Silver 101 Scrap, Recovery & Refining

Introduction
Written by Gold-N-Scrap
Published: 09 September 2011

Vote 5 Rate

Silver (AKA poor mans Gold), amongst the 8 precious metals (Gold, Silver, Platinum, Palladium,
Rhodium, Ruthenium, Iridium,
Osmium) is probably the most used metal in the different industries, e.g. -
electronics/electrical/jewelry/photography/printing etc' and
with good reasons.

Despite Silver's low price, it holds superior physical properties over most other non precious metals.
In most applications Silver is used as part of an alloy rather then in pure form (mainly due to its high
malleability), it is then when its physical properties are shown in all of their glory, in terms of electrical
and thermal conductivity, oxidation resistance, jewelry and jewelry coloration.

Examples: Electrical contact point, high temp' solder, electrodes, green gold and more

Silver and its compounds have countless other applications in all sorts of fields, Such as: Jewelry,
silver plating applications, laboratory usage as catalysts, film and printing (fixer solutions, litho
printing), Dental works, Gold and Platinum group metals refining, water purification, cloud seeding,
cosmetics you name it the sheet is too short to count them all.

As you probably realized by now, Silver is all around us in our daily life and demand is ever growing.
Taking this information with some reports on dwindling worldwide Silver natural resources (assumed
to be even less availability then gold), one can truly appreciate holding on to Silver Bullion & Silver
bearing scrap.
In some cases silver scrap is not worth recovering (due to current low price of Silver) and in others it
does. It all depends on Silver availability within the scrap and how straight forward the recovery
process is.

In our recovery section, we will present in the following articles some of the main sources of Scrap
Silver, propose and demonstrate a recovery method for each source.
Here are a few examples for scrap silver:
- Spent Fixer solutions, Lithographic ink and x-ray films.
- Sterling Silver jewelry and flatware.
- Different Silver alloys.
- The use of Scrap Silver in Gold refining.
- Contact points

Same as any other noble metals, silver, once recovered needs to go thought a refining process, we
will also discuss the different refining routs that fits each recovery method and its product. The goal
of refining is of course achieving 999.5 fine silver, even though some methods are able to produce
999.9 Fine silver.
Examples for Silver refining methods:
- Metal displacement (using more reactive metals, also called cementing)
- Chemical reduction from Silver bearing solutions.
- Electrochemical deposition of silver bearing solution (i.e. silver cell)

Dou to Silver's rather unique chemical behavior, most refiners (including the writer) does have some
kind of love / hate relationship with Silver and its halides compounds (e.g. bromide, iodide and
chloride).

Why Hate? Silver halides are very insoluble and when formed, they tend to trap with them some
dissolved values from main liquor, they are quite inconvenient to handle and conversion methods to
elemental silver are usually long and tedious.

Why Love? Scrap silver comes cheap. Silver is sometimes a by product from other precious metals
recovery/refining efforts and in most cases is a freebie

Silver Refining First stage (Pt. 1)

Written by Gold-N-Scrap

Published: 06 December 2011

Vote 5 Rate
Our starting material for this demonstration is probably the simplest and most common case of silver
Recovery and Refining: A nitrate solution of silver and other metals.
The following process will describe how to separate the majority of metals contaminates from the
Silver and preparing the Silver for the final refining process, of electrowinning in a Silver cell to
produce 99.9 + Fine Silver.

The Silver Nitrate (AgNO3) solution may be obtained by the different recovery/ refining processes
such as Inquarting or dissolving Scrap Sterling Silver with dilute Nitric Acid and other sources of
Silver bearing Scrap such as electronics.

The following metals are the usual contaminates in most solutions:

Copper (Cu), Nickel (Ni), Zinc (Zn), Lead (Pb), Palladium (Pd) and Platinum (Pt).
The concentration of each metal is, of course dependent on the starting scrap material.
{googleAds} {/googleAds}

Abstract of the process:

1. Filtering.
2. Palladium removal with DMG (optional).
3. Cementing the Silver with Copper.
4. Washing the Silver powder.
5. Melting and pouring anodes.
1. Filtering.
First, we must make sure the Silver bearing solution is free of any solids such as: ceramics, organic
material, glass, gold and platinum powders etc'
Filter the solution through filter paper into a clean and relatively graduated vessel.
Wash the filter well with Distilled water to drain all of the Silver bearing solution.

2. Palladium removal with DMG (optional).

It is not widely known, that most silver and gold karat scrap is slightly contaminated with Platinum
Group Metals (PGM) such as Platinum and Palladium in trace amounts, where the later one (Pd) is
the most common..
Luckily, there's a rather simple way for removing Pd from the acidic nitrate solution by adding few
drops of basic DMG (Dimethylglyoxime) solution and stirring well.

The DMG will selectively and quantitatively remove any traces of Pd in a form of fluffy orange/yellow
precipitate (looks like orange juice pulp) Pd[HDMG]2.

The reaction should not happen immediately, if it does, that means a high Pd content in the solution.
Allow the solution to stand for at least 24 hours for a complete reaction.
Of course, if there's no Pd in the solution, nothing will precipitate.
If Nickel is also in the solution, it will appear for a short while as a pinkish/red solid that will soon re-
dissolve upon stirring, as the Nickel-DMG complex is very soluble in acidic conditions.

You will notice that the Palladium precipitate will not settle completely, but remains as a "cloud" at
the bottom of the vessel.

Given enough time, say a week or so, at room temperature, some Platinum that may be present
will also precipitate in similar manner as the Palladium does. The only difference is the color, which
is blue.

Filter the solution through a clean filter paper. Again, use a rather graduated receiving vessel.
Try and keep the bulk of the Pd/Pt precipitates at the bottom of the vessel to be filtered last.
I have found that gravity filtration works best in this case, where vacuum filtration fails miserably, the
filter paper clogs immediately, rendering the process to a halt.
{googleAds}

{/googleAds}
The DMG Solution
Prepare 1N NaOH solution by dissolving 4 Grams of NaOH in 100 ml of distilled water.
To this solution add 5.8 Grams of DMG powder, and stir until completely dissolved.

43 ml of the prepared DMG solution will remove from solution 1 Gram of Palladium.
Approximating that 1 drop equals to about 0.2ml, each drop of this DMG solution will remove about
0.0046 Grams, or 4.6 mg of Palladium from solution.

Of course, you can play with the proportions of DMG in the solution to whatever suits you. A 1N (1
molar concentration) NaOH solution is capable of dissolving up to 11.6 grams of DMG.

Assuming that Palladium/Platinum presence in solution is only at trace amounts, one can apply just
a few drops per liter of solution to rid himself from this precious contaminate.

Silver Refining First stage (Pt. 2)

Written by Gold-N-Scrap

Published: 06 December 2011

Vote 5 Rate
3. Cementing the Silver with Copper.
Now, that our solution is free from all of the starting materials contaminates and PGM's, we are
ready to recover the Silver metal from the nitrate solution in a form of powder.

Following the Reactivity Series, we will find that Copper is just above Silver (and PGM's).
In simple words, Copper is more eager to give up its electrons (go into solution/oxidized) and
Silver/PGM's are more eager to gain back their electrons (Go out of solution/reduced).

Any metal that is above Copper in the Reactivity Series will stay in solution.

Once introducing a solid Copper slab (could be a piece of pipe, a bus bar or rod), an immediate
reaction will occur. Silver crystals will start growing on the surface of the Copper coating it with ever
thickening layer until it collapse under its own weight and falls down to the bottom, thereby exposing
new copper surface to react with more Silver ions.
That's why, a very efficient way to cement Silver, is to hang the copper slab about half way through
the solution height and that is why you were suggested before to use a relatively graduated vessel.

Leave the Copper hanging in solution over night. When done, mix thoroughly for a minute and allow
settling for few minutes.

Test for left over silver in the solution by mixing 3 drops of the solution with one drop of HCl
(Hydrochloric acid) in a cavity plate or a test tube.
If it becomes somewhat cloudy after about 30 seconds, that means there's still silver in the solution
and more copper is needed to cement the rest of the silver.
If there's no more silver in the solution, all you will notice is a momentarily yellow color flash in the
solution with no cloudiness.

{googleAds}

{/googleAds}

Advertisement
What happens in this reaction?

We start with a solution of Silver nitrate salt AgNO3, the atoms of the copper give away their
electrons to the Silver cations, therefore Reducing them back to Silver metal and take their place in
the ionic bond with the nitrate anions.
As you can see, the nitrate anion (NO3-) plays no role in this reaction, so we can also call it a
'spectator ion'.

2 AgNO3 (aq) + Cu (s) = 2 Ag (s) + Cu(NO3)2 (aq)

This equation shows that each copper atom will reduce 2 Silver ions.
From that, we can calculate that each Gram of Copper will reduce 3.39 Grams of Silver.

In case you did not remove Pd/Pt before, they will also cement onto the copper. They tend to cement
after the majority of the Silver, but that's not always the case as they may also co-cement with the
silver.
They cement as black powder. Sometimes adheres to the copper rather tightly.
PGM's will be separated from the Silver in the following refining process.
{googleAds} {/googleAds}
4. Washing the Silver powder.
Now, you are left with Silver powder and a royal blue Copper nitrate solution.
This step is about separating the two. Not an easy task as it may sound.

Take a piece of polyester cloth or just a regular cloth (an old white T shirt will do) or a large coffee
filter to be used as your filter and wrap it around the moth of the receiving vessel. Make sure to leave
enough of a dent in it to accommodate all of the Silver powder.
See an example in the attached video.

The reason for using a cloth, which obviously, will not catch all of the very fine powder, is speed. You
will soon find that trying to filter through a fine filter paper proves to be very inefficient, and may take
hours just to catch those few grams in very fine powder.

Pour off the bulk of the blue copper solution through the filter, leaving the bulk of the powder in the
original vessel. Drain as much as possible.
Now, boil some tap water in a kettle and cover the Silver powder, use plenty of water, at least double
the powder hight, and mix vigorously for a minute.
The hot water will leach out the Copper nitrate solution entrapped in the Silver powder. Once cooled
and settled, drain the bulk of the solution to the filter and leave the bulk of the powder in the original
vessel.
Repeat that wash two more times, at least.

After the last wash, just wash all of the powder into the filter and allow it to drain for few hours. Next,
allow it to dry for several days or force dry it in a glass/porcelain pan on top of a heat source.

You will find that it is next to impossible to remove ALL of the Copper solution with just 3-5 water
washes, and that's OK, as the Copper contaminate now is probably less then 1% by mass. Good
enough for the next electro-refining process. (Separate article)
As to the fine particles that did pass through the filter, just allow the solution to stand for about 24-36
hours to let silver powder settle completely.
Siphon the bulk of the solution to your waste acid bucket and filter the last portion with the fine
powder though a regular filter paper.
I found that filtering the Silver powder that way, especially with more then 5-7 ounces of silver is the
most practical way.
5. Melting and pouring anodes
As we arrive to the final step of this tutorial, we are actually making the first step toward the second
and most vital stage in Silver refining process, one of which all of our Silver recovery & refining
efforts funnels down to eventually - The electrowinning cell. We will dedicate a whole different article
for this one.

So, melting the dry Silver powder can be done by different ways, you choose your own way, just
consider the following guidelines:
- Make sure while melting and pouring, you keep a "reducing" environment (see attached video
blow).
- Use a rectangle mold.
- Always heat the mold before
- Season the mold with a layer of soot or burned motor oil.
- Pour the metal while it is about 100-150 degrees C (212-302 F) above its melting point.

As you melt, you will probably notice brown fumes, this is NO 2 being given off by the traces of nitrate
compounds that are still locket in with the Silver powder.
NO2 is a nasty nasty gas which can prove deadly in high enough concentration, so always make sure
the room is very well ventilated while melting the Silver powder.

The anode purity at this stage usually ranges from 98% - 99.5% Silver content.
 {googleAds} {/googleAds}

Tip: To help raise the purity even further. Before melting the Silver powder, add to the powder half a
tea spoon of Borax and a pinch of nitrate salt (Sodium/potassium).