umt poster
DESCRIPTION
Poster summary of selected research conducted at the University of Montana towards a PhD in chemistry.TRANSCRIPT
Purity Systems, Inc.
Dr. Ed Rosenberg (Chemistry)
Dan Nielsen (Ph.D. Student – Chemistry)
Joel Clancey (Research Assistant)
Jeff McKenzie (Research Assistant)
Functionalized Silica Polyamine Composites for Metal Recovery from Hazardous Mining Wastewater and Acid Leach Solutions
Toxic and polluting metals contaminate waters worldwide. The reported materials exhibit exceptional metalselectivity and capacity at high flowrates. Functionalized silica polyamine composites were utilized to recovercopper(II), zinc(II) and manganese(II) from Berkeley Pit Lake water (Butte, MT). Additional composite materialswere used to separate five rare earth elements from an authentic acid leach matrix. Iron(III) was removed froma synthetic copper(II) electrowinning solution. All reported process strategies allow for continuous high flowtreatment. Bench-scale studies show the potential for these materials to be used at an industrial-scale.
Acknowledgments
• Dr. Bob Fischer
• Dr. Johnnie Moore
• Carolyn Hart
• John Deming
• Montana Board of Research &
Commercialization Technology
• Department of Energy
The target metals Cu(II),Zn(II), and Mn(II) have beenselectively removed producingrecovery solutions concentrated10 - 50 fold, with high purity(83 - 99.98%). Molecularstructures illustraterudimentary metal coordinationfor clarity. Bench scaletreatment used 5.0 mLcolumns, and data is reportedas a function of columnvolume. CuWRAM was able toseparate Cu(II) directly fromBerkeley Pit Lake water in thepresence of Fe(III) and Al(III).Treated effluent from CuWRAMwas then adjusted to pH 5.2and the produced Fe(III) andAl(III) hydroxide precipitatewas removed by filtration. HighZn(II) capacity using WP-2 wasthen achieved with very highpurity. Mn(II) was nextrecovered with the use of BP-2.
In 2003 the U.S. Geological Survey had identifiedover 230,000 abandoned hardrock mines in thewestern U.S., 6,000 of these are located inMontana state. 350 of Montana’s sites have beendetermined to affect water quality designatingthem as high priority sites. The Berkeley Pit (Butte,MT) contains Cu(II), Zn(II), and Mn(II)concentrations ideal for metal recovery using silicacomposite technology. These three metals areubiquitous among mining waste sites as acid minedrainage (AMD), and their recovery offsets the costof waste treatment. Multistage treatment begins bythe extraction of copper from the Berkeley Pit Lakeutilizing the picoline silica poly(allylamine)composite “CuWRAM.” Fe(III) and Al(III) are thenprecipitated and removed as the metal hydroxidesat pH 5.2. The acetate silica poly(ethyleneimine)composite “WP-2” is next used to concentrate andpurify zinc. Manganese is subsequently recoveredvia “BP-2” (acetate silica poly(allylamine)composite) in the sodium ion (base form). Montana State’s High Priority Cleanup SitesAbandoned Hardrock Mines in the Western U.S.
The Berkeley Pit 1981 (top), 1999 (bottom) Diagram of Treatment Process
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
Major Species Conc. (mg/L) of Berkeley Pit Lake Water (at Various Depths)
Depth (ft) Fe Zn Mg Ca Al Mn Cu Cd As
0 270 378 430 512 195 179 86.8 1.84 <0.22
50 892 578 538 494 281 212 145 2.39 0.34
500 986 580 536 494 281 209 177 2.43 0.78
Schematic Structure of BP-2 (base form)
P
P
NO
N
H O
N
H
N
OSi N
O
O
Si
H
O
O
O
O-
O-
O-
H
HMn2+
Na+
Na+
Berkeley Pit Lake Metal Ion Recovery Data
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
Schematic Structure of CuWRAM
Cu2+
P
P
N
H
N
H
N
OSi N
O
O
Si
H
O
O
H N
N
H
N
H
L L
L = H2O, HSO4-, or SO4
2-
CuWRAM Cu(II) Extraction/Recovery
0.50 CV/min., Feed pH = 2.2, 32 mg/g Cu(II) Capacity
0
100
200
300
400
500
600
700
0 50 100 150 200 250
Column Volume (CV = 5.0 mL)
Meta
l C
on
c.
(mg
/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
0.50 CV/min., 9.0 N H2SO4, 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.
(mg
/L)
Cu(II) 32 mg/g
Fe(III) 1 mg/g
Al(III) 0.0 mg/g
Zn(II) 0.0 mg/g
Mn(II) 0.0 mg/g
Berkeley Pit Precipitation/Filtration Study
P
P
O
O-
NN
OSi N
O
O
Si
O
O
H
NNN
O
HO
H
H
O
HO
P
Zn2+
Schematic Structure of WP-2
0
100
200
300
400
500
600
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5
pH
Meta
l C
on
c.
(mg
/L)
Zn
Fe
Al
Mn
BP-2 Mn(II) Extraction/Recovery
BP-2-CF Breakthrough Curve
0.50 CV/min., Feed pH = 4.9, 23 mg/g Mn(II) 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.
(mg
/L)
Mn(II) Feed = 255 mg/L
Ca(II) Feed = 407 mg/L
Mg(II) Feed = 501 mg/L
0.50 CV/min., 9 N H2SO4, 83% Mn(II) Purity
0
2000
4000
6000
8000
10000
12000
1 2 3 4 5
Column Volume (CV = 5.0 mL)
Meta
l C
on
c.
(mg
/L)
Mn(II) 30 mg/g
Ca(II) 4 mg/g
Mg(II) 2 mg/g
WP-2 Zn(II) Extraction/Recovery
WP-2-CF Breakthrough Curve (4 CV 0.010 M NaOH to pH 1.9)
0.50 CV/min., Feed pH = 5.3, 26 mg/g Zn(II) Capacity
0
100
200
300
400
500
600
700
0 20 40 60 80 100 120
Column Volume (CV = 5.0 mL)
Meta
l C
on
c.
(mg
/L)
Zn(II) Feed = 620 mg/L
Mn(II) Feed = 248 mg/L
WP-2-CF Strip Fractions
0.50 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.
(mg
/L)
Zn(II) 22 mg/g
Mn(II) 0 mg/g
The phosphonic acid silicapoly(allylamine) composite (BPAP)exhibits superior metal exchangekinetics compared to a leadingcrosslinked polystyrene resin(Diphonix®). Additionally, BPAP wascapable of removing Fe(III) from a 2 MH2SO4 synthetic electrowinning solutioncontaining 10 g/L Cu(II). Areproducable second load/strip cycleconfirms complete stripping of Fe(III).Rare earth elements (REEs) wereseparated from an authentic sulfuricacid leach solution to 99% REE purity.This was accomplished by removingFe(III) using the oxine poly(allylamine)composite (WP-4), followed by REEseparation using BPAP. Secondload/strip cycles were identical to thefirst for both WP-4 and BPAP (resultsnot shown for clarity). Eu(III) andFe(III) can both be stripped from BPAPusing either EDTA (pH 10.6) or H3PO3,although slow flow rates must beemployed for Fe(III).
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
/L
Fe(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
BPAP Fe(III) Extraction/Recovery
87% 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.
P
P
NH
N
H
N
H
N
OSi N
O
O
Si
H
O
O
H
H
N
OH
NHO
Schematic Structure of WP-4
REE Acid Leach Metal Ion Recovery Data WP-4-CF 101205-DN Strip Profile
0.50 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
Column Volume (CV = 12 mL)
Meta
l C
on
c.
(mg
/L)
Fe(III)
Ti(IV)
Ce(III)
Nd(III)
La(III)
WP-4-CF 101205-DN Breakthough Curve
0.50 CV/min., Feed pH = 1.30, 25 mg/g Fe(III) Capacity
0
1000
2000
3000
4000
5000
6000
0 5 10 15 20 25
Column Volume (CV = 12 mL)
Fe(I
II)
Co
nc.
(mg
/L)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Fe(III)
WP-4 Fe(III) Extraction/Recovery
BPAP-CF 041504-DN Breakthrough Curve #2
0.50 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)
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)]
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)M
eta
l C
on
c.
(mg
/L)
Ce(III)
La(III)
Nd(III)
Sm(III)
Pr(III)
Al(III)
BPAP REE Extraction/Recovery
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
Column Volume (CV = 5.0 mL)
Fe
(III)
mg
/L
1.5 M EDTA (99% stripped)
5.0 M H3PO3 (94% stripped)
5.0 M H3PO4 (78% stripped)
0.50 CV/min., Various 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
Column Volume (CV = 5.0 mL)
Eu
(III
) m
g/L
1.0 M EDTA pH 10.6 (100%)
5.0 M H3PO3 (100%)
5.0 M H3PO4 (99%)
4.0 M HNO3 (92%)
9.0 M H2SO4 (80%)
10 M HCl (39%)
BPAP Eu(III) & Fe(III) Stripping Studies
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
Schematic Structure of BPAP
Berkeley Pit Water Treatment using BPAP-CF (120902-DN)
0
0.2
0.4
0.6
0.8
1
1.2
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0
Colume Volume (CV = 33.1 mL)
C/C
o
Iron (516 mg/L)
Copper (113 mg/L)
Zinc (671 mg/L)
Aluminum (310 mg/L)
Flow Rate = 1.0 CV/min.
pH Feed = 2.3
BPAP-CF 120902-DN Breakthrough Curve1.0 CV/min., Feed pH = 1.5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 5 10 15 20 25
Column Volume (CV = 33 mL)
Meta
l C
on
c. (C
/Co)
Feed pH = 1.5
1.0 CV/min. Flowrate
Fe(III) Feed = 1,250 mg/L
Cu(II) Feed = 9,570 mg/L
Berkeley Pit Water Treatment using BPAP-CF (120902-DN)
0
0.2
0.4
0.6
0.8
1
1.2
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0
Colume Volume (CV = 33.1 mL)
C/C
o
Iron (516 mg/L)
Copper (113 mg/L)
Zinc (671 mg/L)
Aluminum (310 mg/L)
Flow Rate = 1.0 CV/min.
pH Feed = 2.3
BPAP-CF 120902-DN Breakthrough Curve1.0 CV/min., Feed pH = 1.5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 5 10 15 20 25
Column Volume (CV = 33 mL)
Meta
l C
on
c. (C
/Co)
Feed pH = 1.5
1.0 CV/min. Flowrate
Fe(III) Feed = 1,250 mg/L
Cu(II) Feed = 9,570 mg/L
Diphonix® Resin (top), BPAP (bottom)
Berkeley Pit Water Treatment using BPAP-CF (120902-DN)
0
0.2
0.4
0.6
0.8
1
1.2
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0
Colume Volume (CV = 33.1 mL)
C/C
o
Iron (516 mg/L)
Copper (113 mg/L)
Zinc (671 mg/L)
Aluminum (310 mg/L)
Flow Rate = 1.0 CV/min.
pH Feed = 2.3
BPAP-CF 120902-DN Breakthrough Curve1.0 CV/min., Feed pH = 1.5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 5 10 15 20 25
Column Volume (CV = 33 mL)
Meta
l C
on
c. (C
/Co)
Feed pH = 1.5
1.0 CV/min. Flowrate
Fe(III) Feed = 1,250 mg/L
Cu(II) Feed = 9,570 mg/L
Berkeley Pit Water Treatment using BPAP-CF (120902-DN)
0
0.2
0.4
0.6
0.8
1
1.2
0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0
Colume Volume (CV = 33.1 mL)
C/C
o
Iron (516 mg/L)
Copper (113 mg/L)
Zinc (671 mg/L)
Aluminum (310 mg/L)
Flow Rate = 1.0 CV/min.
pH Feed = 2.3
BPAP-CF 120902-DN Breakthrough Curve1.0 CV/min., Feed pH = 1.5
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 5 10 15 20 25
Column Volume (CV = 33 mL)
Meta
l C
on
c. (C
/Co)
Feed pH = 1.5
1.0 CV/min. Flowrate
Fe(III) Feed = 1,250 mg/L
Cu(II) Feed = 9,570 mg/L