# cementation with copper



## arthur kierski (May 29, 2010)

to an ar solution which i suspected having some pm that was undetected with stanous chloride, i diluted and added copper plates and heated
the solution became brown(rusty collour) and this brown material passed thru filter paper----to the brown solution which already i suspected to be iron,i added sulfuric acid and the solution became dark green with no metal powder in it----this showed that no pms was present-----
the question is:does copper cements base metals? sometimes when using copper i obtain the pms (blacl powder) mixed with a white powder------i need help to clear my mind
thanks 

Arthur


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## philddreamer (May 29, 2010)

Hi Arthur!

The Reactivity Series. You need a copy of it. As I understand copper will drop silver, gold, Pt. Read about how it works in the posts or do a search on the internet. I have a copy, but cannot attach. 

Try this. http://www.zephyrus.co.uk/thereactivityseries.html

philddreamer


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## Barren Realms 007 (May 29, 2010)

This is from one of Steves post's.

Most Reactive 
Lithium 
Potassium 
Calcium 
Sodium 
Magnesium 
Aluminum 
Manganese 
Zinc 
Chromium 
Iron 
Lead 
Copper 
Mercury 
Silver 
Platinum 
Gold Li+ 
K+ 
Ca2+ 
Na+ 
Mg2+ 
Al3+ 
Mn2+ 
Zn2+ 
Cr2+, Cr3+ 
Fe2+, Fe3+ 
Pb2+ 
Cu2+ 
Hg2+ 
Ag+ 
Pt2+ 
Au+, Au3+ 
Least Reactive


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## lazersteve (May 29, 2010)

arthur kierski said:


> to an ar solution which i suspected having some pm that was undetected with stanous chloride, i diluted and added copper plates and heated
> the solution became brown(rusty collour) and this brown material passed thru filter paper----to the brown solution which already i suspected to be iron,i added sulfuric acid and the solution became dark green with no metal powder in it----this showed that no pms was present-----
> the question is:does copper cements base metals? sometimes when using copper i obtain the pms (blacl powder) mixed with a white powder------i need help to clear my mind
> thanks
> ...



Arthur,

As the copper saturates the PM solution, the PMs are cemented and copper I chloride (off white to gray colored) is precipitated as the acid levels drop. Add some 31% muriatic acid to the white powder and see if it dissolves. 

Not sure about the brown sludge, but it sounds like an iron compound to me. Could be the copper you are using is an alloy and contains a metal higher than iron on the chart.

Steve


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## arthur kierski (May 29, 2010)

thanks Steve for the coments----the copper i use are those square heat sinks from cpus which i first leave in a hcl bath to eliminate the tin coloured plating---they are normal copper to me(i do not know if they are an alloy) i have many kilos of this deplated copper heat sinks
regards from
Arthur kierski


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## lazersteve (May 29, 2010)

The cpu heat spreaders are a usually tungsten copper alloy.

They also may contain some nickel.

Steve


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## arthur kierski (May 29, 2010)

steve,but i cemented pms with them-----only this time iron??? formed but dissolved in h2so4


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## lazersteve (May 29, 2010)

arthur kierski said:


> steve,but i cemented pms with them-----only this time iron??? formed but dissolved in h2so4



Arthur,

Something about the material or the solution had to be different, i have no idea what.

Steve


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## rewalston (Jun 2, 2010)

Steve, I've seen mentioned numerous times that all of our washes should be put into a stock pot for later processing to catch any minute amounts of PM's. I've seen mentioned to put HCL washes, water washes, etc into the pot. What kind of container would be good to use as a stock pot? Also can all of the chemicals that we are using go into the pot? I'm assuming that nitric won't go in there because most often we are boiling off the nitric or chlorine before precipitation. I'm asking because once I'm done reading and digesting everything I can, that I don't want to put into the stock pot anything that would cause a mess later...or worse explode or catch fire or fume like a failed lab experiment. 

thanks

Rusty


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## lazersteve (Jun 2, 2010)

rewalston said:


> Steve, I've seen mentioned numerous times that all of our washes should be put into a stock pot for later processing to catch any minute amounts of PM's. I've seen mentioned to put HCL washes, water washes, etc into the pot. What kind of container would be good to use as a stock pot? Also can all of the chemicals that we are using go into the pot? I'm assuming that nitric won't go in there because most often we are boiling off the nitric or chlorine before precipitation. I'm asking because once I'm done reading and digesting everything I can, that I don't want to put into the stock pot anything that would cause a mess later...or worse explode or catch fire or fume like a failed lab experiment.
> 
> thanks
> 
> Rusty



Rusty,

Great question. 

I don't know how everyone else does it, but I keep a few five gallon buckets for the various by products. One for copper nitrate, one for SMB left overs, sulfuric cell dilution settling bucket, etc. I typically let them sit uncovered in an open air outdoor space which is protected from the rain. I add the same type of reaction left overs to the appropriate bucket.

Once a bucket is full or evaporated to saturation (a crust starts forming), I siphon off the bulk of the liquid and process it for disposal or recycling as the case may be. The sediment in the bottoms of these buckets is processed for precious metals along with any PM's that I harvest from the solution as part of the disposal process.

Once the disposal or recycling routine is completed, I combine the neutralized liquids and responsibly dispose of the separated solids as appropriate. The combined solutions are put in 35 - 55 gal fiber drums for hauling.

The only exception to this is solutions that contain the ammonium ion. These are immediately acidified, settled, siphoned, and then combined with the appropriate bucket of waste liquid. The solids are processed for PMs (usually silver).

Here's a simplified overview of the buckets and their uses and or by products:

1. Copper Nitrate solutions from sterling silver dissolution:
a. recycled as silver cell electrolyte by reverse plating out copper sponge
b. recycled as dilute nitric acid by precipitating silver chloride with HCl
c. metallic copper sponge from a. above.
d. recycle as Aklai nitrate by neutralizing with base.
e. by product of d. above is hazardous hydroxide or carbonate of base metal. Can be fluxed to form base metals in large furnace or disposed of on amnesty day at landfill. 
f. Regenerate nitric acid by destructive distillation of the copper nitric in a glassware apparatus. Brown gas is bubbled into cold distilled water. Copper Oxides can be converted to Acid Peroxide with HCl.

2. AR or HCl-Cl solutions after SMB:
a. Residual PMs precipitated by Cu saturation, let settle, and siphon, PMs in black powder.
b. Mixed metal Copper sponge cemented with scrap iron.
c. Neutralized with Lime, filtered, disposed of in drums.
d. Filtered Iron hydroxides / carbonates dehydrated to solids.

3. Sulfuric acid Cell diluted electrolyte
a. Siphon bulk of liquid off of settled residual black impure gold powder. 
b. Copper harvested by carbon electrodes from diluted liquid.
c. Recycled as cell electrolyte by dehydration until concentrated. 

4. Acid Peroxide Solutions:
a. Regenerate with air bubbler or peroxide additions.
b. Regenerate with electricity forming copper sponge.
c. Treat as 2 above for complete disposal.

5. PGM solutions:
a. 1-2 L beaker as appropriate for volume of PGM leftovers.
b. Dehydrates over time forming colored salts.
c. When enough colored salts are present, rehydrate and process with zinc.
d. Zinc left over solutions combined and dehydrated. 

There are more left over solution types, but these are the most common ones. As a general rule of thumb, don't mixed residual solutions from different types of reactions. Lie stays with like.

Hopefully some of the other guys will post there 'stock pot' set ups ofr comparison.

Steve


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## rewalston (Jun 2, 2010)

Thank you Steve for the response. A little bit on the confusing side, but once I get my feet wet (so to speak) things should start making more sense.

Rusty


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## Barren Realms 007 (Jun 2, 2010)

Since most of what I work with is HCL/peroxide. I put all my solutions into a 5 gal bucket with some iron and let it set, hard copper crust has formed and almost all the steel has been eaten so maybe one more go round and then new steel. But I like the electrical recovery better just don't have a good place to set it up right now. I have to set up a seperate bucket for my SMB solutions after Steve told me not to mix them.


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## lazersteve (Jun 2, 2010)

rewalston said:


> Thank you Steve for the response. A little bit on the confusing side, but once I get my feet wet (so to speak) things should start making more sense.
> 
> Rusty



Rusty if you are having problem with the abbreviations you need to read the Guided Tour Link and study the reactions list. Don't worry with time it will all start to make sense, just take it slow, don't reinvent the wheel, and be safe and responsible.

Steve


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## qst42know (Jun 3, 2010)

Steve.

Do you see an issue in including the ammonia rinse directly in the stock pot. The majority of the ammonia is already boiled off and the stock pot is already acidic.


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## lazersteve (Jun 3, 2010)

qst42know said:


> Do you see an issue in including the ammonia rinse directly in the stock pot. The majority of the ammonia is already boiled off and the stock pot is already acidic.



The ammonia rinse likely contains silver that's why you use the ammonia rinse, to remove any silver chloride. If you add it to a chloride containing stock pot directly, the silver chloride will accumulate in the bottom of your stock pot along with any other precious metal sediment. 

In my opinion, make the ammonia rinse acidic with HCl, let it settle, then siphon off the liquid and add the liquid to the acid stock pot. You'll harvest a nice clean silver chloride this way that is well suited for direct reduction with lye and sugar, or any of the other method silver chloride conversion methods. If it's only a small amount of silver chloride store it under a layer of water until you accumulated enough to warrant conversion.

Steve


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## Nopyrite (Jun 15, 2010)

Steve, would you please amplify on #3 in your bucket list. As I am now trying to learn the Sulfuric Cell process from start to finish, I will make some assumptions and you can correct me if they are wrong please. 

Sulfuric acid Cell diluted electrolyte
a. Siphon bulk of liquid off of settled residual black impure gold powder.
b. Copper harvested by carbon electrodes from diluted liquid.
c. Recycled as cell electrolyte by dehydration until concentrated. 

a. Siphon bulk liquid and set aside for next cell run. (this gets no treatment)
b. "diluted liquid" this is the solution left over from the washes and filter cleanup and consists mostly of water, but may contain HCL and Suluric. 
b. "Copper harvested by carbon electrodes". Is this done in the same manner as the stripping cell, except using Carbon Electrodes? Do you have these available?
c. After the copper is harvested, the solution is dehydrated until concentrated. The concentrated residue can now be mixed back in with the original electrolyte for another cell run.

Thanks again for your help.


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## HAuCl4 (Jun 15, 2010)

Thanks Steve for a great recycling post of procedures.


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## lazersteve (Jun 15, 2010)

Nopyrite said:


> Steve, would you please amplify on #3 in your bucket list. As I am now trying to learn the Sulfuric Cell process from start to finish, I will make some assumptions and you can correct me if they are wrong please.
> 
> Sulfuric acid Cell *diluted* electrolyte
> a. Siphon bulk of liquid off of settled residual black impure gold powder.
> ...



Read the heading again and you will see this section applies to the Diluted Acid from the cell and washes. This section does not apply to concentrated electrolyte, which is the only portion that is directly reusable. The diluted portion must be made free of black sediment, free of base metal, and concentrated by dehydration before it is reused.



Nopyrite said:


> b. "diluted liquid" this is the solution left over from the washes and filter cleanup and consists mostly of water, but may contain HCL and Suluric.



No HCl should be in the mix. No where in the sulfuric cell process do we add HCl.



Nopyrite said:


> b. "Copper harvested by carbon electrodes". Is this done in the same manner as the stripping cell, except using Carbon Electrodes? Do you have these available?



Yes, Yes. Carbon is not the only available choice of electrodes, but is an inexpensive option.



Nopyrite said:


> c. After the copper is harvested, the solution is dehydrated until concentrated. The concentrated residue can now be mixed back in with the original electrolyte for another cell run.



Correct. In practice you will have already used the original concentrated electrolyte in another batch long before you perform the clean up process above on the diluted electrolyte. I accumulated my diluted electrolytes in a five gallon bucket for settling. Once I get a bucket full I siphon, let dehydrate to approximately 50% or less of it's original volume in the heat of the day (actually a few days depending on the weather), plate out the base metals, then force dehydrate the balance of the water using a large heated beaker or bucket heater in some cases.

Steve


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## lazersteve (Jun 15, 2010)

HAuCl4 said:


> Thanks Steve for a great recycling post of procedures.



It's the great questions that make possible the great answers. The hardest part of helping each other is proper communication. When members ask insightful questions everyone benefits, including me. By typing out my processes I often find ways to improve them.

This thread speaks volumes to the benefits of members doing their home work before asking questions. When the question is based upon a real life puzzle, we get real world solutions. When questions are posed from hypothetical events the solution is only as good as the hypothesis. Too often noobs (no offense to noobs ) jump in head first and ask the age old questions all noobs have before they gain experience in the real world. If these same noobs had taken the time to study the forum passionately, they would be asking questions that help not only themselves, but everyone. It's an excellent example of how noobs can contribute to the forum simply by asking an educated question.

Steve


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## HAuCl4 (Jun 15, 2010)

Indeed. What do you think of making ferrous sulphate instead of throwing away iron carbonates, hidroxides, etc.?


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## lazersteve (Jun 15, 2010)

HAuCl4 said:


> Indeed. What do you think of making ferrous sulphate instead of throwing away iron carbonates, hidroxides, etc.?



I've actually toyed with the idea a bit but I have not implemented any of my ideas on a large scale. I've done some small scale base metal hydroxide and carbonate precipitations on my spent solutions, but the hazards of the by products must be considered on larger scales. I feel the key is to immediately convert the hydroxides and carbonates to less hazardous forms before storing for later use. Then you would have to remove the bulk of the water from the left over solutions to obtain useful reagents for the next run.

The up side to this approach is that you will have a continuous supply of reagents if you design systems to use or sell all of the ingredients and by products in a closed loop process. In several of my videos I make mention of these 'closed loop' uses for certain reactions.

Steve


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## Nopyrite (Jun 15, 2010)

Lasersteve, thank you. I did a re-read on your bucket list and sure enough #3 says "sulfuric acid cell DILUTED electrolyte." I must learn to pay closer attention. I also seem to have gotten off track trying to use HCL to clean-up black residue from the cell. I note that you do not mention the use of HCL in any of your Sulfuric Cell posts. I believe I picked this up from another poster's method on a different thread. I am now back on track, however, I have erred in my ways as I have used a small amount of HCL on my cell residue. The black substance is now sitting in a beaker of muddy looking water, sulfuric and HCL. Could you advise as to how to proceed with this material? Also, the diluted electrolyte in the bucket contains some HCL. is it polluted beyond further use?


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## lazersteve (Jun 15, 2010)

Nopyrite said:


> ... I have erred in my ways as I have used a small amount of HCL on my cell residue. The black substance is now sitting in a beaker of muddy looking water, sulfuric and HCL. Could you advise as to how to proceed with this material? Also, the diluted electrolyte in the bucket contains some HCL. is it polluted beyond further use?



The diluted solution is fine to have residual HCl in it. When you boil it down the HCl will go 'up in smoke' as it is volatile and sulfuric acid is not.

The black powder is treated as listed here:

Black Powder From Cell

I used to do preliminary washes and such, but found no difference in the end product quality since I dissolve all gold twice anyway. So now days I go straight to AR after several hot water wash, settle, siphon, cycles.

Steve


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## HAuCl4 (Jul 6, 2010)

Do you guys think that an AR or HCL-CL closed loop be economically implemented, that would require little/none new chemicals and produce little/none wastes?.

I have been thinking around this process for a while and can't find a solution that satisfies me to improve this loop (as initially posted by Steve):

2. AR or HCl-Cl solutions after SMB:
a. Residual PMs precipitated by Cu saturation, let settle, and siphon, PMs in black powder.
b. Mixed metal Copper sponge cemented with scrap iron.
c. Neutralized with Lime, filtered, disposed of in drums.
d. Filtered Iron hydroxides / carbonates dehydrated to solids.


The copper/nitrate loop I can see it producing little wastes and requiring only a little nitric and Hydrogen peroxide, and re-generating most of the nitric acid for re-use with electricity, etc.

But what about the HCL/Au/Cl loop?.
I can see how one can do away with the nitric by using CL or NaCLO, but not much else. What would be the best way to re-generate chemicals AFTER precipitation of the gold with whatever.

Any ideas?.


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## Harold_V (Jul 7, 2010)

HAuCl4 said:


> Do you guys think that an AR or HCL-CL closed loop be economically implemented, that would require little/none new chemicals and produce little/none wastes?.
> 
> I have been thinking around this process for a while and can't find a solution that satisfies me to improve this loop (as initially posted by Steve):
> 
> ...


Please understand that I'm the world's biggest skeptic, and I am not a chemist, so I may not understand your question in a meaningful way. Having said that, here's my comment; 

What you propose appears to me to be akin to perpetual motion. It is well known that we must use energy to transform from one state to another. Even in an efficient system, there are losses. If you can replace the losses with such things as electrical power, or even by a heat source, I can see how it might be possible----but I'll believe it when I see it, and even then I'd have serious questions. Sort of like the BS thing that was going around the net for a while, where a guy lights a small lamp by inserting nails in two candles, then attaches a lead from one nail, through the (small) light, then the other end to the other nail, inserted in the other candle. He lights the candles, you hear a snap (switch being thrown, and out of sequence) and the light is lit. Did anyone ever wonder how a complete circuit was established, and why such a setup, even if it did produce voltage, would provide flow when each candle was wired identically? Wouldn't each of them be either + or -? Seems to me you must hook + to - to establish flow. What am I missing?

Show me! 8) 

Harold


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## Barren Realms 007 (Jul 7, 2010)

Harold_V said:


> HAuCl4 said:
> 
> 
> > Do you guys think that an AR or HCL-CL closed loop be economically implemented, that would require little/none new chemicals and produce little/none wastes?.
> ...



I have never herd of that one with the candles. If you have a link to it I could use a good laugh.


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## Harold_V (Jul 7, 2010)

Barren Realms 007 said:


> I have never herd of that one with the candles. If you have a link to it I could use a good laugh.


I haven't seen it in a while, and didn't keep it, although it was a great source of a belly laugh, to think how stupid some people must think others are. It was present as if it was sincere, and you're supposed to figure it out. I can see it all now---people plunging nails in to candles, attaching their wires, ighting their candles and wondering where the light went. 

I wonder----could this have come from a candle maker, somewhere?

very heavy sigh!

H

An after thought---you may be able to find it on youtube. I think that was the source, but I'm not sure. Look for candles and making electricity. Might help, not sure. Do report what you find, if you do. Others might enjoy a laugh on this one, too.


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## HAuCl4 (Jul 7, 2010)

It would consume, at least electricity. And probably a small % of the chemicals need constant replenishing.

Lazersteve has achieved this for the silver/copper/nitric circuit.

I was wondering if a loop for the HCL-CL-Au could be devised. All the possible solutions I have explored, consume one chemical to produce another. Like for example:

1-Leach Au with HCL+NaCLO (bleach) to produce AgCL, HAuCl4 and other chlorides.
2-Filter the solids, extract with BDG.
3-Drop the Au from BDG using H2O2. Recycle the BDG. Recycle HCL?
4-Drop the Pt group in solution from 1 with Copper (after BDG extraction of course). Filter solids.
5-Recover the copper and HCL with electricity?. Recycle the HCL.

In the process above one consumes electricity, H2O2, and leach to produce more HCL than is needed, some of it can be recycled into the process, so it is not a closed loop.

Ideas?.

The nitric loop is closed mostly. It consumes nitric and electricity to process copper and silver, and mostly all nitric is recycled.


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## Barren Realms 007 (Jul 7, 2010)

Harold_V said:


> Barren Realms 007 said:
> 
> 
> > I have never herd of that one with the candles. If you have a link to it I could use a good laugh.
> ...



I will do some searching and see what I can find.


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## HAuCl4 (Jul 7, 2010)

Found this link that wastes no H2O2 but H2 instead:
http://catalogue.nrcan.gc.ca/opac/extras/unapi?id=tag:catalogue.nrcan.gc.ca,2010:biblio-record_entry/7898219/-&format=htmlholdings-full

Hardly an "improvement" imho.


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