umt presentation
DESCRIPTION
Presentation summary of research conducted in partial fulfillment of PhD in chemistry at the University of Montana.TRANSCRIPT
Synthetic Development of Novel Silica Polyamine Composites
and Reclamation of Hazardous Mining Wastewater
Acknowledgments
Acknowledgments
Dr. Bob Fischer
Carolyn Hart
Dr. Ed Rosenberg
Joel Clancey
Jeff McKenzie
Rosenberg Research Group
Pacific Northwest National Laboratory
Purity Systems, Inc.
Montana Board of Research & Commercialization Technology
Department of Energy
Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery
Advantages Over Competing Technologies
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.
Crosslinked Polystyrene
Self-Assembled Monolayers
on Mesoporous Supports
• Faster capture kinetics
• Lower back-pressures
• No shrink/swell upon load/strip cycles
• Longer material lifetimes
• Higher metal capacities
• More stable to radiolytic decomposition
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
Synthesis of Silica Polyamine Composite
O- Na
+
O- Na
+
OH
O- Na
+
OH
OH
OH
OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
1. Acid Wash2. Dry Humidify
OHO
H
H
OH
OH H
OH
H
OH
OH
Hydration of Crosfield Silica Gel
0
1
2
3
4
5
6
7
0 40 80 120 160 200
Hydration Time (hr)
% H
2O
(m
/m)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
H2O
: S
i-O
H
% H2O
H2O : Si-OH
3 Foot Column:
Top Foot: 6.1%
Middle Foot: 6.3%
Bottom Foot: 6.1%
O- Na
+
O- Na
+
OH
O- Na
+
OH
OH
OH
OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
1. Acid Wash2. Dry Humidify
OHO
H
H
OH
OH H
OH
H
OH
OH
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Cl
Cl
Cl3Si(CH2)3Cl
(d) Lateral Polymerization
Synthesis of Silica Polyamine Composite
Synthesis of Silica Polyamine Composite
O- Na
+
O- Na
+
OH
O- Na
+
OH
OH
OH
OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
1. Acid Wash2. Dry Humidify
OHO
H
H
OH
OH H
OH
H
OH
OH
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Cl
Cl
Cl3Si(CH2)3Cl
Poly(allylamine)
(e) Silica-Polyamine Composite (d) Lateral Polymerization
N
N N
OSi N
O
O
Si
Si
O
O
Si
O
O
O
O
N
N
N
N
N
P
P
Synthesis of Silica Polyamine Composite
O- Na
+
O- Na
+
OH
O- Na
+
OH
OH
OH
OH
(a) Raw Silica Surface (b) Cleaned Silica Surface (c) Hydrated Silica Surface
1. Acid Wash2. Dry Humidify
OHO
H
H
OH
OH H
OH
H
OH
OH
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Cl
Cl
Cl3Si(CH2)3Cl
Poly(ethyleneimine)
P
P
N
N
N
NH
H
N
N
N
N
OSi
O
O
Si
Si
O
O
Si
O
O
O
O N
H
N
H H
H
Ligand Modification
NH
POHO
H
NH
POHO
OH
NH
OP
OOMe
OMe
R = H/Me (1.2:1) (2.5:1)
NH
P OMe
OR
O
NH
O
O HO
NH
ON
OHO
N
HO
O
NO
HO
HO
O
excess
+
NH2
n
NN
O
HO
N O
O
O
O
O
O
DMSO, 75 C, 24 hr.
Triethylamine
NH
O N
O
HO
N
HO
O
NO
HO
OH
O
n
Anhydride Synthesis
excess
+
NH2
n
THF, reflux, 24 hr.O
OO
NH
O
O HO
n
• Mass/density gains
• Elemental analysis (Schwartzkopf Microanalytical Laboratory)
• Solid state NMR (Pacific Northwest National Laboratory)
Composite Characterization
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.
Variable Amplitude - Cross Polarization Magic Angle Spinning
Schafer and Stejskal (1976)
• Batch Capacity pH Profile
• Breakthrough Performance
Composite Performance Testing
• Batch Capacity pH Profile
Composite Performance Testing
C = v ( [c] - [e] )
m
C = composite metal capacity (mg/g) v = volume challenge solution (L) c = conc. challenge solution (mg/L)e = conc. extraction solution (mg/L)m = mass of composite (g)
BPAP-CF 041504-DN
0
10
20
30
40
50
60
70
80
-2 -1 0 1 2 3 4 5 6
pH (H2SO4)
Me
tal C
ap
ac
ity
(m
g/g
)
Fe(III)
Eu(III)
• Batch Capacity pH Profile
Composite Performance Testing
C = v ( [c] - [e] )
m
C = composite metal capacity (mg/g) v = volume challenge solution (L) c = conc. challenge solution (mg/L)e = conc. extraction solution (mg/L)m = mass of composite (g)
BPAP-CF 041504-DN
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
-2 -1 0 1 2 3 4 5 6
pH (H2SO4)
Meta
l C
ap
acit
y (
mm
ol/
g)
Fe(III)
Eu(III)
• Breakthrough Performance
Composite Performance Testing
Pump5
10
100
BPAP-CF 041504-DN Precision Study
0.50 CV/min., Feed pH 1.0, Eu(III) FT Capacity 50 ± 2 mg/g
0
500
1000
1500
2000
2500
3000
0 5 10 15 20
Column Volume (CV = 5.0 mL)
Eu
(III)
mg
/L
Ave.
Composite Performance Testing
BPAP-CF 041504-DN Precision Study
0.50 CV/min., Feed pH 1.0, Eu(III) FT Capacity 50 ± 2 mg/g
0
500
1000
1500
2000
2500
3000
0 5 10 15 20
Column Volume (CV = 5.0 mL)
Eu
(III)
mg
/LBT#1
BT#2
BT#3
Pump5
10
100
• Breakthrough Performance
Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery
Mixed Silane Gels
CPTCS (66:33) 58:42 (33:66) 28:72 MTCS
Cl3Si(CH2)3Cl
Cl3SiCH3
+
OH
OH
H
OHO
H
H
OH
H
OH
OH
OH
H
OH
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Si
OO
A B C D
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
Cl
Cl
Mixed Silane Gels
OSi Cl
O
OH
Si
O
OCl
Si
OH
OCl
OH
OH
OH
OH
Gel Silane O3SiR O2Si(OH)R OSi(OH)2R
Coverage
(umol/m2) (%) (%) (%)
A 4.6 28 59 13
B 5.3 30 56 14
C 5.8 - - -
D 6.6 48 44 7.3
CPTCS (66:33) 58:42 (33:66) 28:72 MTCS
Cl3Si(CH2)3Cl
Cl3SiCH3
+
OH
OH
H
OHO
H
H
OH
H
OH
OH
OH
H
OH
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Si
OO
A B C D
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
Cl
Cl
Mixed Silane Gels
CPTCS (66:33) 58:42 (33:66) 28:72 MTCS
Cl3Si(CH2)3Cl
Cl3SiCH3
+
OH
OH
H
OHO
H
H
OH
H
OH
OH
OH
H
OH
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Si
OO
A B C D
OSi Cl
O
O
Si
Si
O
O
Si
O
O
O
O
Cl
Si
OO
Cl
Cl
Cl
BPAP-QH (Mixed Anchor Study)
0
500
1000
1500
2000
2500
3000
0 2 4 6 8 10 12 14 16 18 20
Column Volume (CV = 5.0 mL)
Fe(I
II)
mg
/L
BPAP-QH 041104-DN A
BPAP-QH 041404-DN B
BPAP-QH 042004-DN C
BPAP-QH (Mixed Anchor Study)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0 1 2 3 4 5 6 7 8 9 10
Column Volume (CV = 5.0 mL)
Fe(I
II)
mg
/L
BPAP-QH 041104-DN A
BPAP-QH 041404-DN B
BPAP-QH 042004-DN C
Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery
Boduszek, B. Phosphorus, Sulfur, and Silicon 1996, 113, 209-218.
PCl
Cl
O
Cl HO+ PO
O
O
Cl +
NH2
n
n
6 M HCl 6 hrs.
O
NH
P
O
O
OH
NH
P
O
OH
n
THF (0.5% DMSO)
reflux, 24 hrs.
4 hrs. neatambient
Chloromethylphosphonic Dichloride Pathway
Elemental analysis: N*/P = 10
Chloromethylphosphonic Dichloride Pathway
N
N N
OSi N
O
O
Si
Si
O
O
Si
O
O
O
O
N
N
N
N
N
P
P
Elemental analysis: N*/P = 10
Bhattacharya, A.K.; Thyagarajan, G. Chemical Reviews, 1981, 81, 415-430.
MeOP
OMeOMe
+ POMe
OMe
O
OCl +
NH2
n
dry C2H3N
CH3OH
pH 9 (NaOH)80 C, 24 hrs.
Cl
O
Cl
ice bath1 hr.
Si
Br
MeMe
Me
NH
OP
OOH
OH
n n
NH
OP
OOMe
OMe
Michaelis-Arbuzov Rearrangement
Elemental analysis: N*/P = 5.9
Dimethyl(3-bromopropyl)phosphonate
Br P
O
OMe
OMe
OMe
P
MeOOMe
Br Br +
4 eq. eq.
150oC
45 min.
15 mmHg
65oC
Maguire, A.R. et al. Bioorg. Med. Chem. 2001, 9, 745-762.
Michaelis-Arbuzov Rearrangement
Michaelis-Arbuzov Rearrangement
ppm (t1) 30.035.0
31P
ppm (t1) 1.502.002.503.003.50
1H
ppm (t1) 1020304050
13C
1H
Br P
O
OMe
OMe
a
b
c
d
e
f
a
b/c
e/f
e/f b a
c
d
b/c
ppm (t1) 30.035.0
31P
ppm (t1) 1.502.002.503.003.50
1H
ppm (t1) 1020304050
13C
1H
Br P
O
OMe
OMe
a
b
c
d
e
f
a
b/c
e/f
e/f b a
c
d
b/c
Maguire, A.R. et al. Bioorg. Med. Chem. 2001, 9, 745-762.
Phosphonate Composite (BP-6)
Br P
O
OMe
OMe
60oC
pH 9 (NaOH)24 hrs.
+
NH2
n R = H/Me (1.9:1)
NH P OMe
OR
O
n
Elemental analysis: N*/P = 1.5
Phosphonate Composite (BP-7)
Elemental analysis: N*/P = 1.7
Br P
O
OMe
OMe+
NH2
n
60oC
TEA, EtOH22 hrs.
R = H/Me (1:1.5)
NH P OMe
OR
O
n
The Mannich Reaction (Acid Catalyzed)
+
. .
. .
H
C
O
H
P
P
P
N
P
OOH
OH
H
- H+
+ H+
- H2O
N
H
C
H
H
+
PHO
HOH
O
P
OHHO OH
BPAP
N
H
OH
+
HCl Activated BP-1
PN
H
H
H
PN
H
H
. .
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.
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.
Elemental analysis: N*/P = 0.75
Phosphonic Acid Composite (BPAP)
+
. .
. .
H
C
O
H
P
P
P
N
P
OOH
OH
H
- H+
+ H+
- H2O
N
H
C
H
H
+
PHO
HOH
O
P
OHHO OH
BPAP
N
H
OH
+
HCl Activated BP-1
PN
H
H
H
PN
H
H
. .P
P
N
H
P
O
OH
OH
N
H
P
OHHO
N
OSi N
O
O
Si
H
O
OH
O
N
POH
OH
P
O
OH
OH
O
BPAP 1H - 31P HETCOR NMR
CH
2
NH
N((CH2P(O)(OH)2)2
NH(CH2P(O)(OH)2)
CH
2
NH
N((CH2P(O)(OH)2)2
NH(CH2P(O)(OH)2)
P
P
N
H
P
O
OH
OH
N
H
P
OHHO
N
OSi N
O
O
Si
H
O
OH
O
N
P
OH
P
O
OH
O
HO
HO
Crick, D.W.; Alexandratos, S.D. Magn. Reson. Chem. 1994, 32, S40-S44.
1H
(ppm)
31P
31P
Phosphinic Acid Composite (BP-5)
excess excess
+ CH2O + H3PO2
NH2
n
2.0 N HCl, reflux, 20 hr.
NH
POHO
H
n
Elemental analysis: N*/P = 0.58
Varga, T.R. Synthetic Communications 1997, 27, 2899-2903.
BPAP-QH 121403-DN Strip Profile of BT#'s 1, 2, 10, 20 & 309 N H2SO4 (25%), 0.42 slowing to 0.27 CV/min. at 70 psi (4.7 bar)
0
500
1000
1500
2000
2500
3000
3500
4000
0 1 2 3 4 5 6
Column Volume (CV = 490 mL)
Fe(I
II)
mg
/L
SP#1
SP#2
SP#10
SP#20
SP#30
BPAP-QH 121403-DN BT#'s 1, 2, 10, 20 & 303.1 g/L Fe(III), pH 1.5, 0.32 CV/min. at 33 psi (2.2 bar)
0
500
1000
1500
2000
2500
3000
3500
4000
0 2 4 6 8 10 12 14 16
Column Volume (CV = 490 mL)
Fe(I
II)
mg
/L
BT#1
BT#2
BT#10
BT#20
BT#30
BPAP-QH 121403-DN Pilot Scale Cycle Testing Results
0
5
10
15
20
25
30
35
40
45
50
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Cycle Number
Cap
cit
y (
g/k
g)
Flowthrough Capacity
Strip Capacity
Fe3+ Removal – Copper Electrowinning Solutions
BPAP-CF 041504-DN0.050 CV/min., 1.5 M EDTA (pH 10.6), 5.0 M H3PO3, 5.0 M H3PO4
0
1000
2000
3000
4000
5000
6000
7000
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Fe(I
II)
mg
/L
1.5 M EDTA (99% stripped)
5.0 M H3PO3 (94% stripped)
5.0 M H3PO4 (78% stripped)
Fe3+ Removal – Copper Electrowinning Solutions
BPAP-CF 041504-DN0.050 CV/min., 1.5 M EDTA pH 10.6, 99% Stripped
0
1000
2000
3000
4000
5000
6000
7000
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10 S-11-12 S-13-14
Fe(I
II)
mg
/LFe(III) #1 (30 mg/g)
Fe(III) #2 (30 mg/g)
BPAP-CF 041504-DN0.50 CV/min., Feed Solution = 4 N H2SO4, 30 mg/g Fe(III) Capacity
0
100
200
300
400
500
600
0 10 20 30 40 50 60 70 80 90
Column Volume (CV = 5.0 mL)
Fe(I
II)
mg
/L
0
2000
4000
6000
8000
10000
12000
Cu
(II)
mg
/L
Fe(III) #1 Feed = 407 mg/L
Fe(III) #2 Feed = 407 mg/L
Cu(II) #1 Feed = 10.3 g/L
Cu(II) #2 Feed = 10.3 g/L
P
P
N
H
P
O
OH
OH
N
H
P
OHHO
N
OSi N
O
O
Si
H
O
OH
O
N
POH
OH
P
O
OH
OH
O
Fe3+ Removal – Copper Electrowinning Solutions
BPAP-CF 041504-DN0.050 CV/min., 1.5 M EDTA pH 10.6, 99% Stripped
0
1000
2000
3000
4000
5000
6000
7000
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10 S-11-12 S-13-14
Fe(I
II)
mg
/LFe(III) #1 (30 mg/g)
Fe(III) #2 (30 mg/g)
BPAP-CF 041504-DN0.50 CV/min., Feed Solution = 4 N H2SO4, 30 mg/g Fe(III) Capacity
0
100
200
300
400
500
600
0 10 20 30 40 50 60 70 80 90
Column Volume (CV = 5.0 mL)
Fe(I
II)
mg
/L
0
2000
4000
6000
8000
10000
12000
Cu
(II)
mg
/L
Fe(III) #1 Feed = 407 mg/L
Fe(III) #2 Feed = 407 mg/L
Cu(II) #1 Feed = 10.3 g/L
Cu(II) #2 Feed = 10.3 g/L
P
P
N
H
P
O
OH
OH
N
H
P
OHHO
N
OSi N
O
O
Si
H
O
OH
O
N
POH
OH
P
O
OH
OH
O
93% Fe3+ Recovery
87% EDTA Recovery
10 mL + 50 mL 3 M H2SO4
BPAP-CF 041504-DN Breakthrough Curve0.50 CV/min., pH 1.0
0
500
1000
1500
2000
2500
0 5 10 15 20 25 30
Column Volume (CV = 5.0 mL)
Meta
l C
on
c. (m
g/L
)
Ga(III) Feed = 2,140 mg/L
Al(III) Feed = 1,840 mg/L
BPAP-CF 041504-DN Breakthrough Curve0.50 CV/min., 1 M EDTA pH 10.5, 92% Ga(III) Purity
0
1000
2000
3000
4000
5000
6000
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Meta
l C
on
c. (m
g/L
)
Ga(III) 25 mg/g
Al(III) 2 mg/g
Phosphorous Based Ligand Composites (Ga3+)Ga(III) Batch Testing
0
10
20
30
40
50
60
BPAP BP-5 BP-6 BP-7
Ga(I
II)
mg
/g
pH 1.0 (HNO3)
pH 2.1 (HNO3)
Th4+ Batch Capacity TestingTh(IV) Batch Capacities
0
20
40
60
80
100
120
140
160
0 1 2 3
pH (HNO3)
Th
(IV
) C
ap
acit
y (
mg
/g)
BPAP
BP-5
BPSU
BP-1
WP-2
WP-4
BP-7
BP-6
Th4+ Breakthrough Testing
Breakthrough Curves 0.50 CV/min., Feed pH 2.9
0
500
1000
1500
2000
2500
3000
3500
4000
4500
0 5 10 15 20 25 30 35 40 45
Column Volume (CV = 5.0 mL)
Th
(IV
) C
on
c.
(mg
/L)
BPAP 131 mg/g
BP-5 123 mg/g
BPSU 117 mg/g
BP-7 68 mg/g
Strip Profiles at 0.20 CV/min. using 2 M H3PO3 Strip Solution
0
5000
10000
15000
20000
25000
30000
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Th
(IV
) m
g/L
BPSU (99% Stripped)
BP-7 (34% Stripped)
BPAP (7% Stripped)
BP-5 (3% Stripped)
• 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
Phosphonic/Phosphinic Acid Composites
Phosphonic Acid Phosphinic Acid
NH
POHO
OH
n
NH
POHO
H
n
(BPAP) (BP-5)
• 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
Phosphonate Composites
R = H/Me (2.5:1)
NH P OMe
OR
O
n
BP-6 BP-7
R = H/Me (1.2:1)
NH P OMe
OR
O
n
Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery
Rare Earth Element (REE) Sulfuric Acid Leach SolutionWestern Australia
Rare Earth Element Purification87% to 99% Ln(III) Purity [ <1% Al(III), <<1% Ca(II), Fe(III), Ti(IV)]
0
1000
2000
3000
4000
5000
6000
Ce(III) La(III) Nd(III) Sm(III) Pr(III) Fe(III) Mn(II) Ca(II) Mg(II) Al(III) Zn(II) Ti(IV)
Meta
l C
on
c.
(mg
/L)
REE Feed (50%)
WP-4 Flowthrough
BPAP Recovery Sol.
WP-4-CF 101205-DN Breakthough Curve0.50 CV/min., Feed pH 1.30
0
200
400
600
800
1000
1200
0 5 10 15 20 25
Column Volume (CV = 12.0 mL)
Fe(I
II)
Co
nc.
(mg
/L)
BT #1
BT #2
WP-4-CF 101205-DN Strip Profile0.50 CV/min., 9 N H2SO4, 26 mg/g Strip Capacity, 100% Stripped
0
2000
4000
6000
8000
10000
12000
14000
16000
S-1 S-2 S-3 S-4 S-5 S-6
Column Volume (CV = 12.0 mL)
Fe(I
II)
Co
nc.
(mg
/L)
SP #1
SP #2
P
P
NH
N
H
N
H
N
OSi N
O
O
Si
H
O
O
H
H
N
OH
NHO
WP-4-CF 101205-DN Breakthough Curve0.50 CV/min., Feed pH 1.30
0
1000
2000
3000
4000
5000
6000
0 5 10 15 20 25
Column Volume (CV = 12.0 mL)
Fe(I
II)
Co
nc.
(mg
/L)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Fe(III)
WP-4-CF 101205-DN Breakthough Curve0.50 CV/min., Feed pH 1.30
0
50
100
150
200
250
300
350
0 5 10 15 20 25
Column Volume (CV = 12.0 mL)
Me
tal
Co
nc
. (m
g/L
)
0
200
400
600
800
1000
Fe
(III
) C
on
c.
(mg
/L)
Mn(II)
Ca(II)
Mg(II)
Al(III)
Zn(II)
Ti(IV)
Fe(III)
P
P
NH
N
H
N
H
N
OSi N
O
O
Si
H
O
O
H
H
N
OH
NHO
WP-4-CF 101205-DN Breakthough Curve0.50 CV/min., Feed pH 1.30
0
1000
2000
3000
4000
5000
6000
0 5 10 15 20 25
Column Volume (CV = 12.0 mL)
Fe(I
II)
Co
nc.
(mg
/L)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Fe(III)
WP-4-CF 101205-DN Strip Profile0.50 CV/min., 9 N H2SO4, 25 mg/g Fe(III) Capacity
0
2000
4000
6000
8000
10000
12000
14000
S-1 S-2 S-3 S-4
Me
tal
Co
nc
. (m
g/L
)Fe(III)
Ti(IV)
Ce(III)
Nd(III)
La(III)
P
P
NH
N
H
N
H
N
OSi N
O
O
Si
H
O
O
H
H
N
OH
NHO
BPAP-CF 041504-DN Breakthrough Curve #10.50 CV/min., Feed pH = 1.31
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
0 1 2 3 4 5 6 7 8
Column Volume (CV = 9.0 mL)
Me
tal
Co
nc
. (m
g/L
)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Ca(II)
Mn(II)
Al(III)
BPAP-CF 041504-DN Strip Profile #10.50 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)]
0
500
1000
1500
2000
2500
3000
3500
4000
4500
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Column Volume (CV = 9.0 mL)
Meta
l C
on
c. (m
g/L
)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Al(III)
P
P
N
H
P
O
OH
OH
N
H
P
OHHO
N
OSi N
O
O
Si
H
O
OH
O
N
POH
OH
P
O
OH
OH
O
BPAP-CF 041504-DN Breakthrough Curve #20.50 CV/min., Feed pH = 1.31
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
0 1 2 3 4 5 6 7 8
Column Volume (CV = 9.0 mL)
Me
tal
Co
nc
. (m
g/L
)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Ca(II)
Mn(II)
Al(III)
BPAP-CF 041504-DN Strip Profile #20.50 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)]
0
500
1000
1500
2000
2500
3000
3500
4000
4500
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Column Volume (CV = 9.0 mL)
Meta
l C
on
c. (m
g/L
)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Al(III)
P
P
N
H
P
O
OH
OH
N
H
P
OHHO
N
OSi N
O
O
Si
H
O
OH
O
N
POH
OH
P
O
OH
OH
O
BPAP-CF 041504-DN Eu(III) Strip Profile ComparisonVarious Strip Solutions (percent strip)
0
2000
4000
6000
8000
10000
12000
14000
16000
S-1-2 S-3-4 S-5-6 S-7-8 S-9-10
Eu
(III)
mg
/L
EDTA (100%)
H3PO3 (100%)
H3PO4 (99%)
HNO3 (92%)
H2SO4 (80%)
HCl (39%)
Outline
• Synthesis, Characterization, and Testing of Composites
• Mixed Silane Gel
• Phosphorous Based Ligand Composites
• Rare Earth Element Recovery
• Berkeley Pit Lake Metal Recovery
Empire Mill - 1888
Abandoned Hardrock Mines in the Western U.S.
Montana State’s High Priority Cleanup Sites
The Berkeley Pit 1981 (top), & Lake 1999 (bottom)
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
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
Pump
Berkeley Pit
Feed Reservoir
Treated Solution
pH
Meter
Settling
Tank
Mixer
Sludge to Dump
pH Adjustment & Floculation Chamber
- Raise pH to 5.2 (using base)
- Add ~0.1% (by volume) floculant
Recycle Filtrate Filter Press
Pump
Sludge to Dump
C
u
Z
nM
n
Pump
Pump
Holding
Tank
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
CuWRAM-CF Breakthrough Curve0.50 CV/min., pH 2.2, 32 mg/g FT capacity
0
100
200
300
400
500
600
700
0 50 100 150 200 250 300 350 400
Column Volume (CV = 5.0 mL)
Meta
l C
on
c. (m
g/L
)
Cu(II) Feed = 193 mg/L
Fe(III) Feed = 300 mg/L
Al(III) Feed = 253 mg/L
Zn(II) Feed = 602 mg/L
Mn(II) Feed = 172 mg/L
CuWRAM-CF Strip Fractions0.50 CV/min., 9 N H 2 SO 4 , 97% Cu(II) Purity, 3% Fe(III)
0
2000
4000
6000
8000
10000
12000
1-2 3-4 5-6 7-8
Column Volume (CV = 5.0 mL)
Meta
l C
on
c. (m
g/L
)
Cu(II) 32 mg/g
Fe(III) 1 mg/g
Al(III) 0 mg/g
Zn(II) 0 mg/g
Mn(II) 0 mg/g
Cu2+
P
P
N
H
N
H
N
OSi N
O
O
Si
H
O
O
H N
N
H
N
H
NaOH pH Adjustment of Berkeley Pit Water
0
100
200
300
400
500
600
2 2.5 3 3.5 4 4.5 5 5.5 6 6.5
pH
Meta
l C
on
c. (m
g/L
)
Zn
Fe
Al
Mn
WP-2-CF Strip Fractions0.50 CV/min., 9 N H2SO4, 99.98% Zn(II) Purity
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
10000
1 2 3 4 5 6
Column Volume (CV = 5.0 mL)
Meta
l C
on
c. (m
g/L
)Zn(II) 22 mg/g
Mn(II) 0 mg/g
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
0
100
200
300
400
500
600
700
0 10 20 30 40 50 60 70
Column Volume (CV = 5.0 mL)
Me
tal
Co
nc
. (m
g/L
)
Zn(II) Feed = 620 mg/L
Mn(II) Feed = 248 mg/L
P
P
O
OHNN
OSi N
O
O
Si
O
O
H
NNN
O
HO
H
H
O
HO
P
BP-2-CF Breakthrough Curve0.50 CV/min., pH 4.9, 23 mg/g FT capacity
0
100
200
300
400
500
600
700
800
0 10 20 30 40 50 60 70 80 90 100
Column Volume (CV = 5.0 mL)
Meta
l C
on
c. (m
g/L
)
Mn(II) Feed = 255 mg/L
Ca(II) Feed = 407 mg/L
Mg(II) Feed = 501 mg/L
BP-2-CF Strip Fractions0.50 CV/min., 9 N H2SO4, 83% Mn(II) Purity
0
2000
4000
6000
8000
10000
1 2 3 4 5 6
Column Volume (CV = 5.0 mL)
Meta
l C
on
c. (m
g/L
)
Mn(II) 30 mg/g
Ca(II) 4 mg/g
Mg(II) 2 mg/g
P
P
N
HO
N
H
O
N
H
N
OSi N
O
O
Si
H
O
O
O
O-
O-
O-
H
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$
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
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
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
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)
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)
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Si
OO
N
N
H
H
NH
H
N
H
H
N
H
H
P
P
OSi
O
O
Si
Si
O
O
Si
O
O
O
O
Si
OO
N
N
H
H
NH
H
N
H
H
N
H
H
P
P
Synthetic Development of Novel Silica Polyamine Composites
and Reclamation of Hazardous Mining Wastewater