Refining MLCC´s for Palladium and Silver !

[Geo]

Hello !
Soo many thanks !!!
I believe I got the hang of it and have made it quite succesfully to -"The sollution should be some color of red". That is exactly what I´m having ! And I tried to get rid of de silver just by decant/siphon it. But now... -"Precipitating the Pd with ammonium chloride + chlorine gas will give you a red salt of Pd" sounds very scary to me...(even me...) ! Chlorine gas ? How can I work with Chlorine gas ? Sounds better to -"cement onto copper to obtain a slightly impure palladium metal in one go". But how does it work (I have never done it) ? Do I just put sticks of copper into the fluid and wait for it to stick ? For how long ? How can i be sure to get it all ? And wont the copper disolve into the acid ?
Sorry for all my questions...but I think I got the red fluid right and I don´t want to spoil it all now...

The chlorine gas can be produced in situ. If I am in a hurry (bad idea any time) instead of setting up a chlorine generator by decomposing sodium chloride in sulfuric acid and bubbling the resulting gas through the solution, I just sprinkle in some trichloro pool chlorinator. It comes in a solid "puck" or powder. I use the powder. This is not a chemical where more is less. This is a chemical where a little goes a long way. By reading the label, most trichloro up in the high 90% pure chlorine. It will dissolve in acidic solution producing copious amounts of chlorine gas. After adding the ammonium chloride, add just a pinch and stir it in well. The red salt will start forming. You can't get it all this way. There is a certain balance that will be maintained in the solution that is determined by the volume of liquid. The more free liquid available, the more Pd that will be left in solution so it's always better to work with a concentrated solution.

 

[Lars100]

Hi Orvi !
Thanks for input !
And I fully understand. I only work in batches that I can handle. Been working with about 600g MLCCS per shot.
What I mean with "solid process" is simply that I will finish the whole lot into the "burgundy red fluid" + silver and then READ and LEARN how to move forward (yes, test the batch also).
I must find a way which I then (rather easily - hopefully) can "copy/paste" over and over until I've processed it all.

 

[Lars100]

Many thanks Geo !
This sounds like a path forward. I will study it more.
- But it still looks like I will end up with a "mix of metals" in the ready soup.
We can discuss this later when Ive tested a bit but my big concern is how to

I use copper when copper is already in the solution. The "go to" when cementing PGM's is normally zinc powder or turnings. Add small amounts incrementally as the reaction is exothermic and can get out of hand quickly. The reaction is complete when the solution loses all color except maybe a light green tint that will not cement out, The hotter it gets, the more violent the reaction becomes. Other sacrificial metals that are used to cement precious metals is iron and aluminum. Iron can be obtained through bare steel scrap metal. It leaves a dirty solution as it will cement nearly every metal in the reactivity series. But, you will be sure to get all metals out. Aluminum will react the same way zinc does. Aluminum will create a filtering problem by the nature of the metal. Aluminum chloride is a gelatinous mass in solution, depending on amount dissolved, and will clog filters that seemingly looks empty. Each one has it's pro's and con's. You have to safely experiment and see which is best for your particular needs.

separate and refine the PD ?

 

[kurtak]

What I mean with "solid process" is simply that I will finish the whole lot into the "burgundy red fluid" + silver and then READ and LEARN how to move forward

Per the bold print (in above quote) --- you have it all wrong - as in you have it backwards - you are putting the cart before the horse

When working with PGMs (Platinum Group Metals) including Pd - you do NOT go putting the PGMs into solution first --- & then READ & LEARN how to move forward

You READ & LEARN FIRST - then start working on putting the - "lot into the "burgundy red fluid"

Working with recovery & refining of PGMS is a EXTREMLY RISKY & TOXIC process - you are working with POISON

PGM POISONING is very much like lead or mercury poisoning - it doesn't kill you right away (today - tomorrow - this month - next month - this year &/or even next year) that is because it gets in your system/body & STAYS there & starts killing you over time - which can be several years

A few things to know/understand about platinum (GROUP metal) poisoning/toxicity -------

platinum (group metals) toxicity vary depending on the amount you are currently exposed to, which can/will lead to the following

• Allergic reactions of the skin & or mucous membranes
• Kidney disease’s
• Intestinal & digestive problems
• Muscle spasms
• High blood pressure (Hypertension)
• Deafness
• Cancer

Everyone that has been trying to help you here has tried to WARN you about this & has tried to tell you that the VERY FIRST thing you MUST do is LEARN & READ - and THEN set up to do this SAFELY - then - and only then - put "the whole lot into the "burgundy red fluid"

If you do not follow this advise to FIRST - get everything you NEED to do this safely - & then set up to do this safely - YOU ARE GOING TO POISON YOURSELF - AND POISON EVERYONE that comes into your back yard where you are doing this

PLEASE put what you are doing off to the side & STOP what you are doing - until you FULLY understand how to do this safely AND set up to do this safely

We can & will help you with this (setting up to do it safely)

Other wise you are on a path to self destruction - you just don't realize it because you are blinded by the high price of a small amount of metal

Edit to add; - I just hope - that with the way you are currently going about this that you don't have a wife & kids around what you are doing - because if you do - you are POISONING then to

Kurt

 

[kurtak]

One more thing - just because you see others - on YouTube - that don't know any better - doing stupid stuff - doesn't mean you have to be stupid to


We are here to help you from being stupid

Kurt

 

[MicheleM]

@Lars100 in my opinion working with " 600 g for shot" is too much for a beginner. You should try with a smaller batch, around 50 g , random sorted. They generate a lot of acidic liquid waste. All this without mentioning that this is a very dangerous activity, with around 50 g, is more manageable, and in the end you will decide what to do with the rest of them.

 

[Lars100]

Hi Kurt !
Many thanks for Your concern.
- To reach the level of "burgundy red fluid" I believe I have worked out a safe process. I´m done up to 95% and just finishing up the rest.
The fluids are put away nicely in bottles.

But You are correct. I am a bit worried about the next steps (safety, process and refining

Per the bold print (in above quote) --- you have it all wrong - as in you have it backwards - you are putting the cart before the horse

When working with PGMs (Platinum Group Metals) including Pd - you do NOT go putting the PGMs into solution first --- & then READ & LEARN how to move forward

You READ & LEARN FIRST - then start working on putting the - "lot into the "burgundy red fluid"

Working with recovery & refining of PGMS is a EXTREMLY RISKY & TOXIC process - you are working with POISON

PGM POISONING is very much like lead or mercury poisoning - it doesn't kill you right away (today - tomorrow - this month - next month - this year &/or even next year) that is because it gets in your system/body & STAYS there & starts killing you over time - which can be several years

A few things to know/understand about platinum (GROUP metal) poisoning/toxicity -------

platinum (group metals) toxicity vary depending on the amount you are currently exposed to, which can/will lead to the following

• Allergic reactions of the skin & or mucous membranes
• Kidney disease’s
• Intestinal & digestive problems
• Muscle spasms
• High blood pressure (Hypertension)
• Deafness
• Cancer

Everyone that has been trying to help you here has tried to WARN you about this & has tried to tell you that the VERY FIRST thing you MUST do is LEARN & READ - and THEN set up to do this SAFELY - then - and only then - put "the whole lot into the "burgundy red fluid"

If you do not follow this advise to FIRST - get everything you NEED to do this safely - & then set up to do this safely - YOU ARE GOING TO POISON YOURSELF - AND POISON EVERYONE that comes into your back yard where you are doing this

PLEASE put what you are doing off to the side & STOP what you are doing - until you FULLY understand how to do this safely AND set up to do this safely

We can & will help you with this (setting up to do it safely)

Other wise you are on a path to self destruction - you just don't realize it because you are blinded by the high price of a small amount of metal

Edit to add; - I just hope - that with the way you are currently going about this that you don't have a wife & kids around what you are doing - because if you do - you are POISONING then to

Kurt

) and that´s why Im writing here on the forum.

 

[Lars100]

Dear Michele (and Kurt),
At this time I dont think I dare to tell you in detail what Ive done so far.
- But I found a workable way to come to this point.
Basically I added 0.4L Nitric acid to the "tin free" 600g MLCCs. Let them stay so for a week (just rotated and mixed well a couple of times).
- It was bad if I let them stay longer as it resulted in thick cream (impossible/very hard to filter).
After a week I decanted and filtered. Components/mass in a "big box" (still there...maybe a 2nd round later ?) and the black/green fluid into bottles.
Added about 0.3dl of HCL and waited overnight.
The fluid changed color into "burgundy red" and with a white/beige/red layer at the bottom (silver ?).
Decant/siphon/separated the white from the red. Thats where we are today.
Im still waiting for my tin so I can make stannous test.

@Lars100 in my opinion working with " 600 g for shot" is too much for a beginner. You should try with a smaller batch, around 50 g , random sorted. They generate a lot of acidic liquid waste. All this without mentioning that this is a very dangerous activity, with around 50 g, is more manageable, and in the end you will decide what to do with the rest of them.

 

[Geo]

@Lars100
I concur with Kurt. Storing ionized Pd is a dangerous situation. Accidents happens, an act of god, an earthquake or storm. It's better to keep that kind of toxin in metallic form until you are ready to go from start to finish. This reduces the time that the metal is most deadly. There was two great people from this forum that I knew personally, and a third that's suspected, that has died from complications of platinosis.
Since the Pd came from MLCC's, it should be pretty pure as it is. Move the solution to a large enough beaker to hold the solution and still have 2/3 to 3/4 of the volume empty. Add 50ml's of HCl to drop the silver as silver chloride. Filter the silver out and replace the solution to the beaker. Dilute the solution to double it's volume. Start adding small amount of steel wool while stirring. The steel wool will have the tendency to float. It needs to stay submerged as much as possible. This will produce a small amount of aerosol from the reaction, so wear gloves and a mask if you are not working in a fume hood. Keep adding the steel wool until the solution loses it's red color and turns slightly green. It will produce a light, fluffy black powder. You may see small bits of steel wool that does not react. Don't be alarmed as steel contains carbon. What you are seeing will be the carbon retaining the shape. It is of no consequence to the recovery or melting of the powder. Ideally, you would continue adding steel until you get a negative stannous chloride test result. You will have to settle for a colorless solution except for the before mentioned light green color. Filter all black powder out of solution. Now you have a mostly purified black powder of Pd called (PGM blacks). You can melt as is or store and add more to it later. Don't be surprised at the volume of the black powder. It makes a huge volume of powder that dries to a much smaller mass. It dries up next to nothing to be honest. It will make you think it evaporated off but that's just the nature of cemented powder. Now your palladium is much less dangerous than it was as a liquid. The powder will be very fine and light and can be lifted into the air by a small puff of wind. The black powder is still just as toxic as the liquid so take great care to capture all of the powder and store it damp until you are ready to melt it.

 

[Geo]

For tin, go to your local walmart and buy lead free fishing weights. The pure tin "split weights" will be a lustrous white metal that will look like silver. Also, lead free tire weights is pure tin. If you have to order tin to make stannous chloride, you can just buy stannous chloride crystals from Amazon or Ebay. Just add water to the crystals and allow them to dissolve. Keep solution away from heat and strong light (sunshine) to keep it fresh longer.

 

[Lars100]

Dear Geo,
This was really exciting to read and a process that I should be able to handle.
I will definitely test this.
Again, stannous test next week and then also bring together the parts needed to make a first try with Your methode.
Thanks !
Ps. I got many litres of that deep Burgundy red fluid so you can understand I need a workable methode.

 

[Lars100]

@Lars100
I concur with Kurt. Storing ionized Pd is a dangerous situation. Accidents happens, an act of god, an earthquake or storm. It's better to keep that kind of toxin in metallic form until you are ready to go from start to finish. This reduces the time that the metal is most deadly. There was two great people from this forum that I knew personally, and a third that's suspected, that has died from complications of platinosis.
Since the Pd came from MLCC's, it should be pretty pure as it is. Move the solution to a large enough beaker to hold the solution and still have 2/3 to 3/4 of the volume empty. Add 50ml's of HCl to drop the silver as silver chloride. Filter the silver out and replace the solution to the beaker. Dilute the solution to double it's volume. Start adding small amount of steel wool while stirring. The steel wool will have the tendency to float. It needs to stay submerged as much as possible. This will produce a small amount of aerosol from the reaction, so wear gloves and a mask if you are not working in a fume hood. Keep adding the steel wool until the solution loses it's red color and turns slightly green. It will produce a light, fluffy black powder. You may see small bits of steel wool that does not react. Don't be alarmed as steel contains carbon. What you are seeing will be the carbon retaining the shape. It is of no consequence to the recovery or melting of the powder. Ideally, you would continue adding steel until you get a negative stannous chloride test result. You will have to settle for a colorless solution except for the before mentioned light green color. Filter all black powder out of solution. Now you have a mostly purified black powder of Pd called (PGM blacks). You can melt as is or store and add more to it later. Don't be surprised at the volume of the black powder. It makes a huge volume of powder that dries to a much smaller mass. It dries up next to nothing to be honest. It will make you think it evaporated off but that's just the nature of cemented powder. Now your palladium is much less dangerous than it was as a liquid. The powder will be very fine and light and can be lifted into the air by a small puff of wind. The black powder is still just as toxic as the liquid so take great care to capture all of the powder and store it damp until you are ready to melt it.

Again, many thanks for this advice. Im just about to order some steel-wool but there seem to be various qualities (like fine or rough). Any sugestions ?
And you say -"Dilute the solution to double it's volume". Shall I do that with dl water ?
And the silver already been separated (we can discuss about how to refine that one also...).
- Now, Im still waiting for my tin to do the stannous but I can start testing with the steel-wool if that comes first.
- Im a bit worried that I havent got all the good things out of the MLCCs (after decante out the Nitric acid).
I took a part and added HCL. The mass/fluid immediately changed color to orange/red. So there seems to something good still there...
Again, many thanks (so far) !
Lars

 

[Geo]

As long as the MLCC's remain whole, there will be metal left to reclaim. Most people mill or crush them before starting. I don't like milling. It creates too much fine silt that the acid has to struggle to get through unless you have an overhead stirrer. When wet processing, the ceramic bodies have to break down into dust to get a complete leaching. They will break down in the acid by just heating. The bodies are sintered alumina ceramic. They will slowly come apart during the leaching. I find it's better to put an excess of solution in the beaker with the MLCC's and cover and place on heat and forget about it until the evening. It normally takes several days to break down all of the bodies. Unless they are crushed before hand. It's best to avoid chlorine during the nitric acid leach if you want to recover the silver. If silver chloride is formed in the alumina powder, there is no good way to separate the two again. It's just trash. Actually it's best not to introduce HCl to the process at all until all of the nitric acid leaches are complete and filtered. Then add HCl to remove the silver. Or dissolve some non-iodized table salt in water and pour that into the silver nitrate. It has the same effect that HCl does but is much less expensive. Using AR to leach a catalytic metal is a fight against itself. Catalytic metal breaks NO2 down to it's individual atoms. It will dissolve over time but just plain nitric acid works better for me.

 

[dpgold]

Thanks for input !
Ehh...Stannous-test...how do I perform such a test ?
Air-bubbler ? Any brand, type You can recommend ?

it is a liquid comprised of TIN and HCL, I am not sure about the exact proportions but seems like 12g fine grinded TIN or TIN powder dissolved in HCL about 50ml (Muriatic acid concentration) it takes a while to dissolve. Kept in a dark bottle and is good only for a couple of months. If the solution contains PGM or gold it will change color on the test strip. Soak a test strip in the solution which you believe contains these metals dissolved and then put a tiny drop of Stannous solution on it. Depending on the metals contained and concentration the strip will change color indicating their presence

 

[kurtak]

As long as the MLCC's remain whole, there will be metal left to reclaim. Most people mill or crush them before starting. I don't like milling. It creates too much fine silt that the acid has to struggle to get through unless you have an overhead stirrer. When wet processing, the ceramic bodies have to break down into dust to get a complete leaching.

This is one of those things where the old saying - "there is more then one way to skin a cat" - is true

When wet processing, the ceramic bodies have to break down into dust to get a complete leaching.

This is true - in order to leach all the Ag/Pd out of the ceramic bodies of MLCCs the ceramic bodies need to be broke down to the "fine" silt/dust - which will put (dissolve) all the Ag/Pd into the nitric leach solution

Edit to add; - other wise all you are really going to get is the Ag/Pd on each "end" of the MLCC

The problem with "leaching" MLCCs is getting all of the leach out of that "fine" silt/dust - it's like "fine" clay which is next to impossible (if not impossible) to filter --- &/or wash out

Because filtering is "impossible" --- decanting - washing - settling - multiple times is really the only way to get "most" of the leach out of the silt dust --- I say most - because even with washing you won't get it all - there will always be at least traces (or more) left in the silt/dust (depending on amount of washing) you just can't get it all - which (with all the washing) will give you a VERY dilute leach solution

Then - after all the washing - you will likely need to do some (or a lot) evaporation to concentrate the leach back down - otherwise the silver (chloride) & then the Pd will come down ultra fine - making washing/filtering those precipitates difficult

At least that was my experience the first (and one & only) time I tried leaching MLCCs - what a pain in the butt - so much so that I decided that I would never again leach MLCCs

IMO - if you are going to process MLLCs - smelting is the way to go - they still need to be milled to a "fine" dust so that the alumina (ceramic) will slag off AND you need to use cryolite as "part" of your flux make up as cryolite dissolves the alumina allowing it to slag off

Flux for smelting MLCCs - 1/3 borax 1/3 soda ash 1/3 cryolite & "some" fluorspar for thinning

If you do a HIGH temp roast (get them "red" hot) on the MLCCs before milling they will mill easier & more completely to the dust you are looking for

Edit to add; - once red hot let them roast for "at least" one hour - if not two

Use silver as your collector metal in the smelt - then process you dore with nitric - proceed with dropping silver chloride (as normal) then Pd recovery (cementing with copper recommended)

As I said - "more then one way to skin a cat"

Kurt

 

[jphayesjr]

Thanks for the suggestions. I have 25 kilos of old MLCCs, and am in process of planning the refining project. I have technical reasons to believe the material will contain significant AU, PT, RH, as well as AG and PD. Any suggestions how to proceed stepwise to recover all?

 

[jphayesjr]

Thanks for the suggestions. I have 25 kilos of old MLCCs, and am in process of planning the refining project. I have technical reasons to believe the material will contain significant AU, PT, RH, as well as AG and PD. Any suggestions how to proceed stepwise to recover all?

Should add, I'll be getting up to75 k more soon, all from a defunct repair company on original reels, will be looking into professional refiners. The engineers out there know how a scaled up process will differ from benchtop assay methods. I know I need to have a good grasp of the processes and chemical equations involved for all the best reasons, to choose someone who offers the best options.

 

[Yggdrasil]

Thanks for the suggestions. I have 25 kilos of old MLCCs, and am in process of planning the refining project. I have technical reasons to believe the material will contain significant AU, PT, RH, as well as AG and PD. Any suggestions how to proceed stepwise to recover all?

I would expect, if lucky to have significant amount of Ag and Pd in there, the rest is just scam food, which make me think the start is a scam.
There is and have never been, as far as I know, anything else of value, than AG and Pd in high grade MLCCs

 

[orvi]

I would expect, if lucky to have significant amount of Ag and Pd in there, the rest ia just scam food, which make me think the start is a scam.
Ther is and have never been, as far as I know, anything else of value, than AG and Pd in high grade MLCCs

Maybe some super-fancy with gold plated ends I also do not know what else should be in there. Old Soviet MLCCs sometimes used platinum, not palladium. Some batches of mixed MLCCs gave even 50/50 PtPd mix. Never heard about Rh or gold inside. But in modern stuff... I doubt even about palladium. From the point when sinter technology for nickel developed for MLCCs, Pd ones are very scarce.

 

[kurtak]

I have technical reasons to believe the material will contain significant AU, PT, RH, as well as AG and PD

Not sure where you heard that MLCCs have Au Pt or Rh in them (although I have seen "some" with gold "plating" on the ends - but - they are rare)

OLD MLCCs were made with Pd/Ag

Or as orvi said (old) Soviet made stuff will have Pt in place of the Pd

There are two types of MLCCs - NME (Noble Metal Electrode) MLCCS --- & (BME Base Metal Electrode)

NME MLCCS are made of Ag/Pd (the exception being Soviet stuff with Pt in place of Pd)

BME MLCCS are made of copper & nickel

In the "late' 1990s (around 1997) because of the "rising" price of noble metals - & the cost of making NME MLCCS going up significantly the quite making NME MLCCs & started making BME MLCCs

So after (around 1997) the VAST majority of MLCCs are made of copper/nickel NOT Ag/Pd

There is an easy why to test if MLCCS are made of base metals - or made of noble metals

Nickle is magnetic - so a magnet will pick up BME MLCCS because of the 50% nickel alloyed with the copper - but a magnet will not pick up NME MLCCs as Ag &Pd are not magnetic

Should add, I'll be getting up to75 k more soon,

My point is - if you are "buying" these make sure you use your magnet BEFORE paying for these or you will be very disappointed when you get them & find out they are made of Cu/Ni & not mad of Ag/Pd

If you can't test them with a magnet - before buying them - I would walk away as it "may" be a scam

Not saying it is - just warning you to be careful as these kind of scams happen all the time

Kurt