6000
Fe(III) #1 Feed = 407 mg/L
200 Fe(III) #2 Feed = 407 mg/L 4000
Cu(II) #1 Feed = 10.3 g/L
100 2000
Cu(II) #2 Feed = 10.3 g/L
0 0 BPAP-CF 041504-DN
0 10 20 30 40 50 60 70 80 90 0.050 CV/min., 1.5 M EDTA pH 10.6, 99% Stripped
Column Volume (CV = 5.0 mL) 7000
6000
Fe(III) #1 (30 mg/g)
OH H P
HO 5000 Fe(III) #2 (30 mg/g)
P N O OH
Fe(III) mg/L
O P
OH
4000
O OH
O
Si N N P OH
H 3000
O H O
O
Si N
O OH 2000
O
P OH
N
P
1000
H
0
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10 S-11-12 S-13-14

40. Fe3+ Removal – Copper Electrowinning Solutions
BPAP-CF 041504-DN
0.50 CV/min., Feed Solution = 4 N H2SO4, 30 mg/g Fe(III) Capacity
600 12000
500 10000
400 8000
10 mL + 50 mL 3 M H2SO4
Cu(II) mg/L
Fe(III) mg/L
300 6000 93% Fe3+ Recovery
Fe(III) #1 Feed = 407 mg/L
200 Fe(III) #2 Feed = 407 mg/L 4000 87% EDTA Recovery
Cu(II) #1 Feed = 10.3 g/L
100 2000
Cu(II) #2 Feed = 10.3 g/L
0 0 BPAP-CF 041504-DN
0 10 20 30 40 50 60 70 80 90 0.050 CV/min., 1.5 M EDTA pH 10.6, 99% Stripped
Column Volume (CV = 5.0 mL) 7000
6000
Fe(III) #1 (30 mg/g)
OH H P
HO 5000 Fe(III) #2 (30 mg/g)
P N O OH
Fe(III) mg/L
O P
OH
4000
O OH
O
Si N N P OH
H 3000
O H O
O
Si N
O OH 2000
O
P OH
N
P
1000
H
0
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10 S-11-12 S-13-14

41. Phosphorous Based Ligand Composites (Ga3+) Ga(III) Batch Testing
60
pH 1.0 (HNO3)
50
pH 2.1 (HNO3)
40
Ga(III) mg/g
30
20
10
0
BPAP BP-5 BP-6 BP-7
BPAP-CF 041504-DN Breakthrough Curve BPAP-CF 041504-DN Breakthrough Curve
0.50 CV/min., pH 1.0 0.50 CV/min., 1 M EDTA pH 10.5, 92% Ga(III) Purity
2500 6000
Ga(III) 25 mg/g
5000
2000 Al(III) 2 mg/g
Metal Conc. (mg/L)
4000
Metal Conc. (mg/L)
1500
Ga(III) Feed = 2,140 mg/L
3000
Al(III) Feed = 1,840 mg/L
1000
2000
500
1000
0
0
0 5 10 15 20 25 30
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Column Volume (CV = 5.0 mL)

42. Th4+ Batch Capacity Testing
Th(IV) Batch Capacities
160
BPAP
140
BP-5
120 BPSU
Th(IV) Capacity (mg/g)
100 BP-1
WP-2
80
WP-4
60
BP-7
40
BP-6
20
0
0 1 2 3
pH (HNO3)

43. Th4+ Breakthrough Testing
Breakthrough Curves 0.50 CV/min., Feed pH 2.9
4500
4000
3500
Th(IV) Conc. (mg/L)
3000
BPAP 131 mg/g
2500 BP-5 123 mg/g
2000 BPSU 117 mg/g
1500 BP-7 68 mg/g
1000
500
0
0 5 10 15 20 25 30 35 40 45 Strip Profiles at 0.20 CV/min. using 2 M H3PO3 Strip Solution
Column Volume (CV = 5.0 mL) 30000
25000 BPSU (99% Stripped)
BP-7 (34% Stripped)
20000
Th(IV) mg/L
BPAP (7% Stripped)
15000 BP-5 (3% Stripped)
10000
5000
0
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10

44. Phosphonic/Phosphinic Acid Composites
O OH O OH
P P
H OH H H
N N
n n
Phosphonic Acid Phosphinic Acid
(BPAP) (BP-5)
• Very low affinity towards divalent metals such as Cu2+
• High affinity towards metals in the 3+ and 4+ oxidation states:
Fe3+, Ga3+, Al3+, Ln3+, Th4+, Zr4+ (In3+, Co3+, UO22+)
• Strip 3+ metals using either H3PO3 or EDTA (pH 10.5)
• Does not strip well using H2SO4, HCl, HNO3; Fe3+ sulfite redox strip
solutions do not work

45. Phosphonate Composites
O O
H P H P
N OMe OMe
N
OR OR
R = H/Me (2.5:1) R = H/Me (1.2:1)
n n
BP-6 BP-7
• Moderate (Ga3+) to very low (Eu3+) affinity towards 3+ metals
• Moderate affinity towards metals in the 4+ oxidation state (Th4+)
• Possibly strip metal using 1 M EDTA (pH 10.5)
• Does not strip well using 2 M H3PO3
• Difficulties obtaining the diester due to hydrolysis

46. Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery

47. Rare Earth Element (REE) Sulfuric Acid Leach Solution
Western Australia
Rare Earth Element Purification
87% to 99% Ln(III) Purity [ <1% Al(III), <<1% Ca(II), Fe(III), Ti(IV)]
6000
5000
REE Feed (50%)
4000 WP-4 Flowthrough
Metal Conc. (mg/L)
BPAP Recovery Sol.
3000
2000
1000
0
Ce(III) La(III) Nd(III) Sm(III) Pr(III) Fe(III) Mn(II) Ca(II) Mg(II) Al(III) Zn(II) Ti(IV)

48. WP-4-CF 101205-DN Breakthough Curve
0.50 CV/min., Feed pH 1.30
1200
BT #1
1000
BT #2
Fe(III) Conc. (mg/L)
800
600
400
200
0
0 5 10 15 20 25
Column Volume (CV = 12.0 mL) WP-4-CF 101205-DN Strip Profile
0.50 CV/min., 9 N H2SO4, 26 mg/g Strip Capacity, 100% Stripped
16000
H H P 14000
N SP #1
N 12000
SP #2
Fe(III) Conc. (mg/L)
O OH
O 10000
Si N N
H H
O 8000
O
Si N P
6000
O H
N 4000
H HO N
2000
0
S-1 S-2 S-3 S-4 S-5 S-6
Column Volume (CV = 12.0 mL)

49. WP-4-CF 101205-DN Breakthough Curve
0.50 CV/min., Feed pH 1.30
6000
5000
Ce(III)
La(III)
Fe(III) Conc. (mg/L)
4000
Nd(III)
Sm(III)
3000
Pr(III)
Fe(III)
2000
1000
0
0 5 10 15 20 25
Column Volume (CV = 12.0 mL) WP-4-CF 101205-DN Breakthough Curve
0.50 CV/min., Feed pH 1.30
350 1000
300 Mn(II)
H H P 800
N Ca(II)
N 250
Metal Conc. (mg/L)
Fe(III) Conc. (mg/L)
Mg(II)
O OH 600
O 200
Si N N Al(III)
H H
O
O 150
400 Zn(II)
Si N P
O H Ti(IV)
100
N 200 Fe(III)
H HO N 50
0 0
0 5 10 15 20 25
Column Volume (CV = 12.0 mL)

50. WP-4-CF 101205-DN Breakthough Curve
0.50 CV/min., Feed pH 1.30
6000
5000
Ce(III)
La(III)
Fe(III) Conc. (mg/L)
4000
Nd(III)
Sm(III)
3000
Pr(III)
Fe(III)
2000
1000
0
0 5 10 15 20 25
Column Volume (CV = 12.0 mL) WP-4-CF 101205-DN Strip Profile
0.50 CV/min., 9 N H2SO4, 25 mg/g Fe(III) Capacity
14000
12000 Fe(III)
H H P
N Ti(IV)
N 10000 Ce(III)
Metal Conc. (mg/L)
O Nd(III)
OH
O
Si N 8000 La(III)
N
H H
O
O
Si N 6000
P
O H
4000
N
H HO N
2000
0
S-1 S-2 S-3 S-4

51. BPAP-CF 041504-DN Breakthrough Curve #1
0.50 CV/min., Feed pH = 1.31
5000
4500
Ce(III)
4000
La(III)
3500
Nd(III)
Metal Conc. (mg/L)
3000 Sm(III)
2500 Pr(III)
2000 Ca(II)
1500 Mn(II)
1000 Al(III)
500
0
0 1 2 3 4 5 6 7 8
Column Volume (CV = 9.0 mL) BPAP-CF 041504-DN Strip Profile #1
0.50 CV/min., 2 M H3PO3, 59 mg/g Ln(III) Capacity,
99% Ln(III) Purity [< 1% Al(III), << 1% Ca(II), Fe(III), Ti(IV)]
4500
4000
OH H P
HO 3500 Ce(III)
P N O OH
O P La(III)
Metal Conc. (mg/L)
OH 3000
O OH
O Nd(III)
Si N N P OH 2500
H Sm(III)
O H O
O 2000 Pr(III)
Si N
O OH
O 1500 Al(III)
P OH
N
P
1000
H
500
0
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Column Volume (CV = 9.0 mL)

52. BPAP-CF 041504-DN Breakthrough Curve #2
0.50 CV/min., Feed pH = 1.31
5000
4500
Ce(III)
4000
La(III)
3500
Nd(III)
Metal Conc. (mg/L)
3000 Sm(III)
2500 Pr(III)
2000 Ca(II)
1500 Mn(II)
1000 Al(III)
500
0
0 1 2 3 4 5 6 7 8
Column Volume (CV = 9.0 mL) BPAP-CF 041504-DN Strip Profile #2
0.50 CV/min., 2 M H3PO3, 59 mg/g Ln(III) Capacity
99% Ln(III) Purity [< 1% Al(III), << 1% Ca(II), Fe(III), Ti(IV)]
4500
4000
OH H P
HO 3500 Ce(III)
P N O OH
O P La(III)
Metal Conc. (mg/L)
OH 3000
O OH
O Nd(III)
Si N N P OH 2500
H Sm(III)
O H O
O 2000 Pr(III)
Si N
O OH
O 1500 Al(III)
P OH
N
P
1000
H
500
0
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Column Volume (CV = 9.0 mL)

53. BPAP-CF 041504-DN Eu(III) Strip Profile Comparison
Various Strip Solutions (percent strip)
16000
14000 EDTA (100%)
H3PO3 (100%)
12000 H3PO4 (99%)
HNO3 (92%)
10000 H2SO4 (80%)
Eu(III) mg/L
HCl (39%)
8000
6000
4000
2000
0
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10

54. Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery

55. Empire Mill - 1888

56. Abandoned Hardrock Mines in the Western U.S.
The Berkeley Pit 1981 (top), & Lake 1999 (bottom)
Montana State’s High Priority Cleanup Sites

57. Depth Dissolved Species and Elements
(feet) SO4 Fe Zn Mg Ca Al Mn Cu Cd As
0 6345 270 378 430 512 195 179 86.8 1.84 <0.22
50 8994 892 578 538 494 281 212 145 2.39 0.34
500 9105 986 580 536 494 281 209 177 2.43 0.78

58. Depth Dissolved Species and Elements
(feet) SO4 Fe Zn Mg Ca Al Mn Cu Cd As
0 6345 270 378 430 512 195 179 86.8 1.84 <0.22
50 8994 892 578 538 494 281 212 145 2.39 0.34
500 9105 986 580 536 494 281 209 177 2.43 0.78

59. Cu(II) Zn(II) Mn(II)
Berkeley Pit (% purity) 5.0 18 6.0
Recovery (% purity) 97 99.98 83
Berkeley Pit (g/L) 0.17 0.58 0.21
Recovery (g/L) 10 6.5 9.0
pH Adjustment & Floculation Chamber
Mixer
- Raise pH to 5.2 (using base)
- Add ~0.1% (by volume) floculant
pH
Meter
C
u
Z Holding
Pump Settling n Tank M
Tank
n
Pump
Pump
Pump
Filter Press
Recycle Filtrate
Treated Solution
Berkeley Pit
Feed Reservoir Sludge toto Dump
Sludge Dump

60. CuWRAM-CF Breakthrough Curve
0.50 CV/min., pH 2.2, 32 mg/g FT capacity
700
600
Cu(II) Feed = 193 mg/L
Fe(III) Feed = 300 mg/L
500
Al(III) Feed = 253 mg/L
Metal Conc. (mg/L)
Zn(II) Feed = 602 mg/L
400
Mn(II) Feed = 172 mg/L
300
200
100
CuWRAM-CF Strip Fractions
0 0.50 CV/min., 9 N H 2 SO 4 , 97% Cu(II) Purity, 3% Fe(III)
0 50 100 150 200 250 300 350 400 12000
Column Volume (CV = 5.0 mL)
Cu(II) 32 mg/g
10000
Fe(III) 1 mg/g
H H P Al(III) 0 mg/g
Zn(II) 0 mg/g
N
Metal Conc. (mg/L)
8000
Mn(II) 0 mg/g
N
O H 6000
O
Si N P N
O H 4000
O
Si N Cu2+
O H N N 2000
H
0
1-2 3-4 5-6 7-8
Column Volume (CV = 5.0 mL)

61. NaOH pH Adjustment of Berkeley Pit Water
600
Zn
500 Fe
Al
Metal Conc. (mg/L)
400
Mn
300
200
100
0
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
pH

62. WP-2-CF Breakthrough Curve (4 CV 0.010 M NaOH to pH 1.9)
0.50 CV/min., pH 5.3, 26 mg/g Zn(II) FT Capacity
700
600
500
Metal Conc. (mg/L)
Zn(II) Feed = 620 mg/L
400
Mn(II) Feed = 248 mg/L
300
200
100
0
0 10 20 30 40 50 60 70
Column Volume (CV = 5.0 mL)
WP-2-CF Strip Fractions
0.50 CV/min., 9 N H2SO4, 99.98% Zn(II) Purity
10000
9000
O P
P
H 8000
HO N N Zn(II) 22 mg/g
7000
N O
Metal Conc. (mg/L)
Mn(II) 0 mg/g
HO 6000
O
O 5000
Si N O
O 4000
O N N OH
Si 3000
H H
O
2000
P
1000
0
1 2 3 4 5 6
Column Volume (CV = 5.0 mL)

63. BP-2-CF Breakthrough Curve
0.50 CV/min., pH 4.9, 23 mg/g FT capacity
800
700 Mn(II) Feed = 255 mg/L
Ca(II) Feed = 407 mg/L
600 Mg(II) Feed = 501 mg/L
Metal Conc. (mg/L)
500
400
300
200
100
0
0 10 20 30 40 50 60 70 80 90 100
Column Volume (CV = 5.0 mL) BP-2-CF Strip Fractions
0.50 CV/min., 9 N H2SO4, 83% Mn(II) Purity
H 10000
P O
N Mn(II) 30 mg/g
-
O Metal Conc. (mg/L) 8000 Ca(II) 4 mg/g
O Mg(II) 2 mg/g
O O
Si N 6000
H -
O O
O N
Si N
4000
O H H
H
O
2000
N
-
P O
0
1 2 3 4 5 6
Column Volume (CV = 5.0 mL)

64. Proposed large-scale columns = 10,000 L
Flow rate per unit (3 columns) = 5,000 L/min
Flow rate of water to be treated = 11,000 L/min
Units required = 2.2
Cu cap. CuWRAM = 0.55 mmol/g
Cu cap. CuWRAM = 35 mg/g
density CuWRAM = 0.69 g/mL
mass CuWRAM/column = 6.9E+06 g
Cu cap./column = 2.4E+08 mg
[Cu] in BP H2O = 175 mg/L
Cap. BP H2O/column = 1.4E+06 L
Zn cap. WP-2 = 0.38 mmol/g
Zn cap. WP-2 = 25 mg/g
density WP-2 = 0.64 g/mL
mass WP-2/column = 6.4E+06 g
Zn cap./column = 1.6E+08 mg
[Zn] in BP H2O = 575 mg/L
Cap. BP H2O/column = 2.8E+05 L
Rotate CuWRAM column every = 2.8E+02 min
Rotate WP-2 column every = 5.6E+01 min
Cu mass gain as CuSO4 · 5H2O = 393 %
Zn mass gain as ZnSO4 · 7H2O = 440 %
Cu from each strip = 9.5E+02 kg
Zn from each strip = 7.1E+02 kg
Cu recovered per day = 1.1E+01 mt
Zn recovered per day = 4.0E+01 mt
CuSO4 · 5H2O market price = 590 US$/mt
ZnSO4 · 7H2O market price = 180 US$/mt
Gross profit from copper/day = 6.4E+03 US$
Gross profit from zinc/day = 7.2E+03 US$
Total gross profit/day = 1.4E+04 US$
Total gross profit/year = 5.0E+06 US$

65. Conclusions
• BPAP and BP-5 show very high capacities towards 3+/4+ metals,
even from highly acidic media
• BPAP exhibits greater metal capacity than BP-5
• BPAP and BP-5 have an extremely low affinity towards divalent
metals such as Cu2+
• Phosphonate ligands show moderate affinity towards metals in
the 4+ oxidation state
• Phosphorous acid and EDTA can strip 3+ metals from BPAP
• Cu2+, Zn2+ and Mn2+ can be separated from acid mine drainage
• REEs can be separated from an authentic acid leach solution
• Actinides can be sequestered using BPAP with extremely high
formation constants

66. Future Directions
• BPAP and BP-5
– BP-5 studies with Eu3+ using H3PO3 and EDTA
– Copper electrowinning applications
– Arsenic and selenium extraction (BPAP-Zr4+)
– Investigate stripping Th4+ using EDTA
– BPAP has been used for biochemistry applications to selectively
remove Fe(III) from bacterial (Sulfolobus solfataricus) growth
media
Wiedenheft, B.; Willits, D.; Mosolf, J.; Yeager, M.; Dryden, K.; Young, M.; Douglas, T.
Proceedings of the National Academy of Sciences 2005, 102(30), 10551-10556

67. Future Directions
Phosphonates
– Does not appear to offer increased stripping kinetics
– Diesters may not be stable under strong acid or base
regeneration
– May try carboxylate activation using carbonyl diimidazole (CDI)
coupled with a primary amine
Fryxell, G.E.; Wu, H.; Lin, Y.; Shaw, W.J.; Birnbaum, J.C., Linehan, J.C.; Nie, Z.;
Kemer, K.; Kelly, S. J. Mater. Chem. 2004, 14, 3356-3363

68. Future Directions
Mixed Anchor Studies
– Increase the ratio of MTCS:CPTCS
– Investigate capacity and kinetic improvements on composites
such as CuWRAM and WP-4
– Possibly try propyltrichlorosilane
(longevity testing using EDTA strip)

69. Future Directions
Mixed Anchor Studies
– Increase the ratio of MTCS:CPTCS
– Investigate capacity and kinetic improvements on composites
such as CuWRAM and WP-4
– Possibly try propyltrichlorosilane
(longevity testing using EDTA strip)
H H
O P O P
N H N H
Si Si
O O
O O
Si N Si N
O O
O H O H
H H
Si N Si N
O O
O H O H
Si N Si N
O H O H
O H O H
N N
Si Si
O H O H
O O
P P

70. Synthetic Development of Novel Silica Polyamine Composites
and Reclamation of Hazardous Mining Wastewater