A new technique
for the recovery of
PALLADIUM
AND PLATINUM
FROM GOLD ELECTROLYTE
by E. M. Elkin and P. W. Bennett
A new technique for the recovery of palladium and platinum and sludge
from gold electrolyte eliminates many of the drawbacks of the zinc-dust
cementation process.
I nmethod,
the electrolytic refining of gold by the Wohwill
the electrolyte contains about 100 gpl gold
as AuCL. and 100 gpl free hydrochloric acid. Any
palladium and platinum contained in impure gold
dissolve and accumulate in the electrolyte. When their
concentration approaches that of gold, it becomes
desirable to discard the electrolyte and to recover
the gold and the palladium and platinum.
As practiced at Canadian Copper Refiners until
recently, discarded electrolyte was treated with sulfur
dioxide to precipitate the gold.
2AuCI. + 6H.0 + 380 2 ~ 2Au + 6HCI + 3H.SO.
The gold precipitate was filtered off, washed with
water, and melted with scrap anodes.
The wash water was added to the gold-free filtrate
and treated with zinc dust to cement the palladium
and platinum.
PdCI. + Zn ~ Pd + ZnCl 2
PtCI. + 2Zn ~ Pt + 2ZnCL,
The precipitate was separated and sold as pal-
ladium-platinum concentrate, and the barren filtrate
and wash water were discarded. The receipts of
palladium and platinum at this company were too
small to warrant their refining.
The process suffered from a number of disadvan-
tages. Handling the gold-free solution was disagree-
able, as it was laden with sulfur dioxide even after
blowing with air overnight. Subsequent treatment
with zinc dust was also troublesome. A large excess
of zinc dust was required. Spray, acid mist, and vigor-
ous evolution of hydrogen accompanied the reaction.
The palladium-platinum precipitate was grossly con-
taminated with occluded unreacted zinc and with
yellow granules of sulfur, thought to be formed by
the reduction of sulfur dioxide and its derivatives.
E. M. ELKIN and P. W. BENNETT are research supervisor and chief
chemist, respectively, for Canadian Copper Refiners Ltd. Montreal
East, Quebec, Canada. This paper was presented at the 94th AI ME
Annual Meeting.
252-JOURNAL OF METALS, MARCH 1965
Repeated boiling of the precipitate with hydrochloric
acid and washing with water decreased somewhat,
but did not eliminate, the zinc.
After drying overnight, the precipitate hardened
to a clinker-like mass that was difficult to grind.
Grinding, handling, and packing created heavy dust-
ing. Even weighing in an analytical balance gen-
erated dust, indicating that the powder was easily
charged with static electricity. The total palladium
and platinum content of the powder varied from 56 %
to 72%, with an average of 65%. The powder dis-
solved in aqua regia with difficulty, leaving a small
amount of insoluble residue.
However, the main drawback of the process was
the strongly hygroscopic palladium-platinum product.
The powder showed a marked though erratic increase
in weight and a corresponding decrease in assay on
exposure to air, even during the course of laboratory
analysis. Such changes were the source of disagree-
ment between Canadian Copper Refiners and the
buyers of concentrate. The cause of the change in
weight is believed to be hydrogen, liberated by the
action of zinc dust on hydrochloric acid. Some of this
hydrogen was adsorbed so strongly by the precipitate
that it could not be driven off during the drying. On
exposure to air it oxidized catalytically, forming
water.
Experiments soon showed that the entire process
of treatment of discarded electrolyte then in use
would have to be changed. A small quantity of ap-
paratus was moved into the gold room, and experi-
mentation was held to a minimum compatible with
the development of a new process.
PALLADIUM AND PLATINUM
PRECIPITATION
It was thought that zinc could be replaced with a
reagent other than a hydrogen-evolving metal.
Semi-quantitative experiments showed that plat-
inum and palladium could be precipitated completely
from the gold-free solutions with such well known
reagents as sodium formate, formic acid, formalde-
hyde, and paraformaldehyde. Sodium formate was the
preferred reagent, since the other three are volatile
and somewhat toxic. The gold-free solutions used
were those saturated with sulfur dioxide, partly freed
of sulfur dioxide by aerating overnight, completely
freed by boiling, as well as strongly and weakly acidic,
neutral, and alkaline solutions.
The reactions are complex and can be represented
by these overall equations:
PdCI. + HCOONa ~ Pd + NaCI + HCI + CO,
PtCI. + 2HCOONa ~ Pt + 2NaCI + 2HCI + 2CO z
With solutions originally containing sulfur dioxide,
the results were erratic and not reproducible. Con-
sumption of sodium formate was markedly higher
than with solutions free of sulfur dioxide.
Since boiling the solution to drive off the sulfur
dioxide was not practical under the gold refining
conditions, it was decided to precipitate the gold with
a reagent other than sulfur dioxide.
GOLD PRECIPITATION
Hydrogen Peroxide:
2AuCls + 3H 0 z ~ 2Au + 6HCI + 30
2 2

Strongly acidic solutions required as much as five
times the theoretical amount of sodium formate as
did solutions neutralized to pH 4.5.
Increasing the pH decreased the consumption of
precipitant. At a pH of approximately 6 with mild
agitation, the reaction was over in about 10 min.
The finely-divided black precipitate settled rapidly
leaving a clear white or, when contaminated with
Fe H and NiH ions, a greenish solution free of palladium
and platinum. The precipitate was washed easily on
a suction filter and dried to an easily friable cake that
A very large excess of hydrogen peroxide was re-
quired. The unreacted reagent increased the sodium
formate consumption in palladium-platinum precipi-
tation. Under refinery conditions, a much larger
volume of solution would have to be handled. Working
with large amounts of a strong liquid oxidant in a
rather crowded room was thought to be unsafe.
Ferrous Sulfate
AuCI. + 3FeSO. ~ Au + Fe (SO.). + FeCI.
2

had a combined Pd-Pt content of 95-96%. The prod-
uct did not gain weight on exposure to air and dis-
solved readily in aqua regia.
In neutral and alkaline solutions, the Pd-Pt con-
tent of the precipitate decreased to approximately
82 %; and the precipitate was hygroscopic.
As with hydrogen peroxide, a large excess of re-
agent was required. The precipitate was very finely
divided and showed tendency to pass through filter
paper. The gold-free solution was laden with ferric
salts. The palladium-platinum precipitate from this
solution was somewhat hygroscopic.

GOLD ELECTROLYTE
CAUSTIC SODA
OXALIC ACID

_ST_E_A_M_.) -.l-ST PRECIPITATE TO

~ GOLD SCRAP CRUCIBLE

1------1 ) 2-Nq. PRECIPITATE TO

~ DORE FURNACE

!
Flow sheet for recovery of palladium
and platinum from gold electrolyte.
GOLD-FREE SOLUTION
CAUSTIC SODA
SODIUM FORMATE I
----
STEAM
..~tlJ
WATER l
[J-----J
PALLADIUM -PLATINUM
PRECIPITATE l
~ DRYER
WASH WATER
TO WASTE
~
DRY CONCENTRATE
TO MARKET

MARCH 1965, JOURNAL OF METALS-253