Recovery o f Platinum from Concentrated

Sodium Chloride Brine by

Electrodeposition on Vitreous Carbon

J. E. Harrar and F. 8. Stephens

January, 1984

This report was prepared as an account of work sponsored by an agency of the United States
Government. Neither the United States Government nor any agency thereof, nor any of their
employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or
process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark,
manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views
and opinions of authors expressed herein do not necessarily state or reflect those of the
United States Government or any agency thereof.

DISCLAIMER
This report was prepared as an account of work sponsored by an
agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.

DISCLAIMER
Portions of this document may be illegible in
electronic image products. Images are produced
from the best available original document.

Contents

...............................
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Experimental Apparatus and Procedures . . . . . . . . . . . . . . . .
Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Apparatus and Procedures f o r Voltammetry . . . . . . . . . . . . .
Apparatus and Procedures f o r P l a t i n u m . . . . . . . . . . . . . .

Abstract

1
3

4
4

Recovery Experiments

......... 8
P l a t i n u m . . . . . . . . . . . . . . . . . . 15

R e s u l t s and D i s c u s s i o n o f Voltammetric Measurements

R e s u l t s and D i s c u s s i o n o f

Recovery Experiments

Conclusions

.............................

...........................
..............................

18

Acknowledgments

19

References

20

Recovery of Platinum from Concentrated Sodium Chloride Brine

by Electrodeposition on Vitreous Carbon

J. E. Harrar and F. B. Stephens

Abstract
The voltammetric characteristics of Pt( 11) and Pt( IV) have been
examined at a vitreous carbon electrode i n slightly acidic 3 4 ( ~ 1 5
wt.%) NaCl solutions. Pt(1V) is reduced to Pt(l1) at %O V and Pt(I1)
is reduced to Pt(0) at -0.5

V vs. Ag-AgC1.

The rate of deposition of

platinum metal at -0.5 V is very low on bare carbon, but increases as the
coverage o f platinum increases. The potential at which hydrogen is
evolved in this medium is -0.85

V.

A technique has been tested for

the removal o f sub-part-per-million levels of platinum from the

high-salinity brine by controlled-potential electrolysis using a
reticulated, vitreous-carbon, flow-through electrode. However, at
control potentials negative enough to begin to electrodeposit the
platinum at a significant rate, simultaneous reduction of hydrogen ion
reduces the current and energy efficiency t o an unacceptable level.

Introduction
6

In a previous study (Harrar and Raber, 1983), in which a number

of

natural brines were analyzed for precious and strategically-valuable

metals, it was found that one of the brines from the Salton Sea
geothermal field contained approximately 50 pg/kg o f platinum.
Although this concentration i s very low, the large volumes of fluid that
are currently processed for energy extraction makes such a resource
-1 -

attractive if the precious metal could be economically extracted. The

brines of the Salton Sea geothermal field (or KGKA

Known Geothermal

Resource Area) are of extremely high salinity (15-20wt % salts), and are
composed principally of sodium, potassium, and calcium chlorides.
The fluid that would most likely be processed for metals recovery
would be the relatively low temperature (<90C) effluent brine from the
power plant facility, after the principal flash stages for energy
extraction. However, different geothermal plant designs involving
high-temperature crystallizers for solids removal are currently being
tested, and valuable metals recovery is certainly possible at the higher
temperatures (>200C)of the wellhead brine.

A literature survey of

previous studies in geothermal mineral recovery can be found in our

p r e v i o u s r e p o r t ( h a r r a r and Raber, 1983) and a paper by Maimoni ( 1 9 8 3 ) .

To

continue our investigations, two approaches have been examined for

removal of platinum from high-salinity geothermal brines. One involved

the use of various solid chemical media that were known from previous
studies in dilute waters to be effective in precious metal removal. Most
of these media had been tested previously only for non-precious-metal or
gold and silver removal (Acton, 1982) and in low-ionic-strength, low
temperature solutions. The results of this study are being reported
el sewhere (Raber, Thompson, and Gregg 1984).
The second technique examined for platinum recovery was electrolytic
*

deposition on a substrate of vitreous carbon. For some of the elements,

electrodeposition of the metals on inert electrode materials is performed
for both metals recovery (Habashi, 1982; Ettel and Tilak, 1981; Coeuret,
1980), pollution control (Bennion and Newman, 1972; Kuhn, 1972) and for

trace metals analysis (Murthy, Holzbecher, and Ryan, 1982).

However, not

only is there no knowledge of the conditions necessary for quantitative

-2-

electrodeposition of trace amounts of platinum from aqueous solutions in

general, but there is also no information on the electrochemistry of
p 1ati num i n hi gh-chl oride medi a.
Accordingly, our first objective was t o measure the current/electrodepotential characteristics of platinum in solutions of NaCl at
a

concentrations simulating those of the high-salinity geothermal brines.

Then, using these data, a series of experiments were carried out to
attempt to quantitatively electrodeposit platinum from a flowing stream
of brine. The electrode material selected was vitreous or "glassy"
carbon. This material was selected because of its relative inertness,
and because, for the flowing-stream experiments, it could also be
obtained in the form of reticulated-vitreous carbon (RVC).

This material

(see Wang, 1981) is commercially available and is configured as a rigid,

porous matrix that can be used advantageously in processes requiring
large electrode surface area. Both the current-potential (voltammetric)
and the f low-recovery measurements were performed using 3-electrode
controlled-potential techniques so that the applied cathode potentials
would be precisely known.

Experimental Apparatus and Procedures

Reagents. For the voltammetric measurements, the brine solutions
were prepared from J. T. Baker Ultrex-grade NaCl salt. It was found that
Mallinkrodt ACS reagent-grade NaCl contained sufficient heavy-metal
impurities to raise the background current to an undesirably high level
i

in these concentrated solutions. For the recovery experiments, however,

the larger volumes o f solution precluded use of the Ultrex-grade salt, so
the reagent-grade salt was used.

- 3-

Platinum( 11) and p l a t i n u m ( I V ) s o l u t i o n s were prepared by d i s s o l v i n g ,

r e s p e c t i v e l y , (NH4)2PtC14 and (NH4)2PtC16 s a l t s i n water.

These s a l t s

were o b t a i n e d f r o m Engelhard I n d u s t ties as n o m i n a l l y h i g h - p u r i t y

compounds.

The c o n c e n t r a t i o n s of p atinum were c a l c u l a t e d f r o m t h e

assays o f t h e compounds as r e p o r t e d by t h e manufacturer.

For t h e

p l a t i n u m r e c o v e r y experiments, a so u t i o n c o n t a i n i n g 0.168 mg P t / m l and

0.002 M HC1 was used.

Apparatus and Procedures f o r Voltammetry.

To i n v e s t i g a t e t h e

voltammetry o f platinum, equipment c o n s i s t e d o f an EG&G P r i n c e t o n A p p l i e d

Research Model 174A P o l a r o g r a p h i c Analyzer, Model 303 S t a t i c Mercury Drop
E l e c t r o d e Assembly, and a Houston X-Y r e c o r d e r .

A model GO173 g l a s s y

carbon e l e c t r o d e was s u b s t i t u d e d f o r t h e mercury c a p i l l a r y i n t h e c e l l

assembly.

To prepare a s o l u t i o n f o r voltammetry, 5 m l o f b r i n e was

p l a c e d i n t h e c e l l , and 1 m l o f a s t o c k s o l u t i o n o f e i t h e r P t ( I 1 ) o r
Pt(1V) was p i p e t t e d i n t o t h e c e l l t o g i v e a p l a t i n u m c o n c e n t r a t i o n o f 2 x

lo-' M.

The pH o f t h e c e l l s o l u t i o n s was i n t h e range o f 4 t o 6.

S o l u t i o n s were deoxygenated b y b u b b l i n g h i g h - p u r i t y n i t r o g e n through them

f o r a t l e a s t 4 min. p r i o r t o t h e voltammetric scans.
o v e r t h e t o p of t h e s o l u t i o n s d u r i n g t h e scans.

N i t r o g e n was f l o w e d

A l l measurements were

made a t an ambient temperature o f 22-25OC.

Apparatus and Procedures f o r P l a t i n u m Recovery Experiments.

The f l o w

e l e c t r o l y s i s c e l l shown i n F i g u r e 1 was used f o r t h e r e c o v e r y

experiments.

Features o f t h i s f l o w - t h r o u g h RVC c e l l t h a t d i f f e r from

p r e v i o u s designs ( S t r o h l and Curran, 1979; Wang and Dewald, 1983) a r e t h e

d u a l c o u n t e r - and r e f e r e n c e e l e c t r o d e s and t h e use o f low-temperature
(140OC) h e a t - s h r i n k a b l e T e f z e l t o encase t h e RVC.

- 4-

The lower temperature

Solution
outlet

Figure 1.

Sol ution
inlet

Flow electrolysis cell for removal of platinum from simulated geothermal brine.
1. Reticulated vitreous carbon working electrode. 2. Heat-shrinkable Tefzel tubing.
3. Glassy carbon rod counter electrodes. 4. Ag-AgC1 reference electrodes. 5. Ace
threaded-glass connectors. 6. Teflon plugs. 7. Viton O-Rings. 8. Zirconium electrical
connection to working electrode.

would minimize chemical m o d i f i c a t i o n o f t h e R V C d u r i n g f a b r i c a t i o n o f t h e

assembly.

The dual e l e c t r o d e s reduce t h e p o t e n t i a l g r a d i e n t t h r o u g h t h e

I ~ V Cand e f f e c t b e t t e r c o n t r o l o f i t s p o t e n t i a l .

I n o p e r a t i o n , each

c o u n t e r e l e c t r o d e and each r e f e r e n c e e l e c t r o d e i s connected e x t e r n a l l y t o

i t s twin.
The working-electrode c y l i n d e r o f K V C was c u t b y means o f a c o r k

b o r e r f r o m p i e c e s o f R V C o b t a i n e d f r o m Energy Research and Generation,

Inc. Two grades o f R V C were t e s t e d :

45s ( s 4 5 pores/in.

s u r f a c e area) and 100s ($100 pores/in.

and 800 f t / f t

and 2000 f t 2/ f t 3 s u r f a c e a r e a ) .

F o r t h e 45s-grade m a t e r i a l , o u r working e l e c t r o d e volume o f $4.5 cm

would have an e f f e c t i v e s u r f a c e area of 118 cm

By comparison, t h e

s u r f a c e area o f t h e v o l t a m m e t r i c working e l e c t r o d e was 0.096 cm

The c o u n t e r e l e c t r o d e s were r o d s o f g l a s s y carbon o b t a i n e d f r o m

Polycarbon, Inc.

The r e f e r e n c e e l e c t r o d e s were r o d s o f s i l v e r , coated a t

t h e t o p w i t h an i n s u l a t i n g f i l m o f N a r l i n e r s t r i p p a b l e f i l m , and
converted t o AgCl a t t h e t i p b y immersion i n aqua r e g i a .

The g l a s s c e l l

bodies were f a b r i c a t e d f r o m Ace Glass Co. s i z e 15 threaded connectors,

and t h e R V C e l e c t r o d e was h e l d i n p l a c e b y T e f z e l t u b i n g , which, as
mentioned, c o u l d be shrunk a t t h e r e l a t i v e l y low temperature o f 14OOC.
A new R V C e l e c t r o d e was used f o r each experiment; a f t e r reassembly b y

h e a t s h r i n k i n g t h e T e f z e l o n t o t h e RVC, and i n s e r t i n g t h e T e f l o n plugs, a

needle was used t o p i e r c e t h e T e f z e l and t h e n a 0.5-mm-dia

zirconium w i r e

was i n s e r t e d as shown i n F i g . 1 t o make e l e c t r i c a l connection t o t h e

RVC.

The w i r e was t h e n sealed a t t h e o u t s i d e w i t h Dow-Corning 3145 RTV

sealant.

A Technicon AutoAnalyzer p e r i s t a l t i c pump and a p p r o p r i a t e s i z e s

of Tygon t u b i n g were used t o pump b r i n e t h r o u g h t h e e l e c t r o l y s i s c e l l .

Connection t o t h e p o r t s of t h e c e l l were made v i a Cheminert f i t t i n g s .
The b r i n e was f l o w e d t h r o u g h an i n - l i n e ,

- 6-

1-pm Gelman f i l t e r b e f o r e

entering the cell. The reservoir for the platinum-containing brine that
was pumped through the cell consisted of a 2-liter FEP Teflon bottle.
The cap of the bottle was fitted with a fritted-glass gas-dispersion tube
for deoxygenation of the solution, and a section of Teflon tubing
reaching to the bottom of the bottle for withdrawal of the solution.
This tubing was connected to the pump tubing via a 3-way Teflon-plug
e

stopcock so that the cell could first be flushed with brine that did not
contain platinum.
At the beginning of each experiment, exactly 1-liter of brine was
placed in the 2-liter reservoir, 1.000 ml of the stock Pt(I1) solution
containing 168 p g Pt was pipetted into the brine and mixed.
this test solution was 5.1.

The pH of

The solution was deoxygenated with high-

purity nitrogen, and then, while the flow of nitrogen continued, brine
without platinum was pumped through the cell, most of the air bubbles
were removed by tapping the cell, and the working electrode was
preconditioned for a few minutes by polarization at the test reduction
potential. Then, without interrupting the electrolysis current, and
after at least 15-min. deoxygenation, the stopcock was turned to begin
the flow of Pt-containing brine to the cell.
The potentiostat was an EG&G Princeton Applied Research Model 173
with Model 176 Current Follower. Currents were integrated using an ECO
( b e l ) Model 731 Uigital Integrator. All experiments were carried out at
an ambient temperature of 22-25OC.
After the electrolysis, the Tefzel tubing surrounding the RVC
i'

electrode was cut, and the KVC was flushed thoroughly and quickly with
water. The KVC sample was then placed in a HN03-cleaned polyethylene
vial and dried in a desiccator. The samples were analyzed for platinum
by neutron activation analysis by General Activation Analysis, Inc. (San
-7-

Diego) u s i n g t h e f o l l o w i n g procedure.

The samp es p l u s comparator

standards were i r r a d i a t e d f o r 30 min. i n a T R I G

n/cm 2 -sec.

lo1

a t a f l u x o f 1.8 x

w i t h a h a l f - l i f e o f 3.15 days.

Mark I n u c l e a r r e a c t o r

The element p l a t i n u m produces gold-199

A f t e r a decay o f n i n e days, t h e samples

were counted on a Ge(Li) d e t e c t o r coupled t o a m u l t i c h a n n e l gamma-ray

spectrometer.
0.5

The l i m i t o f d e t e c t i o n o f p l a t i n u m i n t h e R V C samples was

pg.

R e s u l t s and D i s c u s s i o n o f Voltammetric Experiments

The predominant species o f p l a t i n u m t h a t would be p r e s e n t i n t h e

2-

, depending

whether p l a t i n u m i s p r e s e n t as t h e +4 o r +2 o x i d a t i o n s t a t e .

Reduction

c o n c e n t r a t e d - h a l i d e geothermal b r i n e s a r e PtC16

2-

or PtCI4

i n

o f t h e these species a t a cathoae wou d i n v o l v e t h e r e a c t i o n s :

PtCl6-

+ 4e-

P t metal + 6 C1-

(3)

R e a c t i o n s ( 1 ) and ( 2 ) would r e p r e s e n t t h e e l e c t r o d e p o s i t i o n process if i t

o c c u r r e d as a stepwise r e d u c t i o n of t h e P t ( I V ) t h r o u g h P t ( I 1 ) t o P t ( 0 ) ;
o r R e a c t i o n ( 3 ) would r e p r e s e n t t h e process i f P t ( I V ) were reduced
d i r e c t l y t o t h e metal.

R e a c t i o n ( 2 ) corresponds t o t h e r e d u c t i o n o f

P t ( 1 I ) t o t h e metal.
There i s some disagreement i n t h e l i t e r a t u r e as t o t h e e x a c t values
of t h e standard p o t e n t i a l s of Reactions 1 t o 3 ( M i l a z z o and C a r o l i , 1978;
L l o p i s and Colom, 1976; Lingane, 1958).

However, a l l o f t h e values f o r

c h l o r i d e media l i e between +0.5 and +0.75 V v s . t h e standard hydrogen

e l e c t r o d e (SHE),

and i t m i g h t be expected t h a t t h e e l e c t r o d e p o s i t i o n o f
-8-

platinum could be effected at quite positive, or at least relatively low

negative potentials.

Unfortunately, however, both polarographic and

voltammetric studies (Llopis and Colom, 1976, et seq.) have revealed that
a rather large overpotential is associated with these reactions at
practical current densities. Although there are no reported
investigations of the voltammetry of platinum using carbon electrodes, or
b

in strong halide media, several studies of the reduction of platinum

chlorocomplexes at platinum metal electrodes (Llopis and Colom, 1976)
have shown that reactions (l),
-0.2 to -0.4 V vs. SHE.

(Z), and ( 3 ) take place in the vicinity of

Accordingly, we anticipated in our studies with

vitreous carbon that we would also be dealing with this electrode

potential region. A practical difficulty with this characteristic is
that hydrogen ion is also reduced (to H2 gas) in this potential region,
and this process would tend to obscure and interfere with the platinum
electrodeposition to a greater extent as the solution pH is lowered. Our
hope, therefore, was to demonstrate that platinum could be quantitatively
deposited from solutions under typical hypersaline geothermal brine
conditions, without consumption of a large fraction of the current by
hydrogen ion reduction.
Our examination of the voltammetry of platinum was limited in the
present work to one specific set of brine conditions: 3 M ($15 wt % )
WaCl, a pH range of 4 to 6, and ambient ( 2 2 - 2 5 O C ; )

temperatures. Higher

temperatures such as those typical o f real geothermal fluids would not be

expected to change the relevant electrode potentials or reaction
("

characteristics significantly, thus it was felt that ambient temperature

tests would be sufficient to determine whether the electrolytic approach
was promising. Atmospheric-flashed hypersaline brine has a pH of 5 to 6,
thus the acidity conditions of these experiments are typical of those
-9-

found in the field. Because of the stability of the platinum

chlorocomplexes, any chloride concentration in the range of 0.2 to 4 M

probably would yield about the same characteristics for the platinum
species electrochemistry. What is not definitely known is the oxidation
state of the platinum in the real geothermal brine, but because the brine
is anoxic, contains H2S, and is generally mildly reducing even after
loss of the H2S through flashing, the platinum is probably present as
Pt(I1).

However, the characteristics of both Pt(1V) and Pt(I1) were

briefly investigated to learn the effect of the platinum speciation on

the electrodeposition process.
Figure 2 shows the results of a series of voltammetric scans of a
solution of Pt(I1) as PtClt- in 3 M NaC1.

Note that this solution of

platinum corresponds to 400 ppm Pt vs. the 50 ppb Pt or less that might
be present in a real geothermal brine.

It is necessary to use these

higher concentrations of platinum to study its electrochemical

characteristics because the typical background currents in voltammetry
would completely obscure the platinum reduction at concentrations below

1 ppm.

Figure 2 shows a series of successive scans of potential,

starting with a clean, bare, glassy-carbon electrode. As each scan was

completed, the potentiostat was disconnected and the solution stirred
briefly.

Then the succeeding scan was initiated with a quiet solution.

Very little reduction of the Pt(I1) is evident at first, but as platinum

metal accumulates on the electrode (in effect making it a platinum
electrode), it becomes easier to reduce the Pt(I1) species, and the
height of the current peak seen in Fig. 2 increases. Apparently the rate
of reduction of Pt(I1) on a pure glassy carbon surface is very low, thus
it would be necessary in an efficient recovery process to first
predeposit platinum on the electrode to ensure rapid subsequent
deposition of the platinum to be recovered.
-10-

100 p A
I

I
0.4

0.2

-0.2

-0.4

-0.6

-0.8

-1.0

-1.2

Potential, V vs. Ag-ASCI

F i g u r e 2.

RedGction o f P t ( I 1 ) t o P t ( 0 ) on a g l a s s y carbon e l e c t r o d e i n
3M (s15 wt.%) NaC1.
P t ( I r ) = 2 x 10-3 M

-11-

Scan Rate = 100 mV/sec

The p o t e n t i a l r e g i o n where P t ( I 1 ) i s reduced i s i n general agreement

w i t h p r e v i o u s work u s i n g p l a t i n u m e l e c t r o d e s as n o t e d above.
Ag-AgC1 r e f e r e n c e e l e c t r o d e i s +0.2 V vs. t h e SHE).

(The

The n e a r l y v e r t i c a l

r i s e i n c u r r e n t a t -0.85 V ( F i g . 2) i s due t o t h e r e d u c t i o n o f hydrogen

i o n t o hydrogen gas, t h u s i t i s r a t h e r c l o s e t o t h e p o t e n t i a l r e q u i r e d t o
P

reduce t h e P t ( 11).
The p l a t i n u m metal t h a t has been d e p o s i t e d on t h e g l a s s y carbon

e l e c t r o d e can be removed b y e l e c t r o l y t i c s t r i p p i n g as shown b y t h e curves

o f F i g . 3.

I n these experiments, t h e p l a t i n u m was d e p o s i t e d f o r a g i v e n

l e n g t h o f t i m e b y h o l d i n g t h e e l e c t r o d e a t -0.7
solution by the bubbling o f nitrogen.

V with agitation o f the

The s o l u t i o n i n t h e c e l l was t h e n

M b r i n e n o t c o n t a i n i n g P t ( I I ) , and deoxygenation was

r e p l a c e d by 3 c a r r i e d o u t f o r 4 min. w h i l e t h e p o t e n t i a l o f -0.7 V was maintained on
t h e electrode.
-0.7

Then t h e q u i e t , deoxygenated s o l u t i o n s were scanned f r o m

t o +0.5 V w i t h t h e r e s u l t s shown i n Fig. 3.

The f a c t t h a t t h e

p l a t i n u m can be removed i n t h i s manner m i g h t be u s e f u l i n an e l e c t r o l y t i c

r e c o v e r y process because t h e carbon e l e c t r o d e m a t e r i a l would n o t have t o
be destroyed and c o u l d be reused.
F i g u r e 4 shows t h e b e h a v i o r of Pt(1V) as PtC16
brine.
F i g . 2.

2-

i n the high-salinity

No background c u r r e n t c u r v e i s shown; i t i s t h e same as t h a t i n

The curves f o r p l a t i n u m r e d u c t i o n were o b t a i n e d i n a s e r i e s of

c o n s e c u t i v e scans s t a r t i n g w i t h a b a r e carbon surface, and again show t h e

increased r a t e o f r e d u c t i o n o f P t ( I 1 ) as p l a t i n u m metal b u i l d s up on t h e
electrode.

The f r s t peak i n F i g . 4, which i s due t o t h e r e d u c t i o n of

Pt(1V) t o P t ( I I ) , i s a p p a r e n t l y n o t s e n s i t i v e t o t h e surface composition

o f t h e electrode.

No f u r t h e r work was done t o unravel t h e c o n t r i b u t i o n

o f t h e two consecutive r e a c t i o n s t o t h e c u r r e n t - p o t e n t i a l c h a r a c t e r i s t i c s ;
i t i s evident t h a t the constant-potential electrodeposition conditions

-1 2-

0.8

0.6

0.4

0.2

-0.2

-0.4

-0.6

-0.8

-1 .o

Potential, V vs. Ag-ASCI

Figure 3.

Anodic stripping of platinum from a glassy carbon electrode

M (c15 wt.%) NaC1.
in 3 Scan Rate
Peak 1:

TOO mV/sec

After 4 min deposition from Pt(I1) solution

Peak 2: After 20 min deposition from Pt(I1) solution

-13-

0.4

0.2

-0.2

-0.4

-0.6

-0.8

-1.0

-1.2

Potential, V vs. Ag-AgCI

F i g u r e 4.

Reduction o f P t ( I V ) t o P t ( I 1 ) and P t ( 0 ) on a g l a s s y carbon

M (*15 wt.%) NaC1.
electrode i n 3 M
P t ( 1 v ) = 2 x 10-3 -

Scan Rate = 100 mV/sec

Peak 1:

Peak 2:

Pt(IV)

Pt(I1)

- 14-

(Pt(I1)

.+

Pt(0)

must be selected to ensure that Pt(I1) is reduced, whether the geothermal

platinum is present as either Pt(I1) or Pt(1V).

Results and Discussion of Platinum Recovery Experiments

Based on the results of the voltammetric measurements, it is obvious
*

that the control potential would have to be at least as negative as

i

-0.6 V vs. Ag-AgC1 for complete electrodeposition of the platinum.

The

two complicating factors are the need to predeposit platinum t o

"sensitize" the carbon electrode and the proximity of the platinum
reduction wave to that of hydrogen ion. A series of electrolytic
recovery experiments were performed, first at -0.60 V to examine the
effect of RVC porosity and flow rate, and then at more negative
potentials. The results are presented in Table 1.
These results show that the recovery of platinum was not very
sensitive to the porosity (surface area) of the RVC, but was influenced
significantly by the flow rate. The lowest flow rate, 1 ml/min, was
comparable to the flow rate found by Strohl and Curran (1979) to be
necessary for quantitative electrolysis of several other species using
the

same porosity and similar size electrode o f RVC.

No

preplating

of

platinum on the electrode was performed before the experimental runs,

thus some of the lower recoveries found for the faster flow rates was due
to

this. At the lowest flow rate, ~ 1 h7 was required for a run; this

was believed to include enough time for.sensitization of the electrode

'I

without loss of a significant fraction o f the platinum.

The data in Table 1 also show that, even at the most negative
potential, -0.80 V, the % recovery of the platinum was still relatively
poor.

It is known that, because of the positioning of the counter and

reference electrodes, the actual potential on the interior of the RVC

-1 5-

Table 1.

Recovery o f P l a t i n u m f r o m NaCl B r i n e b y E l e c t r o l y t i c Reduction.

NaCl : 3 M (%15 w t % )

P t Taken: 168 pg as PtC142-

P t Concentration: 168 pg/l i t e r

pH: 5.1

Flow

Working E l e c t r o d e

R VC

P o t e n t i a l , V vs

Porosity

Rate

P t Recovered

Ag-AgCl

Grade

Recov e r y

m l/mi n

'6

<o. 5

none (blank)
-0.60

4 5s
4 5s

11.5
11.5

none ( b l a n k )
-0.60

100s
100s

11.5
11.5

none ( b l a n k )
-0.60

4 5s
4 5s

3.9
3.9

(0.5
5.2,4.9

3.1

none ( b l a n k )
-0.60

100s
100s

3.9
3.9

<O. 5
7.4. 7.8

4.5

non ( b l a n k )
-0.60

4 5s
4 5s

1 .o
1 .o

(0.5
19,11

none ( b l a n k )
-0.60

100s
100s

1 .o
1 .o

(0.5
12912

100s
100s

1 .o
1 .o

22
29,33

13
18

-0.75
-0.80

-1 6-

2.0,

1.8,

<o.
1.6,

5
1.3

1.9

1.1
0.8

matrix is less negative than the control potential at the exterior edges
(Fleischmann and Oldfield, 1971).

In general, this can be compensated by

employing a significantly more negative control potential. However, in

this instance we must try to establish as negative a potential as
possible for complete platinum reduction on the interior surfaces of the
RVC, while minimizing hydrogen ion reduction and gas evolution on the
edges. At the pH of this brine, 5 to 6, and conceivable, practical
electrolysis cell designs, this would be very difficult to achieve.
A control potential still more negative than -0.80 V could be used,
but then additional electrolysis current would be wasted.

In our

experiments, initial currents were 4-8 mA at -0.60 V and 15-30 mA at

-0.80

V.

In every experiment, the current decayed to ~ 0 . 5mA at the

end of the electrolysis. The reason for this decay or apparent

"desensitization" is not known; however, it should be noted that many of
the impurities in the NaCl that was used to prepare the brine also would
be codeposited with platinum under these conditions. Based on the
measured total charge that was passed, at the flow rate of 1.0 ml/min,
the average current was ~ 0 . 7mA at -0.60 V and ~2 mA at -0.80 V.
comparison, only -2 PA would

be

By

consumed in quantitatively depositing

163 ug of platinum, thus the current efficiency of the process here was

very low.

Real geothermal brines containing additional trace metals

would require still more current; however, if the recovery were carried
out using controlled-potential techniques, only Pb( 11), which is found at
-50-100mg/l concentrations in hypersaliie geothermal brines, would be

important. Copper, gold, silver, and cadmium, if present, also would

codeposit; but manganese and zinc, which are present n high
concentrations in some brines, woula reqJire potentia s more negative
than -1.0 V vs. Ag-AgC1 (Kolthoff and Liligane, '1952).
-1 7-

Conclusions
Our objective in these experiments was to determine whether platinum,
as the chlorocomplex in high-salinity brine, could be deposited
electrolytically as the metal on a relatively inexpensive substrate with
reasonable current efficiency. Reticulated vitreous carbon was found to
be a convenient material to use as a working electrode, and
electrodeposition o f the platinum was clearly observed at millimolar
concentrations (a few hundred ppm).

However, the process was found to

require a significant overpotential, especially at the uncoated carbon

surface. For the slightly acidic solutions typical of the hypersaline
geothermal brine, the required control potential is close to that o f the
reduction of hydrogen ion. The current and energy efficiency of the
process were thus unacceptably low for the very low concentration level
(<1 ppm) found in the geothermal brine.

If the pH of geothermal brine that could be used as the input to the

recovery process were higher, e.g., neutral or slightly alkaline, or if
the concentrations of platinum in the brines were higher, then the
electrodeposition technique would become much more favorable. A more
negative control potential could then be used to obtain quantitative
deposition of the platinum, and the interference by hydrogen-ion
reduction would be lessened. Deliberately raising the pH of a geothermal
brine in a processing plant by the addition of alkali, merely to
facilitate platinum recovery, would not, however, prove to be economical,
because of the amount of alkali that would be required. If the
electrolytic removal o f platinum had been successful, it is probable that
the platinum could also be stripped from the carbon electrolytically by
changing the control potential, thus avoiding destruction o f the
deposition substrate.
-1 8-

It appears that the activated charcoal extraction technique

investigated by Raber, Thompson, and Gregg (1984) should be the method

o f choice for precious metal recovery.

Acknowledgement
4

H. C. Crampton assisted
L

in the fabrication o f the flow-through

electrolysis cell.

-7 9-

References
Acton, C.F.,

1982.

"The Technology o f Gold and S i l v e r E x t r a c t i o n , " i n

Sohn, S.D.

Processing of Energy and M e t a l l i c M a t e r i a l s , H.Y.

J.M.

Wie, and K.V.S.

Sastry, Eds.,

Hill,

American I n s t i t u t e of Chemical

Engineers, Symp. Series No. 216, Vol. 78, American I n s t i t u t e o f Chemical

Engineers, New York.

and Newman, J.,

Bennion, D.N.,

1972.

Electrochemical Removal o f Copper,

Ions f r o m Very D i l u t e S o l u t i o n s , J. Appl. Electrochem.,

Coeuret, F.,

1980.

113.

The F l u i d i z e d Bed E l e c t r o d e f o r t h e Continuous

Recovery o f Metals, J. Appl. Electrochem.,

E t t e l , V.A.,

2,

and T i l a k , B.V.,

1981.

10,687.

' I E l e c t r o l y t i c R e f i n i n g and Winning

of Metals," i n Comprehensive T r e a t i s e of Electrochemistry, Vol. 2,

Electrochemical Processing, J.O'M.
R. E. White, Eds.,

Fleischmann, M.,
Electroanal

Habashi ,

Bockris, B.E.

Conway, E. Yeager, and

Plenum Press, New York.

and O l d f i e l d , J.W.,

. Chem.,

F., 1982.

29,

1971.

Fluidized-Bed Electrodes, J.

21 1.

Hydrometallurgy, Chem. Eng. News, February 8,

pp. 46-58.

Harrar, J.E.,

and Raber, E.,

1983.

Chemical Analyses o f Geothermal

Waters and S t r a t e g i c Petroleum Reserve B r i n e s f o r S t r a t e g i c and Precious

Metals, Lawrence Livermore N a t i o n a l Laboratory P r e p r i n t UCRL-88575,
Rev. 1; June.

- 20-

Kolthoff, I.M., and Lingane, J.J.,

1952. Polarography, 2nd Ed.,

Interscience, New York, Vol. 2, pp. 468,504.

Kuhn, A.T.,

1972. "The Electrochemical Treatment of Aqueous Effluent

Streams," in Electrochemistry of Cleaner Environments, J.O'M. Bockris,

-4

Ed. , Plenum Press, New York, Chapt. 4.

Lingane, J.J.,

1958. Electroanalytical Chemistry, 2nd Ed., Interscience,

New York, p. 647.

Llopis, J.F., and Colom, F., 1976. "Platinum", in Encyclopedia of

Electrochemistry o f the Elements, A.J. Bard, Ed., Marcel Dekker,
New York, Vol VI, Chapter VI-4.

Maimoni, A., 1983. Minerals Recovery from Salton Sea Geothermal Brines:

A Literature Review and Proposed Cementation Process, Geothermics, 11,

239.

Milazzo, G., and Caroli, S.,

1978. Tables of Standard Electrode

Potentials, J. Wiley, New York.

Murthy, R.S.S.,
I

Holzbecher, J., and Ryan, D.E., 1982. Trace Element

Preconcentration from Aqueous Solutions on a Solid Phase, Rev. Anal.

Chem. (Israel), -6, 113.

Raber, E., Thompson, R.T., and Gregg, D.W. 1984. An Evaluation of

Sorbents for Removal of Platinum from Geothermal Bkine, Lawrence
Livermore National Laboratory Preprint.
-21-

Strohl, A.N.,

and Curran, D. J., 1979.

Reticulated Vitreous Carbon

51, 353.
Flow-Through Electrodes, Anal. Chem., -

Wang, J.,

1981. Reticulated Vitreous Carbon

Material, Electrochim. Acta,

-- A

new Versitile Electrode

26, 1721.
i

Wang, J., and Dewald, H.D.,

1983. Deposition o f Metals at a Flow-Through

Reticulated Vitreous Carbon Electrode Coupled with On-line Monitoring o f

the Effluent, 3. Electrochem. SOC.,

130. 1814.

-22-

_ _

_ _

~~

~~
~~

_-

_-

- - - -

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