Saturated Saline & Nitric Acid

There are a number of leaches based upon salt
water but none have shown the kinetics that
SSN demonstrates. In one leach the oxida-
tion potential is created by a combination of
hydrochloric acid and ferric chloride; in an-
other leach hydrochloric alone is used and in
the third electrolytic are employed to create
molecular chlorine. Pourbaix diagrams show
that each of these leaches will dissolve gold;
however, the diagrams will not show the
kinetic behavior involved (speed of lixivia-
tion). This behavior can only be demonstrated
by testing and SSN wins hands down. We
will look into the behavior of this unique
leach one aspect at a time.
chemical supply house. For laboratory ex-
periments you will probably use the nitric
acid provided from a scientific supply, which
is quite expensive compared to the side of
quantity purchase. For example one bottle of
nitric acid (71bs) is, at todays cost, $64 and if
you bought a 55gal drum the same 71bs of
acid would cost only $2.10. Salt may be
bought at $ 1.10 per 501b bag at the hardware
store, and $25 per ton in truck load lots. To
make it simple: check on the commercial
prices in your locale when you calculate
leach cost for production runs, In our area it
could be as low as $0.07 per gallon.
COMPOUNDING THE LEACH
SSN is based upon saturated salt water which
means water with every bit of salt that it will
dissolve at normal temperature and pressure.
The easiest way to create saturated brine
water is to place approximately 3 lbs of rock
salt per gallon of water in a vessel and let it
dissolve. It helps to stir it occasionally. Just
use ordinary tap water for this. Decant the
brine water from any remaining salt (filter if
there is suspended trash from the rock salt).
This is the prime liquor and it is ready to go.
CHEMICALS NEEDED FOR
THIS LEACH
You will need rock salt--not table salt, but
rock salt like you use for water softeners or tc
clear ice from the highway. You will neec
full strength nitric acid (65-70%). Both of
these may be purchased from an industrial
Temperature
apparently not accidental for we repeated the
series and the results were the same.
It is now time to choose a ratio of nitric acid
to saturated brine water. The low end of the
reactions is 20 saturated salt water (SS) to 1
nitric acid (N). [SSN=20:1]. At the top end
we have a ratio of 7 SS to 1 N [SSN=7:1].
The top was determined by tests that show
when SSN=6:1 the amount of gold dissolved
is reduced. In other words there is a point at
which the chemistry turns negative.
When running these tests we attempted to
limit the variables to one and in the following
case that variable was acid ratio, A gold plate
that was 750 fine and an exposed surface area
of 2 square centimeters was used. The 18K
gold behaves more like a nugget than pure
gold and the set amount of surface defines the
other dimension. Temperature was held con-
stant at 31.1° C (88° F)
The left hand column of the graph represents
the milligrams of gold per square centimeter
of gold surface per hour, at 31.1 * C. Across
the bottom is the ratio on nitric acid to Brine.
Starting at SSN=7:1 on the left and ending
with SSN =1:19 on the right. One cannot help
but note the sudden rise between 1:16 and
1:13 and again between 1:10 and 1:7. This is
This graph shows the reaction of SSN with
respect to heat. The left column of figures
represents milligrams of gold leached from
one square centimeter, per hour of exposure.
Reading across the bottom of the graph each
number is equivalent to a ten degree centi-
grade increase in working temperature. The
graph covers 10° C to 90° C. Eighty degrees
Centigrade (176° F) is the highest practical
temperature due to volatilization of fluids.
The upper arc represents SSN at 7:1 and the
lower arc equals SSN at 20:1. The increased
chemical activity is a geometric progression
by two for each unit of 11 to 13 degrees C.
Molality m Pressure p
mol / kg bar
N I.440E+00 N 1.OOOE+00
Na 6.000E+00 Na I.OOOE+00
Cl 6.O00E+0O CI 1OOOE+00
Pourbaix Diagrams (EpH Diagrams) are an excellent
means of visualizing the what, where, and when of
chemical reactions. First it would be advantageous to
explain a few things for those readers who are not
familiar with these diagrams.
Down the Left side you will see the Eh listed as a
voltage. Chemical species by chemical species,
element by element; these are the same as you would
find in the electromotive series as listed in CRC, or
some other reference book. Usually the diagram is
drawn showing from +2.00 to -2.00 volts but we wish
to have a clear view of the area of interest so we ask
the computer to draw only that area above 0.00 volts.
Across the bottom pH is listed and again we have
made a request that instead of the traditional 0 to 14
listing we required an extra two molar on the acid side
and only pH 8 on the alkaline side. The minus
numbers
to the left of 0 represent one mole of acid per number,
in other words one mole of acid would represent a pH
of 0,01 and a second mole would take the pH to -1.0.
The suffix following each chemical species denotes its
state of existence. When there is no parenthetic tetter
the species is a solid crystal. Inmost EpH diagrams
the following designations are used: (a) aqueous, (1)
liquid {such as mercury], (g) gas, (none) solid.
Across the top the first element listed is the element
of interest and the diagram is used to show its
behavior under the chemical, physical and thermal
situation as defined by the temperature (at the top
right) and pressure (at the bottom). By performing
literally millions of calculations the diagram emerges
and we can see the status of (in this case) chlorine (as
combined for SSN) at any pH and Eh combination.
We have darkened the small area at the upper left so
that cationic chlorine will not be overlooked.
Molality m Pressure p
mol / kg bar
CI 4.000E+00 CI I.OOOE+00
Na 6.000E+00 Na I.OOOE+00
N 1440E+00 N I.OOOE+00
Did you notice that there were chlorine atoms
that were no longer associated with sodium
chloride? If you did not go back and look at
the diagram again.
The behavior of nitric acid (70%) in SSN is
the topic for this diagram. Nitrogen is there-
fore the element of interest. We are again
working at 80°C so that the maximum advan-
tage of the chemistry will be well defined. Do
not misconstrue that last statement for the
reaction is the same at 25° C but the tempera-
ture difference will come into play in the next
diagram and if the temperature remains the
same there is less chance of some one misun-
derstanding.
SSN leach solution contains in this instance
about 1.44 molar nitric acid, therefore, you
would expect to see a pH 0 when it is mea-
sured. This is not the case. Actually the pH
reads from pH 0.8 to pH 1.5. So far there is
nothing spectacular in the EpH diagrams, so
let's introduce a metal into the solution.
Molality m Pressure p
mol / kg bar
Au l.0OOE*0O Aul J.OO0E+00
N I.440E+00 N I.OOOE+00
Na 6.000E+00 Na I.OO0E+00
CI 1.O0OE+00 CI I.OOOE+00
Chlorine is still the prime element in this EpH
diagram, with gold as a secondary element.
The SSN leach will convert gold to sodium
aurochlorate NaAuCl
4
(a) but the energy
required shows up at the conventional 1.002
volts. The maximum pH should not exceed
-0.8 for good economics.
This diagram gives a good comparison with
the first one on page 3, but it should be used
for comparison of chlorine behavior and not
the behavior of gold in SSN @ 80° C. For the
true behavior we must consider gold as the
primary element. Turn to pagei 6.
Molality m Pressure p
mol / kg bar
I 6.000E+00 CI 1.0001+00
1.440E+Q0 N 1000E+00
a 6.000E+00 Na 1.000E+00
Au I.000E+00 Au I.000E+00
This is also the point at which any farther
drop in pH will result in a conversion to
Au
2
Oj if the ORP remains high and natural
precipitation of elemental gold if the ORP has
dropped below the line.
From experience; the working window of
normal observed pH has been shadowed so
that you have an actual visual target to ob-
serve.
Before we continue with the description of
the leaching process we will take a brief look
at each of the platinum group metals that are
affected.
With gold as the primary element you will
note some changes from the previous dia-
gram. The most important is the drop in
required ORP (Eh). It was previously run-
ning 1.002 volts and has now dropped to
approximately 0.890 volts making it much
easier to take gold into solution.
Molality m Pressure p
mol / kg bar
CI 6.000E+00 CI I.000E+0O
N I.440E+00 N I.000E+00
Na 6.000E+00 Na L000E+00
Pd I.000E+00 Pd 1.00E+08
Palladium is by all means the most suscep-
tible of the noble metals that dissolve in SSN
leach. In fact the window in which we are
working occupies only a small portion of the
window of opportunity. This metal will
dissolve at any point with a pH below 5.8 and
any Eh greater than 380 millivolts.
While stripping catalytic converter beads the
palladium dissolves with effervescence, turn-
ing the solution a light yellow orange. There
is no necessity to spend money on heating a
leach when palladium is the only element
sought.
Molality m Pressure p
mo! / kg bar
CI 6.000E+00 CI I.000E+00
N 1.440E+00 N I.000E+00
Na 6.000E+00 Na I.000E+00
Pt I.000E+00 Pt I.000E+00
Platinum shows a higher nobility than palla-
dium but takes less ORP in SSN leach than
gold. It needs only about 680 millivolts.
Again we have darkened the window through
which it appears that we are working. If the
Eh remains above 680 platinum will go into
solution clear up to a pH of 4.5. Should the
Eh drop below the 680 millivolt range and/or
the pH exceed 4.5 then the platinum will
precipitate.
Rhodium the most prized of the PGE's has a
much smaller active window but fortunately
it fits within the area in which SSN does its
best and most natural work. The ORP is not
as high as you would expect but the pH
window is quite narrow. Rhodium and alloys
of rhodium have leached without incident in
our experiments.
Molality m Pressure p
mol / kg bar
CI 6.000E+00 CI I.000E+00
N 1.440E+00 N I.000E+00
Na 6.000E+00 Na I.000E+00
Rh I.000E+00 Rh I.000E+00
Molality m Pressure p
mot / kg bar
CI 6.000E+00 CI I.000E+00
N I.440E+00 N I.000E+00
Na 6.000E+00 Na I.000E+00
Ir I.000E+00 Ir 1.000E+00
Iridium offers a very narrow window in
which to operate. In fact it is our opinion that
any iridium recovered will be happen chance
unless the circuit is specifically tailored for
that purpose.
There are exceptions, for instance any man-
ganese ore will generate the release of chlo-
rine gas (this is a common way of identifying
manganese ores).
A few magnetite samples have given off
nitrous oxide for a few minutes and then quit.
Remember if there are carbonates in the ore
you will have to pre-leach it in dilute HC1.
Please do not expect any acid based leach to
work with limestone or dolomite. Soils from
dry lake beds may suffer Prag robbing if the
clays are bentonitic in nature. If this is the fact
there is no leach known that will work.
Liquid Volume
The amount of leach liquor to the amount of
ore is of no great consequence, just as long as
the solution covers the ore. This is true from
raw ore to high concentrates. In fact if you
use a small surplus of liquid you should be
able to draft it off and use it several times
before attempting recovery. Be sure to keep
the rinse water for recovery, it will serve as
dilution water as well as carrying some val-
ues that were clinging to the rock surfaces.
RECOVERY
From our leach liquor we want to
recover gold, palladium, platinum &
rhodium (possibly iridium).
Here is where the practical method collides
head on with environmental considerations.
There are two chemicals that will give a
straightforward precipitation of the entire
group. Unfortunately they are top of the class
cancer causing agents and if you order them
you will be obliged to account, in writing as
well as actually, for every milligram of the
chemical used. Both chrome II sulfate and
vanadium II sulfate will precipitate all four
elements, along with the headaches.
USE A HOOD
For safety sake always use a hood or leach in
the open where fumes may be dissipated.
Most of the ores that we have tested to date do
not give off noxious fumes.
ALL TOOLS THAT ARE USED MUST
BE; WOOD, PLASTIC, GLASS OR CE-
RAMIC. SSN has dissolved every metal that
we have tried thus far. SSN will destroy your
ORP probes by dissolving the platinum side
of the probe. It will also destroy the inexpen-
sive hand held meters. They will lock on to
a reading and stay there, which gives you a
false sense of knowing what is going on. To
date the best that we can offer is to keep track
of the pH and take it for granted that the ORP
is high enough to do the job until we devise
a new way to measure it. We might add that
the chances of overloading the leach with
noble metals is rather remote for its capacity
to retain values is tremendous.
A bucket , a barrel, a cattle tank, a plastic
mortar box, even a plastic lined trench,
should do the job. For 4 kilo leaches we use
a two inch tower and allow the leach to move
through the ground ore by gravity. It is
continuously pumped to the top and allowed
to circulate.
Tools needed
SSN is the first leach that we have encoun-
tered which performs better as a stagnant
leach rather than an agitated leach. The best
results have been derived from a slow trickle
top to bottom as one would expect from a
heap leach. The main difference is that you
would need weep hoses and a covered heap
so that the salt would not build up from
evaporation. When working with one kilo-
grams or less a straight forward stagnate
leach has given excellent results.
Formic acid will precipitate gold, palladium
& platinum but not the most valuable which
is rhodium. The only choice left is cementa-
tion (exchange) with a metal lower upon the
electromotive series. Zinc is the best choice,
the least expensive and the easiest to use.
Traditionally lead sulfate is used so as to keep
the iron in a reduced state. (This keeps iron
from precipitating as Fe
2
0
3
-red iron oxide).
This chemical is also a social no-no for it is
used by the druggies in making MET and if
you order it the FBI will check you out six
ways from Sunday. This leaves us an old
fashion straightforward zinc and cleanup.
Start with the leach liquor diluted with the
rinse water (at least two to one rinse to
pregnant solution). Place it in a vessel and
agitate it well. Check the pH of the solution.
It should be somewhere near pH 1.5. If it is
not use 10% sodium hydroxide and bring it
between 1.5 and 2.0.
Weigh out five and one half grams of zinc
for each liter of solution (21gm/Gal.). For
assay or testing that wouldbe0.55gm/100ml.
Divide the zinc into three beakers: 1/4—1/4-
--1/2.
Add water to the first 1/4 of the zinc and stir
well. (This wets the zinc so that there is no
gaseous insulation or bubble entrapment to
insulate the zinc from contact with the preg-
nant solution). Using several short shots of
the well stirred zinc add this to the diluted
leach liquor. Allow five to 10 seconds be-
tween each shot.
Wet the second 1/4 batch of the zinc and
repeat the last scenario in five to 10 second
shots. If red iron oxide forms just ignore it.
The final l/2ofthezinc should be wetted and
time allowed for any remaining efferves-
cence to subside within the leach liquor.
When the solution is quiescent pour in the
zinc while still stirring it. Most of this zinc is
surplus but it is best to be sure that you collect
the total values from the solution.
Place the solution where it will be warmed
but preferably not boiled. ( This will hasten
the chemical equilibrium and tighten the floe
that forms. Grant about thirty minutes for the
reaction to take place and then allow the floe
to settle. Carefully decant the spent solution
and discard it. Add 5% HC1 to dissolve the
hydroxides that formed and part of the excess
zinc. Allow the material to settle and decant
the greater part of the acid water.
Use 5% to 8% HC1 to dissolve the excess zinc
and unwanted metals. All that remain are
copper, mercury, gold, palladium, platinum,
rhodium and iridium. Filter the solution
through a tight filter such as Whatman #50 or
a boro-silicate glass such as GF/A. Rinse the
filter well and wipe the walls of the precipi-
tation vessel with apiece of damp filter paper
or a second GF/A filter.
In the absence of copper &/ or mercury the
filter may be ashed in a lead boat or the GF/
A placed in lead foil. Fold the foil carefully
and cupel it. The resulting bead will be noble
metals. Should copper &/ or mercury be
present in small quantities the material, filter
and all, should be placed in a crucible, mixed
in with flux (any kind) and fired to a button.
Cupel the button.
High contaminations of copper and mercury
will necessitate that the prepipitates be dis-
solved in aqua regia neutralized to pH 7.5-8.0
with sodium hydroxide filtered and acidified
with a small amount of hydrochloric acid.
Treat this solution as you would any aqua
regia solution.
#
Only sodium hydroxide will drop copper,

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