SAMMS Silver Zinc Report

NOTICE: The information in this document contains proprietary information of Steward that is either Trade Secret or Patent Protected.
It contains forward looking information. Any release to parties other than the intended recipient is expressly forbidden.

1

Replacement of Zinc with SAMMS in Merrill-Crowe Process
Carmine DiNitto, Caroline Spencer, Rick Beatty, Tyler Biss

Steward Advanced Materials 1245 East 38
th
Street Chattanooga, Tennessee
Telephone: (423) 468-1823 sammsadsorbants.com
Mailing Address P.O. Box 2068 Chattanooga, Tennessee 37407-2489 USA


2

TABLE OF CONTENTS PAGE
Summary and Objectives 3
Potential Benefits 3
Technical Background 4
Discussion 5
Experimental 5
Lime Conditioning 6
Binding Affinity 9

Capacity 10

Sodium Cyanide Performance Results 14
Effect of pH on performance 15
Conclusions 15


3
Summary and Objectives:

With the increasing interest in the removal of precious metals from mining solutions, Steward Advanced
Materials (Steward) has taken the lead in determining the capabilities of SAMMS adsorbent THSL-07
and is now positioned to work with a mining company to determine the applicability and the benefits of
using SAMMS in the Merrill Crowe recovery process.

SAMMS adsorbent THSL-07 demonstrated excellent performance in a lime and sodium cyanide
solution. It has the potential to meet processing and precious metal adsorption requirements in the
mining field. Given these findings, we believe substitution of SAMMS for zinc in the Merrill Crowe
process should be further investigated. At no additional capital costs, using SAMMS should increase
absorption levels of precious metals, lower reagent costs, minimize environmental considerations,
reduce operations cost and possibly simplify extraction techniques.
SAMMS has some similarities to activated carbon and polymeric resins as they can all adsorb precious
metals and have high surface area, but SAMMS has added benefits such as extremely fast kinetics, it
wont leach under high volumetric flows, is selective for silver cation and unaffected by an ionic solution
that contains Cl
-
, SO
4
2-
, NO
3
-
, its virtually unaffected by temperature fluctuations, does not swell as
with polymeric resins and can be used over a wide pH range. SAMMS is not an ion exchange resin or an
adsorbent that captures metals and other undesirables by physical attraction such as carbon. It is a
molecularly designed ceramic ligand support system created to tenaciously bond and be selective to
metals such as silver.

As the substitution of zinc with SAMMS it should prove to be economically and technically attractive.
Steward is seeking an opportunity to work with a mining company to pioneer this, process.
The following report summarizes the potential benefits of using SAMMS adsorbent THSL-07 and the
scientific/technical findings that support these opportunities.
Potential Benefits:
Studies show that SAMMS demonstrated extremely fast kinetics, adsorption capacity and selectively
for Silver and Gold. In a sodium cyanide silver leach concentrate at pH 10.8, adsorption was 98.5%
within 10 minutes compared to only 10.5% with zinc during the same period.


4
Based on these findings, SAMMS adsorbents may be preferable to zinc in silver extraction. Using
SAMMS could:

1. Eliminate the zinc metal ions from the Merrill Crowe process;
2. Lower expensive reagent costs;
3. Offer a better overall performance in capturing silver and gold;
4. Simplify the processing by allowing the mining companies to curtail the need to control pH, ORP,
and dissolved oxygen that if not stringently controlled would cause increases in the
consumption of zinc;
5. Minimize long term environmental issues related to zinc ion and other related species;
6. Eliminate process unit operations such as de-aeration/vacuum may be possible;
7. Simplify metal recovery by addition of the pregnant SAMMS to the smelter with minimum
processing;
8. Directly replace zinc for SAMMS without additional capital expenditures;
9. Reduce reaction time since SAMMS has extremely fast reaction kinetics (adsorption within
seconds) allows it to be used where other resin materials may require several hours.

Technical Background:
Historically, the removal of precious metals from mining solutions is expensive and inefficient. These
solutions require a highly basic environment due to safety concerns when using the cyanide process for
extracting precious metals. To address this problem SAMMS was tested in a silver cyanide leach
solution at high pH. Potentially, SAMMS will lower costs and increases productivity while adhering to the
highest safety standards.
To test this potential, performance curves were generated. Single metal and bimetal matrix test were
also of interest.
The following describes the efficacy of precious metal removal using commercially manufactured thiol
SAMMS. Performance data such as capacity, kinetics, and binding affinities for Ag and Au are also
provided.
Architecture of SAMMS is the key to success;
SAMMS- Self Assembled Monolayers on Mesoporous Supports- is a trademark product produced by
Steward based on licensed technology created and patented by PNNL (Pacific Northwest Laboratories).
The adsorbents are carefully constructed by attaching a monolayer of molecules to mesoporous ceramic
supports. THSL-07, a 20 micron silica support material offers a large pore size and pore volume that
enables attachment of the monolayer as well as access to the binding sites within the pores. Its high
surface area allows for many binding sites and therefore has the capacity to adsorb a large amount of


5
the central metal ions. This SAMMS architecture allows for fast kinetics, high material capacity and
excellent selectively.
SAMMS can be constructed by attaching different functional groups at the monolayer interface. The
focus of this work was to functionalize the silica with a bi-molecular ligand that would have a binding
affinity for silver (Ag) and gold (Au).
Discussion:
The Merrill Crowe cyanide process is used to extract silver and gold from mining ore. SAMMS has the
potential to replace the application of Zinc in Silver recovery. The process requires that the pH remain
highly basic due to release of lethal cyanide gas. Therefore to determine performance of SAMMS,
experimentation needed to be conducted on a SAMMS, small particle THSL-07 in a silver leach cyanide
solution. (Lime is commonly used to maintain a high pH in the mining industry).
Experimental (Lime Conditioning):
Step 1- Conditioning
SAMMS adsorbent, THSL-07 was conditioned by tumbling in a lime solution for up to 7 hours in a 500
ml Nalgene bottle. The pH was adjusted at 9.0, 10.5 and 11.25 and a portion of SAMMS was extracted
from the solution at intervals of: 1, 2, 4, 6 and 7 hours. The SAMMS was allowed to dry in air
overnight.
These samples were subsequently used.
Step 2- Metal Content
A 500 ml metal contact solution was prepared by pH adjusting DI water with dilute HCl to pH of ~3 and
spiking the solution with silver and for bimetal test spiking with gold at a low and high concentration
relative to silver. For kinetics performance data, samples were extracted at time intervals of 30 seconds,
1 minute, 2 minutes and up to 5 minutes. They were analyzed on an Agilent ICP-MS for each of the
contact metals, silver and/or gold. The results were used to evaluate performance of SAMMS.
A metal solubility check was done in the contact solution at 3 pH. This was necessary to assure no
precipitated metal was present. The results confirmed the metals were in ionic form.
SAMMS Pre-Wetting:
SAMMS THSL-07 may need to be pre-wetted in CN- solution with ~5 -10 % EtOH prior to application
since it is hydrophobic. When pre-wetted, SAMMS will easily disperse in water.


6
Experimental: (Sodium Cyanide)
SAMMS and Zinc were exposed to a silver cyanide solution at 33.2 ppm Ag. The leached silver
concentrate (elute) was agitated over 72 hours using a ratio of 4 lbs/ton NaCN solution at pH of 10.8 and
20 % solids.
Dosages were:
Zinc: 0.4 gms per 575 mls leach eluate
SAMMS: 1.0 gms per 575 mls leach eluate

Samples were filtered through a 1 micron filter at 5 and 10 minutes and tested for silver using a Perkin
Elmer ICP-OES.

Lime Conditioning:
Physical Properties Reviewed
THSL-07 was conditioned up to 7 hours to determine how SAMMS would perform physically. The
conditioned SAMMS and control was tested on a BET analyzer that provided SSA (specific surface area),
pore size and pore volume. The results are provided in Graph 2, Table 1.
The 0 hour or control sample was prepared by subjecting SAMMS to a DI water solution and tumbled
for 3 hours.
The results indicate that the largest effect on the SAMMS at pH of 10.5 occurred within the first hour of
lime exposure. After that period the SAMMS physical characteristics remained nearly stable. The pore
volume decreased from, 1.20 cm
3
/g to 1.02 cm
3
/g, while the pore size increased from 158 to 171 . The
specific surface decreased from 302 to 237m
2
/g. These changes occurred with the one (1) hour lime
exposure time.
It was necessary to determine if these physical alterations to the SAMMS affects its overall
performance. This was done by performing contact solution tests using the Au and Ag as test metals.
The results are expressed in terms of capacity, SAMMS ability to adsorb the contact metal and its
kinetics, and the speed at which the metal is adsorbed.


7

Table 1- BET properties of THSL-07, conditioning results
Sample time, hrs.
Surface Area
m
2
/g
Pore Volume
cm
3
/g Pore Size
TH07 + Di (0) 302.56 1.20 158.57
1 237.76 1.02 171.93
2 232.58 1.01 174.06
4 224.61 0.97 173.00
6 226.18 0.97 171.94
7 224.96 0.96 170.89
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0
50
100
150
200
250
300
350
0 2 4 6 8
P
o
r
e

V
o
l
u
m
e
S
p
e
c
i
f
i
c

S
u
r
f
a
c
e

&

P
o
r
e

S
i
z
e
Lime Conditioning Time, Hours
Graph 2-THSL-07 Particle Characteristics
during Lime Conditioning, pH 10.5
Surface Area m2/g
Pore Size
Pore Volume cm3/g

NOTICE: The information in this document contains proprietary information of Steward that is either Trade Secret

Generally, (1) the more metal contact time the better the recovery and
time will worsen the performance.

The information in this document contains proprietary information of Steward that is either Trade Secret
contains forward looking information. Any release to parties other than the intended recipient is expressly forbidden.
Generally, (1) the more metal contact time the better the recovery and (2) increased lime conditioning

The information in this document contains proprietary information of Steward that is either Trade Secret or Patent Protected.
contains forward looking information. Any release to parties other than the intended recipient is expressly forbidden.
8

(2) increased lime conditioning


9
Adsorption Capacity/Kinetics: A kinetic isotherm curve was developed in a DI water solution using a
0.05wt% SAMMS dosage to determine the effectiveness of SAMMS in a 10ppm Ag contact solution,
Graph 5.

As shown SAMMS kinetics are extremely fast in capturing silver. Within seconds a reduction of >97%
was realized. SAMMS continued to remove silver up to 99.96% after only 5 minutes.
In silver mining ore there is usually a small amount of gold, possibly 5% in relation to silver present. It is
therefore important to understand SAMMS binding affinities for both these precious metals to
calculate benefits. The following study presents the capacity equilibrium curves for both gold and silver,
illustrating the ability of SAMMS to adsorb these precious metals at nearly double its weight!.

9990
233
494
325
23 18 4 3
0
2000
4000
6000
8000
10000
12000
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
p
p
b

A
g
Contact time, minutes
Graph 4-THSL-07 SAMMS, Ag Kinetic Chart (Small Particle)
unconditioned (no lime), 0.05wt% SAMMS


10
The equations used for calculating binding affinity and capacity (Langmuir Equation), are:
Binding Affinity ( mls/g)
Kd=((C
o
-C
f
)/C
f
)*V/m
g

Where: C
o
is the initial concentration
C
f
is the final concentration at 5 minutes
V is the volume in, mls
m
g
is the mass of SAMMS used in the test

Capacity Static Beaker test (g/g)
Cp = (C
o
-C
f
) *V/m
g

Binding Affinity:
Both silver and gold were tested at a C
o
of

~10 ppm in a 500 ml DI water solution. SAMMS was added at
0.05wt% and tumbled for 4 hours. The resultant affinities were determined;

Ag Au units
9871 10750 g/L, C
o

4 2 g/L, C
f

500 500 mls, V
0.25 0.25 m
g
, SAMMS

Affinity 10.7E+06 4.93E+06 mls/g, Kd Au>Ag

The binding affinity for both metals is very high. This means that with gold and silver present in solution
they may, (1) adsorb nearly proportionally into the SAMMS and (2) be highly selective for these
precious metals over other minor metals such as Cu, Zn, Co, and Ni . When tested, the capacity for these
metals was equal to the total saturated capacity for SAMMS. (These findings are presented in the
section on metal capacity).
Adsorption Capacity:
The capacity for each metal was determined in a Mock solution (DI water). The SAMMS was not lime
conditioned although conditioned SAMMS should give very similar results.


11
Silver, Ag:

The Equilibrium curve for silver at four different metal contact concentrations is shown in Graph 5.
The tests were conducted in a 4 liter vessel using 0.05 gms (0.00125wt%) of THSL-07 SAMMS. The
solution was tumbled for 4 hours and a sample withdrawn and filtered through a 0.45 um syringe filter.
The sample was analyzed on an Agilent ICP-MS. The capacity was calculated using the Langmuir
Equation.

Those results show a very high capacity for silver in a 100 ppm contact solution. The equilibrium
adsorption capacity was 0.99 g Ag/g SAMMS.
At 10 ppm Ag concentration, a typical concentration in mining ore solution, the binding affinity and
capacity can be compared as follows:

Binding Affinity, mls/g 4.93E+06
Capacity, g/g 0.26

This means that SAMMS will adsorb 26% of its weight in Ag and will preferentially select Ag over other
minor metals present. At 100 ppm Ag, SAMMS will nearly double in weight.

0.01
0.1
1
10
10 100 1000 10000 100000 1000000
C
a
p
a
c
i
t
y
,

g
A
g
/
g

S
A
M
M
S
Equilibrium Concentration, ug/L (ppb)
GRAPH 5- Silver Ag, Equilibrium Isotherm Curve
in Mock solution


12
Gold, Au:
The Equilibrium curve for gold at four different metal contact concentrations is given in Graph 6.
The tests were conducted in a 4 liter vessel using 0.05gms (0.00125 wt%) of THSL-07 SAMMS. The
solution was tumbled for 4 hours and a sample withdrawn and filtered through a 0.45 um syringe filter.
The sample was analyzed on an Agilent ICP-MS. The capacity was calculated using the Langmuir
Equation.

Those results show an extremely high capacity for gold in a 100 ppm contact solution. The equilibrium
adsorption capacity was 1.45 g Au/g SAMMS.

At 10 ppm Au concentration we can compare the binding affinity and capacity. The capacity test was
done in a 4 liter vessel. The capacity and affinity is:

Binding Affinity, mls/g 10.7E+06
Capacity, g/g 0.51

This means SAMMS will adsorb 51% of its weight in Au twice (2:1) that of Ag. At 100 ppm, 1 gram of
SAMMS will have increased its weight to 2.45 grams.

These high capacities and selectivity should translate into SAMMS being a better candidate
economically when compared to the present use of zinc.


13

Although the binding affinities for gold and silver are similar magnitude, the equilibrium
capacity between 100 ppb and 100 ppm is lower for silver. The table below gives a direct comparison:
Capacity, g/g Capacity, g/g
Metal, ppm Au Ag

1 0.09 0.08
10 0.51 0.26
100 1.45 0.99

It is important to note that the % efficiencies for the capacity testing at 100 ppm test is nearly at
equilibrium saturation and can be taken as the saturated capacity. However, for the 1 and 10 ppm
saturation capacity was not fully attained. This suggests the real saturated capacity for 10 ppm may
approximate ~0.3 g/g for Ag and also be slightly higher for gold. While this is only estimation, in fact the
capacity would be higher than reported in the above comparative capacity table. (All capacity values
were taken after a 4 hour mix time).

0.01
0.1
1
10
10 100 1000 10000 100000 1000000
C
a
p
a
c
i
t
y
,

g

A
u
/
g

S
A
M
M
S
Equilibrium Concentration, ug/L (ppb)
GRAPH 6 -Gold Au, Equilibrium Isotherm Curve
in Mock solution


14
The amount of gold was increased to a 60 parts Ag and 40 parts Au solution to determine the effect of
gold on overall kinetics at this higher percentage. The starting concentration C
o
and C
f
final
concentrations were 9084 ppb Ag and 5606 ppb Au.

Sodium Cyanide Exposure Results:

The performance of SAMMS in a silver leach solution at pH 10.8 demonstrated excellent kinetic
performance. SAMMS removed 98.4% Ag in 10 minute contact time compared to only 10.5% with zinc
during the sample period. At an initial Ag concentration of 33.2 ppm the SAMMS quickly reduced Ag
down to 0.753 ppm in 5 minutes while zinc decreased to 31 ppm, although the Zn test did not include
de-aeration or ORP control that may have affected its optimum performance. In both high pH and a
cyanide solution, SAMMS performance appears to be unaffected, Graph 7. At 10 minutes SAMMS
adsorbed nearly 60 times more silver when compared to zinc. (Silver adsorption may have been faster
than demonstrated by the graph since sampling intervals were 5 minutes.)

31
29.7
0.753 0.521
0
5
10
15
20
25
30
35
0 2 4 6 8 10 12
p
p
m

A
g

Contact time, minutes
Graph 7- Silver Leach Cyanide Solution
[SAMMS & Zinc] Ag removal @ 33.2 ppm Ag, pH 10.8 @20% solids,
4lbs /ton NaCN
Zinc
SAMMS


15
Effect of pH on Kinetic Performance:

The conditioning pH was studied at a pH of 9, 10.5 and 11.25. Typically process time exposure kinetic
times may be 20 minutes to 2 hours. Therefore, the experimentation was done based on 1, 2, and 4
hour lime conditioning times.

The operating pH and exposure time need to be considered in the application of SAMMS. For example:

pH Exposure time, hours
Estimation
<9.0 >7
10.5 ~6
11.25 <4

Conclusions:
THSL-07 SAMMS has shown to have excellent kinetics and capacity for both gold and silver. With nearly
2:1 capacity difference and high binding affinities for each of these precious metals, SAMMS will readily
remove both of these metals simultaneously.
In a silver cyanide leachate solution at pH of 10.8, SAMMS removed 98.4% of silver in 10 minutes when
compared to 10.5% precipitate with zinc during the same period. Reduction of Ag after 5 minutes was
97.7%. After 10 minutes SAMMS adsorbed nearly 60 times more silver compared to zinc. SAMMS
performance appears to be unaffected by both high pH and a cyanide enriched solution.
SAMMS is an excellent adsorbent for extracting precious metals such as gold and silver from water.
Even when SAMMS is lime conditioned to a pH of 9.0 to 11.25 prior to adsorption, it continues to
perform extremely well. It would be suited were precious metals are of interest to be removed from
mining operations and/or other applications requiring metal recovery.
Processing variables such as pH, SAMMS exposure time, operation conditions, methods of application
etc. should be understood as part of the overall performance of SAMMS. SAMMS shows excellent Ag
equilibrium adsorption capacity at 100 ppm, approaching 1.0 gram of recovered Ag for every gram of
SAMMS. However, the potential user will need to determine what concentration of precious metal is
required to be economically attractive.
SAMMS performed excellent in a lime conditioned and sodium cyanide solution. It has the potential to
meet processing and precious metal adsorption requirements. Substitution of SAMMS for zinc should
be investigated since no additional capital cost should be incurred, reagent cost decreased,
environmental considerations minimized, operations cost reduced and extraction techniques simplified.
pH/time
Kinetics


16
Steward is looking for a partnership to help demonstrate SAMMS performance as described herein. We
believe that SAMMS is a unique product, different from ion exchange, carbon and polymeric resins and
is worthy of additional testing to prove out it capabilities.

SAMMS Silver Zinc Report

Загружено:

Сведения о документе

Исходное описание:

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

SAMMS Silver Zinc Report

Загружено:

Авторское право:

Доступные форматы

NOTICE: The information in this document contains proprietary information of Steward that is either Trade Secret or Patent Protected.

Вам также может понравиться