# Wastes - The Elephant in the Room



## goldsilverpro

There is a misunderstanding that occasionally crops up on the forum about base metals that are dissolved in acids. Many people think that the reason for dropping out these metals, with iron or aluminum, is to recover them so that they can be sold, as is, or after melting. *Not so*. No one will want to buy the powder and melting the powder is most probably cost prohibitive for most all of you. You'll never get the stuff melted with a torch.

So, what is the reason for dropping out the base metals? It is to convert highly toxic heavy metal solutions to much less toxic iron or aluminum solutions. 

The copper, nickel, etc., solutions are definitely considered by the EPA to be highly hazardous waste. I don't exactly know they classify the Fe and Al solutions, but surely they must be ranked a peg lower.

As far as solids are concerned, I know basically how the EPA tests them. They mix up enough acid (and water) to make a solution with a pH of about 3 or 4 (I think), add the solid to this solution, and then they analyze this solution for heavy metals. In the 2 photos of copper powder that Steve posted on the link below, the pink copper metal in the 1st photo wouldn't dissolve and would, therefore, be legal, as I understand it. In the 2nd photo, the green copper compound would dissolve in the pH 4 acid solution and, therefore, it would not be legal.

http://goldrefiningforum.com/phpBB3/viewtopic.php?t=1066

The old way to make solutions legal to dump was to drop out the base metals with an alkali, such as sodium hydroxide, sodium carbonate, or lime. The base metals start dropping as hydroxides, carbonates, etc., at a pH of 5.5, depending on the metal(s) involved. The problem is that these hydroxides, etc. will redissolve at a pH of 4 and will fail the EPA test. You're just trading one form of hazardous waste for another. Another problem is that these metal hydroxides are very voluminous. I have dropped the metals out of a drum of acid solution and ended up with a drum full of metal hydroxides.

I haven't kept up with the EPA rules. When I owned refineries, I always had my own wastes hauled off legally and, every place I have worked for (at least in the last 25 years) either had their wastes hauled or had legal treatment facilities. However, I have had a few garage operations, although not for quite a few years. I have been where you are. I know.

Some one here should find, study, and interpret the latest laws and post them under this "Legal Things" category. Legal stuff bores me to tears. I will, however, help work on the technical aspects of how to comply. If we work on it, I'm sure we can come up with a cheap way to handle these wastes.

The best technology and knowledge for handling wastes comes from the electroplating industry. Their wastes are almost identical to ours. At one time, this industry was notorious for dumping toxic wastes illegally. When the EPA and OSHA clamped down, they made an example of these people. The plating shops had to comply or, they had to shut down. Probably 80% of them went out of business. Lots of great new waste control technology has resulted.

The thing that would bring you people and this forum down is if you all dumped these solutions illegally. This is a taboo subject that no one likes to discuss. It's a big elephant in the room that everyone ignores. If we would openly talk about it, we could come up with viable solutions (no pun intended). Be good citizens. Don't ruin this for everybody else.


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## Never_Evil

This is just me blurting out ideas so if you dont want to waste time please stop reading NOW.

Since there is a of hydrogen, oxygen, a depending on what other solution, carbon, chlorine and such, Is there a way to turn this into a fuel? By adding baking soda it is neutralizing the solutions, but can we turn this left over solution into a hydro cell or combustable fuel? I dont have the chemical equations infront of me to know what is turned into what so I may be way off.

Is there another chemical that could push out the metals from the solution? Rather than using steel to push out the copper, could there be another chemical that could push out the copper itself? This way we can have a chem solution without and possibly break them down to other chemical solution that can be useful in other ways.


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## goldsilverpro

On paper, these components exist in the solution. On a small scale, however, separation would be impractical.

There are selective chemicals for copper. Offhand, I don't know what they are.

A very unique chemical, Sodium Borohydride, will drop out most all metals, as metallics (I think). At last look, it was very expensive. I have a good IPMI article on this chemical that I will reread and report back. It's very powerful. If I remember right, 1 pound will drop 8 pounds of silver. If it's gotten cheaper, it may be the way to go.

I just found a patent using SBH to drop Pt directly as metal, and not a salt.

http://www.google.com/patents?id=6a4fAAAAEBAJ&dq=5304233


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## Irons

There comes a point where extracting values becomes uneconomical. The problem is how to deal with these materials without spending a fortune.
On another thread, there was a discussion of using a commercial polysulphide compound to recover values but it precipitates everything. It's what it was designed to do.

If you have to pay to dispose of hazardous waste, the trick is to reduce the volume to where the cost per ton is economical. 

Precipitation as sulphides works well in this respect. If done properly, there is little odor involved and the effluent is clean enough to recycle or dispose of in municipal waste streams.

one trick I use to reduce volume is store the liquids until winter and as they freeze, the ice pushes the salts to the bottom, leaving a very concentrated solution. The nice thing about it is I don't have to expend any energy to evaporate the solutions. All I have to do is leave a loop of rope in the top of the solution so that I have a handle to pull out the block of ice.

everything but the squeal.


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## goldsilverpro

The problem with the metal sulfides is that many of them are soluble in dilute acids. They probably wouldn't pass the EPA test.

The neat thing about sodium borohydride, NaBH4, is that the metals drop as metals, even platinum. I imagine it's gotten cheaper. The original method of manufacture used sodium metal and that's why it was expensive. It's basically made from boric acid and water. There's tons of info on the net about this chemical, including new ways of making it.


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## blueduck

I just looked on ebay and a fella there has 100 grams of it for $42.00 claiming that that is less than half the normal cost of it.... but we all know that ebay is over exaggerated for a lot of things related to recovery of precious metals.....

the chemistry store has boric acid for 90 bux for a 55 pound bag , and 5 bux for a one pound jar..... interesting idea to make it into a useful compound if such can be accomplished inexpensively by the "basement chemist" in our labor-a-tories <----- best Lon Chaney type voice in my head from the bugs bunny cartoons of my misspent youth.

now i have to go crack open a few of those chemistry books that other folks uploaded and ive got on my harddrive as pdf files...... just to figure out how to do such effectively or if it can be....... or find another source for procuring an already made product..... 

AS far as handling wastes, I wonder if a carbon arc would reduce the wastes to a small footprint in an economical manner..... such a unit was proposed to be built in Montana in the late 70's to mid 80's and that it would reduce a ton of material to a few grams of ash with virtually no emitted gas [dont know much more about it, I was kid at the time] it sounded to good to be true but it would have stopped a lot of landfills and that would mean less dollars somewhere and the thing was scrapped.... but it may be a viable thing to build even on a small scale......

William


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## Never_Evil

Sounds like we may have a new path to take to recovery platinum off hard drives and possibly out of the honeycomb in catalytic converters. I appreciate the feed back on my ideas.

dennis


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## Lou

goldsilverpro said:


> The problem with the metal sulfides is that many of them are soluble in dilute acids. They probably wouldn't pass the EPA test.
> 
> The neat thing about sodium borohydride, NaBH4, is that the metals drop as metals, even platinum. I imagine it's gotten cheaper. The original method of manufacture used sodium metal and that's why it was expensive. It's basically made from boric acid and water. There's tons of info on the net about this chemical, including new ways of making it.




I've used sodium borohydride many, many times. It's a very good reducing agent that only slowly reacts with water and primary alcohols (destroyed in a few hours' time, it is hygroscopic as well). It is used very much in organic chemistry as it is a clean, mild reductant and is much safer than lithium aluminum hydride which is pyrophoric. Many hydrides are becoming cheaper as they have potential use for storing hydrogen.

I know of only two effective ways (industrially) to make sodium borohydride. I am sure that it cannot be made from boric acid and water, even at high temperature.

The first method is that which uses sodium hydride, not sodium metal. Sodium hydride is nasty stuff, and unlike borohydride, is not a mild and selective reducing agent; it reacts dangerously with water, often catching fire. This is made by reacting sodium with hydrogen gas at high temperature and the process is the same for all alkali and alkaline earth metal hydrides. This is easy enough with a tube furnace, stainless piping, sodium metal, and a tank of hydrogen. After you have your hydride, you go about it industrial style, and react it with borane (BH3<->B2H6) which is NOT a good thing to work with as it is highly flammable, plus it's hard to buy, and extremely dangerous to make. 
It does react very nicely with NaH, NaH+BH3->NaBH4, and is clean. The borohydride is extracted with triethylamine or diglycol methyl ether (diglyme). That gives the best yields. You can use borosilicate glass (as in what beakers are made of) instead of borane, but yields are crap.


The other method is the trimethyl/ethyl borate with sodium hydride at 420F/270C from the late fifties, I think it's called the Schlessinger Process, and this isn't terribly useful, unless you have borohydride to begin with (since you can make trimethylborate from it).


Borohydride is nice, agreeable stuff for reducing platinum quickly and selectively, but it's expensive. Cheapest I've ever seen it was about $500 USD for 5 kilograms.

And Blueduck, for the $42, 100g is really cheap. It would probably cost about twice that from Fisher or Aldrich.

Still, there are other reducers that work just as well and better.
I find that the ammonium formate route works well though, and gives a clean product. Only thing that works better is using hydrazine or one of its salts (amazingly good reducer, and extremely clean, the product is nitrogen gas, ammonium cation). Too bad hydrazine is poisonous as hell, extremely explosive, and almost impossible to buy in this day and age. Straight up stuff still finds use in high performance rockets and ICBMs.

The salts are easier to work with though, and can be made very cheaply (about $15/kilogram), if anyone wants to know how, just ask.



Back to the pertinent topic, waste disposal. For me, it's always been a question of quantities and what it is. Somethings, like mercury, cadmium, lead, thallium, silver chromium, manganese, copper and vanadium just don't go down the drain and must be disposed of properly. As goldsilverpro mentioned, solubility changes depending on the compound and the pH. Some compounds won't be soluble in a base, but will dissolve right up in an acidic environment and vice versa. I always try to reduce the metal to the lowest oxidation state possible, preferably its metal form with a few exceptions (mercuric sulfide, for instance, is better than free mercury metal). Sulfides and hydroxides are generally not soluble at pH 5-8, but still won't be fit to sit at a landfill. 

Silver chloride is practically insoluble at the small scale, but get enough solvent (water) and it will dissolve and carry Ag+ ions away. How much depends on its Ksp, or solubility constant for that particular metal salt.

I am not saying that you should let the professionals do it all, as they'll charge you a lot to do it and eat up your profits, but rather to be smart about it and use chemical sense. For metals that are bad, it's about reducing their cations, for nasty anions, it's about oxidizing them. Cyanide is a good example--paying to dispose of sodium cyanide is absolutely stupid. Add the cyanide to bleach, either calcium or sodium hypochlorite, let it oxidize to cyanate, and then dump it down the drain.

Let the pros handle mercury, cadmium, and cobalt compounds...


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## Anonymous

Here's what i do to clean up the waste materials. React the spent acids with sodium carbonate to precipitate out the heavy metals then vacuum filter the carbonates out then put in a jar, when there is enough of them they are roasted to drive off the co2 and form oxides. The oxides are then mixed into concrete and disposed of. 

I reckon you could salvage the metals such as copper and nickel via electrolysis if you really want to, but it's more work than it's worth for small part time refiners. Any thoughts?


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## Noxx

I have no idea if this could work but one could heat Metal Chlorides upon decomposition to give Metal + Chlorine gas. The gas could be neutralized easily.

Just an idea...


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## peter i

Quite a few metal chlorides are rather volatile, and will evaporate rather than decompose.

In Denmark it is easy: As a private person any chemical waste can be handed in at the local “recycling station”. No price to pay, and no questions asked. They realized long ago, that this was the easiest way to avoid people flushing things that should not be flushed.

Iron ions are “mostly harmless” and dropping with iron would be my second choice.


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## geekzilla

goldsilverpro said:


> There is a misunderstanding that occasionally crops up on the forum about base metals that are dissolved in acids. Many people think that the reason for dropping out these metals, with iron or aluminum, is to recover them so that they can be sold, as is, or after melting. *Not so*. No one will want to buy the powder and melting the powder is most probably cost prohibitive for most all of you. You'll never get the stuff melted with a torch...



I am a newbie so maybe there is something I am missing. I figured that recovering the heavy metals and recycling them (copper, nickel and aluminum) was the natural next step in the refining process. One reason I am interested in the whole refining process is not just for the money from the gold and platinum, but the whole idea of recycling as much as possible because that is environmentally responsible. And then, of course, money from the rest of the base metals…

Also, I don’t understand your comment about never being able to melt the powder. The melting temperature for copper is 1,984 F, gold is 1,947 F, and aluminum is 1,220 F. Nickel is extremely high at 2,651 F. However all these temperatures should be achievable with a simple propane torch.

An oxy-acetylene torch achieves temperatures of 5,800 to 6,300 F and a propane torch maximum is 3,623 F.

So, why couldn’t the copper, nickel and aluminum be recovered through melting?


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## Rag and Bone

They can be recovered if you want them bad enough. The trouble is finding a market for the metals recovered from solutions. You're right to utilize everything, I share that goal. Also, the amounts of base metals recovered on the hobbyist level is small. At this point I'm just accumulating the base metals from solutions until there are more options.


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## Harold_V

geekzilla said:


> So, why couldn’t the copper, nickel and aluminum be recovered through melting?


You've missed the point. 

You can, indeed, melt all of the recovered values. The problem is the cost of melting and fluxing, both for the cost of materials, and the wear and tear of equipment. Flux has a nasty way of cutting short, VERY short, the useful life of furnaces and crucibles, and you can't melt them without fluxing because of the nature of the recovered materials. 

If you do some research, I think you'll find there is no market for the base metals recovered by conventional methods. That's not to say they are valueless----it's just that the typical foundry can't use them, and isn't willing to accept them. That leaves only the scrap yards, and my experience indicates they don't want them, either. 

Because of the nature of the recovery procedures, the metal you recover is very finely divided, and well oxidized and contaminated with other elements. Anything you do to improve the condition of the metal will reduce any hoped for profit, eventually exceeding the value of the metals you may recover. 

Understand I'm speaking from the perspective of one that has melted these metals------and in the end discarded two 55 gallon drums of recovered copper because there were no takers-----not even free. 

You may enjoy a different outcome in today's market, assuming you're willing to do some research. My experience dates back to the mid 90's, when copper was worth only about $1.20/lb at the refinery. For all I know, the Chinese market may be willing to accept them. 

Harold


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## geekzilla

Thanks for clearing that up for me Harold. I appreciate it.


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## Harold_V

You're welcome. I wish the message was more positive, but what I reported is what I have concluded in my attempt to do "the right thing" by trying to keep these elements in the pipeline. Sometimes you have to do what you don't want to do to preserve your sanity! :wink: 

Harold


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## Anonymous

I read an article about electrowinning and it stated that copper cloride was
25 percent more efficient to recover than copper sulfate and copper nitrate was 15 percent less efficient. It also stated that it takes 3kwh to produce 2 kilograms. This being a little over 4 lbs of cathode copper in one solid chunk would be worth at my local scrap dealer about $10.00 - $12.00 and cost only .25 cents worth of electricy and should yeild your acid(s). 

I am very interested in this because I think from electronic scrap there is more values in base metals than there is PGM content. So, in my own little way I am trying to learn how to get the Tin, Copper, Lead, and Zinc each seperated as I can sell them all. Getting the Tin at 90 percent purity sells for about $5.00 a lb.

Judging from all of the people on this forum and the marketing of various e-scrap hobby(ist) refiners there would be a large market for such service. Even if only to send them back they own copper so they can use it to cement more silver.


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## markqf1

The ideal situation would be to recycle it all.
The question is, what is financally and economically feasable with present technology?
With the price of all metals continuing to rise, it may be just around the corner.

Mark


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## Anonymous

I tried a little experiment with the copper chloride did not go so well. I did get an initial deposit of copper but it did not stay solid for long. I 
I hoping that was because my solution was rather spare of copper.
I did notice that it produced hydrogen and chlorine gases not the HCL back into solution as I had wanted.

I am going to try again with a saturated solution.


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## Harold_V

Your problem is typical of what I experienced when I tried parting copper. Unless you can keep the feed metal quite pure, as well as the electrolyte, you get poor results. I do feel the recovering the metals electorlytically is the way to go-----just work out the kinks!

Harold


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## Anonymous

My solution was way to acid. I had 100 ml of hcl diluted to 125 with water
and 1 gram of copper chloride the solution was a very light green.
I am going to make some copper chloride test solution today and reduce to a saturated solution, then add only 1 ml of acid, and reduce my voltage to 2 volts. I used a 6volt battery from an exit light the first time further reseach has made me think the high voltage was also bad for my process.


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## Harold_V

As a suggestion, instead of creating a theoretical solution, try working with one of the solutions you generate in the process of eliminating base metals --so you're working with what would be representative of the solutions you'll deal with. I would assume the level of concentration would be much higher---and you'd have the contaminants present that are possibly troubling. That's the real world you'd have to overcome. 

I might suggest, also, that you get a Variac, so you can control the output voltage---which is likely going to be critical if you expect a decent recovery in a form that is useful. 

While I never made the attempt to recover my copper electrolytically when I refined, I had a working relationship with a scrap yard that did business with another small refiner in my old home town. This guy had an education in chemistry and was recovering his copper by plating it on copper starter sheets. I saw them once, at the scrap yard. The deposit was somewhat nodular in nature, but was firmly affixed to the starter sheets, and was readily marketable as scrap copper. I wish I had more information, but that's the extent of what I learned. The guys at the scrap yard didn't know much about his process, and I never met the gentleman. 

Harold


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## Anonymous

I am going to try and use SS starter plates from the information that I have gathered the copper can be, heres the key word - easily peeled off of them for reuse.

Harold I do not have much to refine and was more working towards developing information that I could provide to the forum to help guys sell that copper they are making, more of a for the public good thing.

I do have about 25lb of boards and a couple whole computers but I would like to get results with a known solution then work towards the unexpect because I think if I can not get a solution that is just HCL and CuCL then I am pretty much dead in the water.


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## Harold_V

james122964 said:


> I am going to try and use SS starter plates from the information that I have gathered the copper can be, heres the key word - easily peeled off of them for reuse.


Mine were made of stainless, but the copper deposited in a solid film only briefly, then it started depositing as a furry mess, as I recall. 

If you have any options at your disposal, 316 stainless is the most chemical resistant----so it might be the best choice. 304 would be my second choice. 

Prior to starting my machine shop, I worked in a shop that made starter sheets for Kennecott Copper Corp., a huge copper producing company in Utah, which I have mentioned before. They were trying titanium sheets, with the same idea in mind. Titanium is pretty much inert, so it's an excellent choice for such an operation, so if you can obtain some reasonably, it's a good choice. It is difficult to machine----so be aware. 



> I do not have much to refine and was more working towards developing information that I could provide to the forum to help guys sell that copper they are making, more of a for the public good thing.
> 
> I do have about 25lb of boards and a couple whole computers but I would like to get results with a known solution then work towards the unexpect because I think if I can not get a solution that is just HCL and CuCL then I am pretty much dead in the water.


Your cause is noble as hell! I congratulate you. 

The problem, as I see it, is that the solutions that you will process in practice are likely to be very different from a solution that is made with specific concentrations and elements in mind. That is likely to have a profound effect on how things work, or don't work. Too bad GSP isn't commenting----he has an extensive background in plating, and understand very well the ramifications of miniscule changes in electrolyte and voltage/current in plating, which, for all practical purposes, is what you're trying to accomplish. 

Were it not for seeing the copper that was recovered by my competitor, I'd suggest you're wasting your time, but it's obvious the problems can be worked out. Be sure to keep us all posted on how things go. You'd provide a much needed service, especially for guys that process a lot of silver. 

Harold


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## Anonymous

Harold, I have some real world stuff brewing now copper pins with gold and palladium. I have them going in the acid (HCL) and hydrogen peroxide. When its done cooling I will proceed to try and get the copper by electrowinning. I have gotten a couple of resisters so I can lower the voltage, I am only going to work at 1volt this time instead of 6v from a lead battery so really closer to 7v.


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## Palladium

James check this for some good copper info :arrow: http://goldrefiningforum.com/phpBB3/viewtopic.php?p=19690#19690


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## Harold_V

Looking forward to your next report, James. 

Harold


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## goldsilverpro

To make the metal deposited separate easily from the SS cathode, several things can be done.

You can passivate clean 300 series SS by soaking it for an hour or two in a 50/50 nitric solution. Rinse well afterwards. This will help prevent the metal from adhering to the SS.

Although I never liked this method, some people very lightly oil the SS. Don't use an oil that contains silicone.

The deposited metal will tend to wrap around the edges of the SS sheet, which makes its removal difficult. This can be solved by wrapping plastic plater's tape (3M) on the edges of the SS sheet.


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## Scott2357

What about a SS ladle? I saw a 3 1/2" diameter one for about $3 the other day. Cut the handle and bend it to hook on the edge of the process tank. To avoid metal plating on the edge, adjust the hook so at least top 3/16" of the parabola is above solution.


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## Anonymous

I got some copper flashing today I am going to use that for my starter sheets. Also I do have a plan B. This may be the best way to go.
Concentrate the Cu chloride solutions, then convert them with sulfuric to cu sulfates then I can boil off my HCL, since summer is coming I may even use solar power to do that and to concentrate the the chlorides.
Then electrolys the CuSO4 giving me copper and my sulfuric back, Hoo Rah I have a realistic plan.

Also making a tube to pack the copper slug to run through the electrolyte before depleating to acid.


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## Anonymous

Well I have two solutions ready to test the first is from AP process on copper with Gold plating and PD content mixed the second is just copper 
reacted with the commonly used formula for AR that is nitrate and HCL based - I use KNO3 for the nitrate. I will be attempting the plate out with 
1.5v from for ease of use rechargeable D Cell batteries. 

I am also going to prepare some Cupric Oxide to add to my solutions to make sure they are used up.

Picture and results tomorrow or monday.


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## Anonymous

Well plated out some copper. I did better than the first time but was still very spongy. Also, I use SS for my anode and it dissolved contaminating my solution. 

I have been doing some more research. I have diluted my solution and have a new lead anode. Also increased the surface area to cut down on amp density. Added 1 teaspoon of sugar to the solution as a lot of
the references state that the solutions contain organic stabilizer but do not say what it is.


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## Palladium

Have you tried Titanium James ?


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## Harold_V

james122964 said:


> Well plated out some copper. I did better than the first time but was still very spongy. Also, I use SS for my anode and it dissolved contaminating my solution.


My anode was comprised of gold alloy and copper, which worked well aside from the spongy deposit. That seems to be a common problem, and was enough to discourage me from any further attempts, considering my purpose was to gather the slimes for further processing. They were too heavily contaminated by the spongy deposit, which regularly fell free from the cathode. It's important to get a nodular deposit, if not a smooth one, when depositing the recovered copper. 

Ralph's recommendation to try titanium is pretty much right on the money. It's commonly used in plating, being inert. I used to use a slab of titanium for stripping watch bands with cyanide, and found it would erode to some degree if allowed to contact the electrolyte. I don't think that will be an issue with sulfuric, but I'm not sure. Could be Lou or Irons can comment in that regard. If lead works, that, too, may be the right thing to pursue. If any transfers, I'd forget it in a hurry. Sort of defeats the purpose, especially if the copper is intended for recovering silver. 

Harold


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## Palladium

Here is a good pdf on Ti :arrow: http://www.timet.com/coresistframe.html


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## Anonymous

I may try some Ti, got lead this time because research indicates it is the 
material used commercially. 

I will keep plugging away. This has consumed most of my free time and I have to work on my new furnace some. I really need to get it done as I have all of the molds ready to cast myself a new milling machine.


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## Bernie Foley

Hi all,
I used to do copper electrowinnig processing the slimes for gold and silver. To get a plating solution to work i used an electrotyping solution of sulfuric acid and copper sulfate. The anode consists of the metals to be refined.. a clean thin sheet of copper for a starter cathode.
from the 1929 metals finishing guidebook solution as follows:
copper sulfate 32 0z per gallon of water
sulfuric acid 8-10 0z per gallon of water current density 20-50 amps/sqft.
at 1-4 volts dc. well filtered power supply..(not a charger)
However for the electrowinning keep the voltage below .38 volts as only the copper will plate out. I used to grow different shaped cathodes and sell them..deposit is nodular to crystal.........Good luck....Bernie


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## Anonymous

It has been a while since I have worked on trying to get the copper to plate out solid. The problem is from what I can see using sulfate and sulfuric works to plate solid, but we have either copper nitrate or chloride or a mixture of these with some other metals in the mix.

My first attempts were with the voltage to high. I did get copper to drop out at the cathode but it was a powder. Harold brought up the point that this is cathode copper even though it is not solid. I think this could be washed and pressed or melted into a salable form. It would definitely be better to get the copper to plate out as a solid deposit.

The problem I have is that everything I use for an anode gets dissolved in the process and ends up messing up my solution. 
I do not have access to the good stuff like Pt or enough pure gold to try. I am not even sure they would work because I have seen a lot of stuff on the internet where they use electricity and different chemicals to dissolve gold and Pt. 

The basic electrowinning process may be best, melt the scrap into an anode and process it in a copper sulfate and sulfuric cell, to get pure copper (hopefully solid) and gold powder to filter out.


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## Jehu

Hi all. I just joined up today so go easy on me. 

I'm not too sure on the orderof how reactive different metals are but I do know that Aluminium will precipitate out the copper from a copper sulfate solution leaving Aluminium Sulfate, which is used as a blueing tonicfor hydranger flowers. I don't know if it will drop the other metals that we're worried about but if it does you could melt them all together and then put them through the electrowinnowing process, recovering each as you go. 

Also on the note of clorine, if you burn it with hydrogen you will get your hydrocloric acid back. So it might be a god idea to try and collect the clorine gas with a fume hood or something and pump it through a bubbler with distilled water in it to scrub it. Then you can get it back later. 

Just a few thoughts


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## Bernie Foley

Hi all,
Welcome to the forum Jehu!
I think aluminum will precip.most all or if not probly all of the values.
I beginning to see why a thum cell has to have 90% silver to work!!
GSP could tell us all about silver cells. Titanium anodes cathodes when i tried them they either anodized or pitted real bad...even in salt which
titanium is sposed to be impervous to salt and seawater!
Would be nice if we could precip. all the nickel&copper out of solution..
Good luck!..........Bernie


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## Jehu

I've heard that Titainium is used in electrolytic cells in submarines to produce extra oxygen for the crew. So it should take the strain of being a good anode.


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## nickvc

Harold_V said:


> james122964 said:
> 
> 
> 
> Well plated out some copper. I did better than the first time but was still very spongy. Also, I use SS for my anode and it dissolved contaminating my solution.
Click to expand...

My anode was comprised of gold alloy and copper, which worked well aside from the spongy deposit. That seems to be a common problem, and was enough to discourage me from any further attempts, considering my purpose was to gather the slimes for further processing. I kow this is an old topic but i wondered if you had problems with the sponge in your wastes would an annode bag not catch all the slimes? i used this method in a silver cell to catch the gold contaminants any sludge at the bottom of the cell should be copper or in my case silver...


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## Gold Trail

Im jumping the gun here becuase I havent done my research. 

What about something like "T-6" (i think its called) sold by gold mine world?

Its actual use is at sewer treatment plants to drop out ALL metals into a sludge, i think. Its supposed to be fast too. I have found it for sale at other places, but not much cheaper than goldmineworld. 

there was some posts on this forum about these precipitants as well. 

just my thoughts

Ryan


----------



## dick b

Anybody:

Could this T-6 be Potash alum?

dickb


----------



## Palladium

http://www.waterspecialists.biz/html/tr_detox___stabilization_techn.html


----------



## Palladium

http://www.waterspecialists.biz/TR-6_PB.pdf


----------



## dick b

Thanks.
I saved that pdf for reference. I never new of any of the treatment plants around here using Thio-red, but they do use alum as a flocculant and it's reasonably cost effective to use.
dickb


----------



## Irons

dick b said:


> Anybody:
> 
> Could this T-6 be Potash alum?
> 
> dickb



It's a polysulfide, so it precipitates metals out a sulfides.


----------



## joehast

This is precisely the reason I no longer refine boards or fingers. I feel the contaminates left over are just too bad. I called our local PCA a while back, got a voice message, called back again and got nothing but attitude from the Receptionists. (Our MN tax dollars at work..!) In my state this Government office is huge with little accountability.) 

None of the local Refineries where I sell my boards will take my contaminates w/o an EPA #, Infact it seems as if they discourage my works. Now I just cut off the fingers, and sell them separately to the refinery, I actually get a good price for them and I know that the contaminates are properly cleaned up.

I know a guy who refines a pretty good amount of fingers on a regular basis due to the amount of PC scrap he has access to. I asked him what he does with his green waste, He smiled and said "I know a Bush that likes it". At first I thought this was a little humorous, then I thought about the watershed he lives in and how the City well is really not that far away from his residence.

I would never encourage or teach anyone how to refine circuit boards.!


----------



## goldenchild

Lou said:


> I've used sodium borohydride many, many times. It's a very good reducing agent that only slowly reacts with water and primary alcohols (destroyed in a few hours' time, it is hygroscopic as well). It is used very much in organic chemistry as it is a clean, mild reductant and is much safer than lithium aluminum hydride which is pyrophoric. Many hydrides are becoming cheaper as they have potential use for storing hydrogen.
> Borohydride is nice, agreeable stuff for reducing platinum quickly and selectively, but it's expensive. Cheapest I've ever seen it was about $500 USD for 5 kilograms.



A bump I know but... say I wanted to give sodium borohydride a whirl. What is the procedure to drop metals? Is it as easy as dropping gold with smb? Being that it's hygroscopic I would think so. I'd like to get a small batch of 100 grams to process a bunch of Pd/Pt scrap I've been sitting on for a very long time now. Where would be the cheapest place to get this 4 years later?



Lou said:


> Still, there are other reducers that work just as well and better.I find that the ammonium formate route works well though, and gives a clean product...
> 
> The salts are easier to work with though, and can be made very cheaply (about $15/kilogram), if anyone wants to know how, just ask.



Was Lou talking about making ammonium formate? Because if he was I'm askin. Where could I find it and what would be the procedure for ppt?


----------



## goldenchild

Anyone?


----------



## ericrm

so... have somebody fund a real green and money friendly way of disposing of theyr garbadge


----------



## NoIdea

Morning All – I am currently working on the waste stream, I to believe in full recycling, or as close as I can get.

The method so far goes like this:

My waste consists of base metals, firstly the waste is put into small 2lt containers along with granulated copper, this form of copper works well, large surface area, and precious metals will drop, and the container is shaken periodically. After 24hr the finally divided precipitates are filtered after being put into suspended solution by shaking. The copper stays on the bottom and is shinny after the strip is complete.

Stage two, the waste is transferred to another 2lt where an iron bar is placed, occasional shacking and in 24hr the solution has gone from darkish blue/green/brown to green. The waste is filtered to obtain copper and anything else below the reactivity scale for iron and forms a stable precipitate.

Stage three, yet again the waste is transferred to another 2lt container in which aluminium foil is added from pyrolized electrolytic capacitors. This will take time, especially if the pH starts to creep up and the remaining acid is consumed. The solution is almost clear at this stage, with a slight greyish look after filtering. I need to do a little bit more work, finding out what is in the filter cake.

Now for the forth stage, this still needs to manifest itself but will any luck it will go like this, aluminium chloride hexahydrate is the main contaminant along with any unstable aqueous metals that aluminium cannot precipitate. I intend to evaporated this solution until the aluminium chloride hexahydrate starts to becomes volatile releasing HCl for reuse.

Forgot to mention the Iron contaminant :roll: 

Well that’s my theory so far. I am at the filtering stage of the aluminium drop of precipitable metals.

Any constructive thoughts on the last portion of the process will be muchly appreciated.


Regards

Deano


----------



## butcher

Aluminum works well, but the slimmy stuff takes ages to dry,heat helps.

How would you get HCl from this? Aluminum gives off Hydrogen as gas when it dissolves, so where is the Hydrogen going to come from to make Hydrogen chloride from the aluminum chloride salts? are you useing the hydrogen from that first reaction (dissolving the aluminum) somehow?


----------



## NoIdea

Hi Butcher, From Wiki – “Hydrated aluminium trichloride is prepared by dissolving aluminium oxides in hydrochloric acid. Heating this solid does not produce anhydrous aluminium trichloride, the hexahydrate decomposes to aluminium oxide when heated to 300 °C:[4] 2 AlCl3 + 3 H2O → Al2O3 + 6 HCl”

The hexahydrate is also formed when aluminium reacts with metal chorides in solution below aluminiums reactivity. As for hydrogen, it is not the reductant, it's the exposed aluminium after the oxide is dissolved by the HCl


I have about 1.5kg of the anhydrous AlCl3 that I can experiment with, and this is very nasty stuff, evolves HCl when exposed to any form of moisture.

Cheers

Deano


----------



## butcher

So if I understand this, the water in the reaction with AlCl3 provides the hydrogen, giving an oxide of aluminum and Hydrochloric acid?

Aluminum is above hydrogen in the reactivity series’ of metals but I did not realize it would split or disassociate the water (or its salts), (I know some of the very reactive metals would but they usually form metal hydroxides), and that this AlCl3 is not elemental aluminum and where metal aluminum may not split water is it something about its chloride or is it the 300 degree heat a major part of this reaction, or combination of both ?

I am not a chemist, but sure like to learn what I can about how these things react, sometimes the language you chemist use is above my vocabulary list. 

Ya know how us hillbilly's R bout talkin.

The HCl I presume would be a gas and need to be bubbled into water?

This would be a good way to deal with the aluminum slime, 

Thanks.


----------



## NoIdea

Hi Butcher, I think the process is called thermal decomposition, degradation or something like that, heat anything hot enough, break the associated bond energy’s, thus allowing them to reform into more stable compounds. With organic compounds, covalent rather than ionic bonds are broken; the reforming of molecules or elements can be rather random due to free radicals produced as a result of high temperatures.

Aluminium Chloride Hexahydrate = AlCl3.6H2O The water molecules supply’s the oxygen for the formation of Al2O3 and the hydrogen for the HCl.

And yes, the HCl needs to be cooled first and then bubbled through water, colder the better, using a bubbler inside an inverted funnel works well to.

Copper oxide which is an unwanted product from the iron drop of the rich copper waste solutions, caused by oxidation during drying, will be reduced using hydrogen, generated by the reaction of aluminium with NaOH, drying the hydrogen through concentrated sulphuric acid. The copper oxide is heated to above 500deg C. and then the dry hydrogen introduced, product? - Copper powder, water and possibly some un-reacted hydrogen. 

This is sort of the reverse when it comes to removing Oxygen from air. Pass air over/through finely divided copper above 500deg C. and copper is oxidised, resulting in an Oxygen free gas.

Hope this sort of helps, I do ramble now and then. :roll: 

Cheers

Deano

Please Note: Due Not under any circumstances perform hydrogen production, using aluminium and NaOH, in a glass vessel in the sun or bright light. Unwanted by-products of this reaction, formed by impurities within both the aluminium and the NaOH, mainly Chlorine, will react violently and may cause an explosion. Be Warned.


----------



## goldenchild

Anyone?


----------



## NoIdea

Afternoon All - Just a wee follow up on my earlier reply.

http://www.youtube.com/watch?v=b3eSsglDNgw

Only just found this, fits in well with what I am doing so far.  


Deano


----------



## ericrm

im sorry i will wrote in french because ,it is very hard for me right now to explain myself in english on this subject.

ce que je veut dire ,c'est que la solution a notre probleme n'est peu etre pas celle que nous croyons, nous cherchons un moyen de se departir de nos dechet de facon economique et nous finissons par envoyer nos dechet de facon illegal a la poubelle mais si nous cherchions des produits qui sont utilisable a plusieur reprise. a titre dexemple (personnellement je ne lai pas encore utiliser)lacide peroxique reoxigener, qui selon plusieur ici est utilisable a repetition avec lajout dun bulleur a poisson.il en revien donc beaucoup moin cher de sens departir legalement etant donner que les cout sont amortis sur plusieur batch.
peu etre devrions nous chercher a rentabiliser nos produit plutot que de sens departir a moindre cout.

sinon il y a la posssibiliter de changer nos produit pour finir avec des truc bon pour lenvironnement ex: le sulfate de cuivre
si au lieu dutiliser de lacide peroxique pour retirer les doigt de carte nous utilisons de lacide nitric ,le residue qui se fais est du nitrate de cuivre, ce meme nitrate de cuivre peut etre reconvertit en acide nitric avec comme produit residuel du sulfate de cuivre qui si je ne me trompe pas est un engrais courant...


----------



## NoIdea

ericrm said:


> im sorry i will wrote in french because ,it is very hard for me right now to explain myself in english on this subject.
> 
> ce que je veut dire ,c'est que la solution a notre probleme n'est peu etre pas celle que nous croyons, nous cherchons un moyen de se departir de nos dechet de facon economique et nous finissons par envoyer nos dechet de facon illegal a la poubelle mais si nous cherchions des produits qui sont utilisable a plusieur reprise. a titre dexemple (personnellement je ne lai pas encore utiliser)lacide peroxique reoxigener, qui selon plusieur ici est utilisable a repetition avec lajout dun bulleur a poisson.il en revien donc beaucoup moin cher de sens departir legalement etant donner que les cout sont amortis sur plusieur batch.
> peu etre devrions nous chercher a rentabiliser nos produit plutot que de sens departir a moindre cout.
> 
> sinon il y a la posssibiliter de changer nos produit pour finir avec des truc bon pour lenvironnement ex: le sulfate de cuivre
> si au lieu dutiliser de lacide peroxique pour retirer les doigt de carte nous utilisons de lacide nitric ,le residue qui se fais est du nitrate de cuivre, ce meme nitrate de cuivre peut etre reconvertit en acide nitric avec comme produit residuel du sulfate de cuivre qui si je ne me trompe pas est un engrais courant...



Hi - is their anyone here know french and possibly translate, or at least a summery pretty please

Thanks

Deano


----------



## Palladium

You have to read into it. 

what I mean is that the solution to our problem cannot just be one we believe, we are looking for a way of to MBRs of our waste in a way economic and we're sending our way illegal waste has the garbage but if we were looking for products that are usable has several recovery. a title example (personally I do lai use yet) lacide peroxique reoxigener, which many here to be usable has repeating with support dun arrays a poisson.il in will therefore much control much of sense MBRs legally being that give the cost is amortized over many batch.
shortly be should pick us up a return our product rather than meaning MBRs at lesser cost.


otherwise there is the posssibiliter to change our product to finish with a good trick to environment ex: copper sulphate
If instead using of lacide peroxique to remove the finger from card we use of lacide nitric, the residue is doing is of copper nitrate, even copper nitrate can be converts acid nitric with as residual of copper sulphate which if I'm not mistaken is a common fertilizer...


----------



## ericrm

palladium that is a terrible translation but thank to do your best, in large what i mean its we try to reduce cost to get rid for cheap... maybe we can find something that cost a lot to get rid of but who will also do for multiple use...

also
maybe theyr is a way to treat our base metal so the end solution garbage (can be a good thing for environnement)as an exemple sodium nitate i use to make nitric acid,nitric acide make copper nitrate,copper niitrate is reuse for to make nitric acide with the en product witch is copper sulfate ,if im right is a fertiliser... grosso modo but it better in french.... :|


----------



## ericrm

At the cathode, electrons are supplied to cations, which migrate to the cathode. The Cu2+ cation is discharged by accepting electrons. At the anode, electrons are supplied to the anions, which migrate to the anode. The half reactions are

Reactions at electrodes during copper(II) chloride electrolysis

Generally speaking, prediction of the nature of the products is complicated by (i) concentration effects and (ii) the rate at which the oxidation and reduction of different ions takes place. Standard electrode potentials can give a rough guide as to what may happen.

As a guide, in fairly concentrated aqueous solution, metals with a positive (reduction potential) will be formed at the cathode.Otherwise, hydrogen is formed by reduction of water or of the H+ ion.

<<<<<<<<<<<<<< Halogens (chlorine, bromine and iodine) are formed at the anode when aqueous solutions of halides are electrolyzed>>>>>>>>>>>>>>>>>.

The sulphate ion is not discharged (oxidized) at the anode in aqueous solution, rather, oxygen is formed by oxidation of water or of the OH- ion. Thus, electrolysis of sulphates produce oxygen at the anode.

the part that i have put in <<>>> doest that mean in a solution of halide we keep our acid when electrolysed or we lost it??? sorry i try my best to understand but im realy not good....

i might be wrong but if to have h+ in solution means to have an acid,electrolising cucl2 would make cu on one side cl on the other side ,keeping the h+ in solution...
if i sound dumb Im NO F...G SCIENTIST i just try to help, so help me too


----------



## NoIdea

Morning All – And what a lovely Saturday morning it is.  

Hi ericrm – For electro stripping of copper sulphate solutions, a passive anode is required, I must admit, I have not tried this approach yet.

The copper sulphate can be treated in the same manner as the copper chloride, instead of aluminium chloride hexahydrate, aluminium sulphate is the final product, this can be dried and heated to produce SO3 gas which can be absorbed into water or existing sulphuric acid.

The sulphate has a higher decomposition temperature than the chloride, which makes me wonder, if a mixed sulphate chloride solution can be dried and then fractionally decompose by monitoring the decomposition temperature.

I guess I’ll find out as I happen to have a mixed solution of sulphate and chloride to work with.

Today is drying day, so I will keep updating as I go. I have around 30+ litres of waste that urgently needs my attention, so far so good.

Check out the tread “Home Made Filter”, it shows the solutions processed in the manner described so far.


Cheers

Deano


----------



## Palladium

Saturday morning. :shock: :shock: :shock: 

Good afternoon. :lol: 

It's 4:30 in the pm on Friday afternoon here.


----------



## NoIdea

Hahaha - I was wondering if anyone was gunna pick that up. :lol: 

It's 10:26am Saturday the 3rd of Sep, We see in the new year before anyone else, apart from the Cook Islands, I think.

Deano


----------



## jimdoc

NoIdea said:


> Hahaha - I was wondering if anyone was gunna pick that up. :lol:
> 
> It's 10:26am Saturday the 3rd of Sep, We see in the new year before anyone else, apart from the Cook Islands, I think.
> 
> Deano



Can you see tonights winning lottery numbers?

Jim


----------



## NoIdea

Sure can - 1,23,32,8,19,.... blast, miss the rest, Sorry :mrgreen: 

LMAO

Gotta love a good morning laugh, thanks. :lol: 

Deano


----------



## Harold_V

ericrm said:


> maybe theyr is a way to treat our base metal so the end solution garbage (can be a good thing for environnement)as an exemple sodium nitate i use to make nitric acid,nitric acide make copper nitrate,copper niitrate is reuse for to make nitric acide with the en product witch is copper sulfate ,if im right is a fertiliser... grosso modo but it better in french.... :|


Do I understand you correctly? You think copper sulfate can be used as a fertilizer?

If that's what you mean, no, it can't. In fact, hell no, it can't. Copper sulfate kills plant life.

Harold


----------



## ericrm

harold im very happy that you told it to me ,because i was realy thinking that it was a fertiliser ...


Copper Sulphate fertilizer 98% (CuSO4.5H2O – 893 Similar from this Supplier

????


----------



## NoIdea

Well I looked it up and sure enough it's used in cereal crop production, not much though. Well I never. I was also sure it was used to kill plants and as a timber preservative. learn something new every day, Live and learn. 8) 

Other contaminants would be my biggest worry, using waste solutions; producing copper with impurities is allot more forgiving than a fertiliser with impurities.

Deano


----------



## qst42know

I wouldn't call it a fertilizer? 

But it does have agricultural uses. Perhaps "fertilizer" refers to a grade of purity or "class" of chemical?

I know of a couple of uses. It's used to suppress wild yeasts in grape crops, and to control algae in ponds. Being an anti fungal it may have many other farming applications, though as a poison the dosage must be critical.


----------



## butcher

Copper sulfate is used as fungicide used on grapes and other crops.
It is also used to remove roots from sewer lines, sold in hard ware stores like wallmart, I save mine for using in electrolisis, or to dissolve metals higher in series than copper.

http://www.google.com/#hl=en&source=hp&q=copper+sulfate+uses+in+agriculture&oq=copper+sulfate+uses+in+agriculture&aq=f&aqi=g1&aql=&gs_sm=e&gs_upl=2578l18172l0l21672l34l34l0l16l16l0l218l2812l2.12.4l18l0&bav=on.2,or.r_gc.r_pw.&fp=e9e4cb08cebaa4fe&biw=988&bih=573


----------



## ericrm

finaly it realy has nothing to do with a fertilizer ,but it can be quit useful when you need it

but in my case it is not to solve the garbadge probleme ,and it even create more probleme nowing that if poeple think it is not that dangerous it will still en up in the toilet....

it is kind of a mind bugger...

can copper be melt on a open fire?


----------



## butcher

ericrm, yes it can.
Copper when heated or trying to melt oxidizes very easily forming copper oxides, but can be melted if oxygen is removed from the melting environment, like adding charcoal or flour to the melt or using some other carbon source, this will take oxygen that would otherwise oxidize the copper, and make CO2 gas, when brazing copper brazing or silver solder rod will contain phosphorous which removes oxygen, copper melts at 1084 degree's C, this is much higher than a normal fire, and would usually need oxygen source to reach these temperature's, you can melt copper but it will cost you much in fuel, probably more than copper could be sold for.

Copper salts would be another issue as far as melting them; you would have acidic gasses generated in the melt, and would most likely end up with copper oxides, depending on your starting materials.

As far as electrolysis, unless the copper was very pure it will not plate to cathode as a solid mass but come out of solution as a fluffy moss.

lets look at a few things we may choose to do with some of the copper solutions we generate, copper II chloride we can reuse in our acid peroxide solutions to dissolve more copper, or we can let it go to copper I chloride powder and use this to dry and store to be regenerated later to CU2Cl, or we can use it to remove gold or silver from solutions (usually in recovery processes), or copper chloride solutions will dissolve metals higher copper oxidizes easily when trying to melt it, using a carbon source like charcoal, flour, in series than copper, which would displace copper from solution and make a chloride solution of that metal, copper sulfate could be made from the copper chloride solutions by adding sulfuric acid and heating to a copper sulfate salt, this copper sulfate can be used in electrolysis cells, 

now say we had copper nitrate solution left after cementing silver from a silver nitrate solution, we could make copper chloride from it or copper sulfate, we can crystallize the copper nitrate to salt’s had heat them to 256 deg C and drive off NO2 fumes which if bubbled into some water with a little H2O2 would make nitric acid, or with the copper nitrate salts we could separate the copper electrically from the nitrates, using a graphite anode (inert) and make nitric acid and copper powders, we also can dissolve metals higher in series than our copper in this nitrate solution, 

The list can go on, of things we can use, from what we could normally consider to be waste.
Solutions take a lot of room, many of these compounds can be evaporated to salts and saved dry, and used later, who knows maybe some could be sold to eBay, or maybe even the chemistry dept at your local high school has use for some of the salts like copper nitrate, or sulfate for experiments, and maybe the teacher would like you to do a demonstration of dissolving silver, cementing with copper and melting the silver for the students, this would be fun to teach the kids, and then maybe the teacher had a few salts he could give you that his lab no longer needed.


----------



## NoIdea

Morning All – Just a quick update on recovering HCl from waste solutions.

Recapping So Far:

1. Waste is treated with Copper fines to drop any PGM’s. Solution is blue/green.
2. Waste is treated with Iron bar to drop copper and anything else below iron. Solution is green
3. Waste is treated with Al to drop Ni, Fe, etc. Solution is clearish
4. The aluminium chloride hexahydrate was evaporated to dryness with Al foil present
5. The dried Hexahydrate is distilled to release HCl gas and possibly some Cl gas
6. HCl and Cl gases are dissolved in cold water to produce HCl/Cl acid.

There were traces of nickel still left after dropping with Al, but did not appear to affect the out come.

Note: Do not evaporate the Hexahydrate solution in stainless steel containers. I checked the pH of the evaporating solution through out the process, showed pH neutral up until the solution became saturated, but no HCl fumes were observed. Checked resulting steam with moist universal pH paper.

The hexahydrate appears to be hydroscopic; this may be due to impurities.

Cheers

Deano


----------



## butcher

Thanks for the progress update, sounds like the HCl is formed in the fusion and attempts to make back aluminum chloride in fusion, is that the way you see it?


----------



## NoIdea

Evening Butcher – Hmm, not sure of the mechanism, but I would suspect it has a lot to do with equilibrium and temperature, at low temperatures the equilibrium will go by way of the hexachloride and as the temperature increases that equilibrium will head towards the aluminium oxide and HCl gas.

I Should Have Noted: I ended up distilling the un-dried hexachloride due to its very hydroscopic nature, brought about by contaminated metal salts, excess aluminium foil added, or just because it likes water. After applying gentle heat, boiling of the goo-wee mass started, producing HCl gas, and water vapour.

In the previous post I noted that the solution became more acid at higher concentrations and that is why I added extra Al foil in an attempt to push the balance of the solution towards the hexahydrate.

To be honest, I am unsure as to what is actually going on, too many variables, but I will stick with it to recover, at least in part, some of my consumed chemicals and reduce my ever mounting waste, which I refuse to “Pour Out”. It’s amazing how much the aluminium pulls out of solution, not to mention the amount of material I have obtained after the iron and copper drop’s, food for thought.

I have, after today, 36lt of aluminium dropped HCl waste solution, with only 2lt reduced to the goo. 

Not sure if I answered your question or not.

Cheers

Deano


----------



## butcher

Yes question was answered very well, what material are you using for a distilling vessel glass, or can it take the temperature?

Why not recover most of the HCl, or other acids early in the waste stage that is what I will normally do. Like distilling the acid peroxide waste, or Iron chloride waste, this will concentrate metals in solution, once thick syrup, I move to another jar on cooling the salts crystal out of solution lowering acid content in them, the cool solution can be decanted and redistilled with more of same more dilute waste (reusing these metal salts in recovery or making other metal salts from them, or re-dissolving them depending on what they are), the distilled solutions I normally use in recovery processes, as sometimes they may contain more than one acid like HCL and nitric. (But these can be cleaned up like removing chloride from nitric acid by using silver nitrate), the HCl or even nitric solutions distill off fairly easily, the sulfates usually end up as salts, and even these can be roasted in retort, bubbling gas into sulfuric acid for making more sulfuric acid from resulting oleum (I have not tried this one yet).


----------



## goldenchild

Any information on sodium borohydride? I posted a few pages back.


----------



## seawolf

I found this, hope it helps.
Sodium borohydride

Sodium tetrahydroborate

NaBH4

NaBH4 Sodium borohydride is so stable in water that a 12% aqueous solution stabilized
with sodium hydroxide is sold commercially. In order to effect decomposition, the solid or
aqueous solution is added to enough water to make the borohydride concentration less than 3%,
and then excess equivalents of dilute aqueous acetic acid are added dropwise with stirring under
nitrogen.

http://www.chemistry.emory.edu/.../ChEmoryWasteDisposal_NEW.pdf


----------



## Joeforbes

NoIdea said:


> ericrm said:
> 
> 
> 
> im sorry i will wrote in french because ,it is very hard for me right now to explain myself in english on this subject.
> 
> ce que je veut dire ,c'est que la solution a notre probleme n'est peu etre pas celle que nous croyons, nous cherchons un moyen de se departir de nos dechet de facon economique et nous finissons par envoyer nos dechet de facon illegal a la poubelle mais si nous cherchions des produits qui sont utilisable a plusieur reprise. a titre dexemple (personnellement je ne lai pas encore utiliser)lacide peroxique reoxigener, qui selon plusieur ici est utilisable a repetition avec lajout dun bulleur a poisson.il en revien donc beaucoup moin cher de sens departir legalement etant donner que les cout sont amortis sur plusieur batch.
> peu etre devrions nous chercher a rentabiliser nos produit plutot que de sens departir a moindre cout.
> 
> sinon il y a la posssibiliter de changer nos produit pour finir avec des truc bon pour lenvironnement ex: le sulfate de cuivre
> si au lieu dutiliser de lacide peroxique pour retirer les doigt de carte nous utilisons de lacide nitric ,le residue qui se fais est du nitrate de cuivre, ce meme nitrate de cuivre peut etre reconvertit en acide nitric avec comme produit residuel du sulfate de cuivre qui si je ne me trompe pas est un engrais courant...
> 
> 
> 
> 
> Hi - is their anyone here know french and possibly translate, or at least a summery pretty please
> 
> Thanks
> 
> Deano
Click to expand...



Deano, here is a rough translation -

"what I mean is that the solution to our problem is not that just be that we believe, we seek a way to dispose of our waste in an economical and we end up sending our waste is illegally the trash but if we were looking for products that are using several times. a reference only (I personally do not use lai) lacide Perox reoxigener, which some here are used repeatedly with a bubbler lajout dun poisson.il in return, therefore, much cheaper to dispose lawfully meaning being given that the costs are amortized over batch number.
should be little we seek to return our product rather than dispose of meaning a lower cost.

otherwise there is the possibility of the change our product to end up with something good for the environment eg copper sulphate
if instead USE OR lacide Perox to remove finger card we use nitric lacide, the residue that is doing is copper nitrate, copper nitrate, the same can be converted into nitric acid as a product with residual copper sulfate if I'm not mistaken is a common fertilizer ..."

You can get the jist of what he's saying..


----------



## ericrm

just tought it has been a long time since i read this topic and i just discover it havent moved much..
does anyone in the end have come with any idea to reduce the garbadge probleme?


----------



## ericrm

here are my latest find with will need aproval from more experience poeple...

potassium sulfate and zinc nitrate are two left over that i got (if i choose to pay a bigger price to run)

potassium sulfate
The principal use of potassium sulfate is as a fertilizer. K2SO4 does not contain chloride, which can be harmful to some crops. Potassium sulfate is preferred for these crops, which include tobacco and some fruits and vegetables. Crops that are less sensitive may still require potassium sulfate for optimal growth if the soil accumulates chloride from irrigation water.[5]

zinc nitrate
Zinc Nitrate Solution is an easily adsorbed liquid fertilizer with zinc and nitrogen compounds which further increase absorption efficiency. Zinc Nitrate Solution stimulates cell formation, increasing leaf size and encouraging good root development and plant growth. Disease and stress tolerance is enhanced. With higher zinc levels in the plant, there is greater uptake and utilization of fertilizer and soil nutrients for significantly higher yields and crop quality.

could i put this on my grass ,fruit, and vegetables and dont worry anymore


----------



## qst42know

Where do you get zinc nitrate from?


----------



## ericrm

i think that i could ciment copper out from copper nitrate with zinc ending with zinc nitrate...


----------



## qst42know

Lazersteve posted how to recover the nitric acid from copper nitrate electrolytically. Recovering copper powder to cement with.


----------



## ericrm

i didnt try to electrolyse nitric acid ,do you keep a strong enuf nitric acid after recovery of the copper to work with,or does it weeken?


----------



## ikielee

hello my name is Ike
I am new to this and am open to any and all criticism
i would much rather ask a dumb question and get ridiculed, than guess and get dead.So with that said i would like some advice on this . i started trying to smelt my material for the gold and found that this process is not as easy as people would make you think , please note that i am working with gold filled items and not pure gold items , so what i keep ending up with is a diferent ball of the same stuff i started with, then i went on to trying to cupleate the stuff (well some of the stuff) amagemite process. built the furnace and all and after 2 hours of fire ended up with a ball of gold but not pure gold. So here i am it is obvious the reason 90 plus percent of gold is processed using chemicals, is it simply works the best. now i am learning any and all i can to begin this process and my biggest concern is what to do with what is left over. so now for the real guestion (sorry). the cuplation process worked in the fact that the plated items i put in it were stripped of the gold and i was able to scrape off the non precious material and simply discard. the cuple process however was far to lengthy and in my opinion non productive , however what if one was to at this point use the chemicle process on the gold / silver rich amalgamite, would this lesson the amount of other metal contaminants in the solution and make for easier recycling and or desposing. again please fire away as i am new and may very well be way of base with this but it just seems to me that a combination of these 2 processes may have some benefits. i apologize for the length of this post and the obvious lack of grammer on my part
thanks


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## butcher

Ike,
My rehearsed answer is to study Hoke's book. go to general chat and read the welcome in post for new members, pay attention to general reaction list, see Laser Steve’s web site, and read the forum.

Reason for this answer is it is the best way to begin to learn all of this.

Since you posted here I see you are already concerned with safety and dealing with waste, great start, keep it up.

Melting a material that is majority base metals and a gold plating or gold fill, is a big mistake, the gold was all together, on the outside of the object, by melting you just mixed all of these metals up in the melt to an amalgam of metals, making it harder to separate the values, the techniques your using are wrong application for the materials involved, these techniques work great when used for their intended purpose.

In recovery or refining is just like other trades, the craftsman needs to learn which tool to use for the job, and how to use it, we do not want the surgeon using a chainsaw on our operation when he should be using a scalpel, we also want him to study and learn how to do the operation before he starts cutting us up.

When we discuss things the words we use are important you did not smelt ore, you melted the metal, and basically all you did in the cupel is melt the metal again, the base metal content was so high, melting it in the cupel in my mind was just wasting a good cupel, and not getting nowhere.

I will not go into any specific's on a process here, You could not learn it all from a hundred posts, but you can learn it if you take my advice and study, welcome to the forum if you like to study a very interesting subject you will like it here.


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## Harold_V

ikielee said:


> I am new to this and am open to any and all criticism


Good! 
Start with discarding all of the nonsense you posted here. Most of it is not a requirement for achieving success. That would include melting gold filled items to recover the values. I recommend they NEVER be melted, so you can limit the potential problems of dealing with the low percentage of gold that is present. 

No, I'm not trying to be rude. What I'm attempting to do is have you see that there are far better approaches to refining. You can learn these methods by reading Hoke's book, which is available by clicking a link found in the sig line of several of the readers of the board. One in particular is Palladium. 

My advise to you is to put everything on the back burner and read the book until you understand what it teaches, and why. If you attempt to refine before you have a firm understanding, you will have no end to questions, proving to seasoned readers that you are not willing to pay dues that are required of readers in order for those with experience to spend their valuable time trying to help you when you are in a corner. 

Harold


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## TheGoldenChild

ikielee said:


> hello my name is Ike
> I am new to this and am open to any and all criticism
> i would much rather ask a dumb question and get ridiculed, than guess and get dead.So with that said i would like some advice on this . i started trying to smelt my material for the gold and found that this process is not as easy as people would make you think , please note that i am working with gold filled items and not pure gold items , so what i keep ending up with is a diferent ball of the same stuff i started with, then i went on to trying to cupleate the stuff (well some of the stuff) amagemite process. built the furnace and all and after 2 hours of fire ended up with a ball of gold but not pure gold. So here i am it is obvious the reason 90 plus percent of gold is processed using chemicals, is it simply works the best. now i am learning any and all i can to begin this process and my biggest concern is what to do with what is left over. so now for the real guestion (sorry). the cuplation process worked in the fact that the plated items i put in it were stripped of the gold and i was able to scrape off the non precious material and simply discard. the cuple process however was far to lengthy and in my opinion non productive , however what if one was to at this point use the chemicle process on the gold / silver rich amalgamite, would this lesson the amount of other metal contaminants in the solution and make for easier recycling and or desposing. again please fire away as i am new and may very well be way of base with this but it just seems to me that a combination of these 2 processes may have some benefits. i apologize for the length of this post and the obvious lack of grammer on my part
> thanks


I recycled my Aqua Regia when I used the chemical process and used it again and again, You only have to add a little hydrochloric but may need some nitric depending on what your processing.


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## TheGoldenChild

If you used right amount of flux and you where at right temperature cupeling you should get 99.9 percent gold. A good flux will remove most non-precious metals before cupeling and you should just have a lead/gold prill when you go to cupel then just gold 99.9 after cupelation. Actually is pretty effecient process for testing how much gold is in precipitants but probally not the best for scrap metal as burning lead is not idea conditions for humans to breath. There are way better ways now not as hazardous to our enviroment. I use a muffle furnace when using lead as most of it goes into your cupel and dosn't burn into the enviroment some people recommend cracking the door on you kiln when cupeling and it does make it faster but burns alot of lead into the air.


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## TheGoldenChild

blueduck said:


> I just looked on ebay and a fella there has 100 grams of it for $42.00 claiming that that is less than half the normal cost of it.... but we all know that ebay is over exaggerated for a lot of things related to recovery of precious metals.....
> 
> the chemistry store has boric acid for 90 bux for a 55 pound bag , and 5 bux for a one pound jar..... interesting idea to make it into a useful compound if such can be accomplished inexpensively by the "basement chemist" in our labor-a-tories <----- best Lon Chaney type voice in my head from the bugs bunny cartoons of my misspent youth.
> 
> now i have to go crack open a few of those chemistry books that other folks uploaded and ive got on my harddrive as pdf files...... just to figure out how to do such effectively or if it can be....... or find another source for procuring an already made product.....
> 
> AS far as handling wastes, I wonder if a carbon arc would reduce the wastes to a small footprint in an economical manner..... such a unit was proposed to be built in Montana in the late 70's to mid 80's and that it would reduce a ton of material to a few grams of ash with virtually no emitted gas [dont know much more about it, I was kid at the time] it sounded to good to be true but it would have stopped a lot of landfills and that would mean less dollars somewhere and the thing was scrapped.... but it may be a viable thing to build even on a small scale......
> 
> William



Almost everything we make comes from something right? So given enough time in a landfill it will turn back into what it was before it was put there but that time could be thousands of years or hundreds depending on the waiste. But a landfill by a fault line or encapsulated volcanic area may be better as it would speed up this process.
A carbon arc probally uses alot of energy from the sounds of it and using alot of energy in return creates more waiste so maybe that's why it wasn't used.
These are all just theories and would love to hear someone elses opinion.


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## butcher

TheGoldenChild,

I have a few questions and some comments in the above posts.

If you reuse your aqua regia how did you precipitate the gold from the last batch, and what are you reusing it for, or what materials are you reusing it on.

The reason I ask is when you evaporate, or use up the acids dissolving metals you drastically weaken the solution, or in the case of de-NOxing the acid remove the nitric acid, and in this case it is no longer aqua regia (but a solution of gold chloride and HCl, and when you use a chemical to precipitate the gold from this solution you change the chemistry of the once aqua regia (actually it is not aqua regia any more at this point but a gold chloride solution with possible a very little free HCl acid diluted), the product or what is left in solution depends on the chemical you used to precipitate the gold, to name a few , if you used SMB would leave some sodium sulfites in solution, or if using ferrous sulfate to precipitate gold it would leave soluble salts of ferric sulfate and ferric chloride in the solution, your solutions could also contain sulfuric acid, or several other chemicals depending on your process, it will also contain metals from your last batch contaminating your solution, which could cause problems in refining the new batch, but what it would not be any longer is aqua regia.


You could distill some of the cleaner acid from the solution and reuse that, but it may contain gases of other solutions, and would not be that strong in the end, and HCl is cheap anyway.

You can distill the nitric from the aqua regia solution when dissolving metals or evaporating the solution, but if you do not use too much nitric in the first place, and do the processes as the should be done, You will not get much from that method, making going to the trouble almost not worth it.

I do reuse many of my solutions depending on what they are or what they contain or what chemical, or metal I can separate from them.

But all the used aqua regia is good for normally is cleaning up base some base metal salts in a recovery process like when recovering values from your stock pot, or removing base metals from some other process, and in these you need to understand the chemistry of the used chemical you are using and how it can effect what you are trying to recover, like silver and sulfates is not normally a good combination, if you do not wish to make silver sulfate.

Also the in the comment on cupelling, why are you using a flux this makes no sense. When you cupel values, the flux is not needed, and get in the way, of what you are trying to do, also the cracked open furnace door is to oxidize the lead so the cupel can absorb the lead oxide, if the door was closed the furnace would soon be out of oxygen and would not oxidize the lead.

Flux is used in a recovery melt or an assay, or sometime to help remove some metals from others, the flux can or reduce metals in a melt, or it can be used to oxidize metals in a melt, the flux can also form slag for these oxidized metals to absorb into, as glass slag, or they can help the melt become more fluid so the melt mixes better and metal beads join together, or collect a metal, much depends on what you are trying to do and what flux is used.

I think you have confused two separate processes used in assaying or recovery of metals.

Have you been reading Hokes Book?


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## TheGoldenChild

butcher said:


> TheGoldenChild,
> 
> I have a few questions and some comments in the above posts.
> 
> If you reuse your aqua regia how did you precipitate the gold from the last batch, and what are you reusing it for, or what materials are you reusing it on.
> 
> The reason I ask is when you evaporate, or use up the acids dissolving metals you drastically weaken the solution, or in the case of de-NOxing the acid remove the nitric acid, and in this case it is no longer aqua regia (but a solution of gold chloride and HCl, and when you use a chemical to precipitate the gold from this solution you change the chemistry of the once aqua regia (actually it is not aqua regia any more at this point but a gold chloride solution with possible a very little free HCl acid diluted), the product or what is left in solution depends on the chemical you used to precipitate the gold, to name a few , if you used SMB would leave some sodium sulfites in solution, or if using ferrous sulfate to precipitate gold it would leave soluble salts of ferric sulfate and ferric chloride in the solution, your solutions could also contain sulfuric acid, or several other chemicals depending on your process, it will also contain metals from your last batch contaminating your solution, which could cause problems in refining the new batch, but what it would not be any longer is aqua regia.
> 
> 
> You could distill some of the cleaner acid from the solution and reuse that, but it may contain gases of other solutions, and would not be that strong in the end, and HCl is cheap anyway.
> 
> You can distill the nitric from the aqua regia solution when dissolving metals or evaporating the solution, but if you do not use too much nitric in the first place, and do the processes as the should be done, You will not get much from that method, making going to the trouble almost not worth it.
> 
> I do reuse many of my solutions depending on what they are or what they contain or what chemical, or metal I can separate from them.
> 
> But all the used aqua regia is good for normally is cleaning up base some base metal salts in a recovery process like when recovering values from your stock pot, or removing base metals from some other process, and in these you need to understand the chemistry of the used chemical you are using and how it can effect what you are trying to recover, like silver and sulfates is not normally a good combination, if you do not wish to make silver sulfate.
> 
> Also the in the comment on cupelling, why are you using a flux this makes no sense. When you cupel values, the flux is not needed, and get in the way, of what you are trying to do, also the cracked open furnace door is to oxidize the lead so the cupel can absorb the lead oxide, if the door was closed the furnace would soon be out of oxygen and would not oxidize the lead.
> 
> Flux is used in a recovery melt or an assay, or sometime to help remove some metals from others, the flux can or reduce metals in a melt, or it can be used to oxidize metals in a melt, the flux can also form slag for these oxidized metals to absorb into, as glass slag, or they can help the melt become more fluid so the melt mixes better and metal beads join together, or collect a metal, much depends on what you are trying to do and what flux is used.
> 
> I think you have confused two separate processes used in assaying or recovery of metals.
> 
> Have you been reading Hokes Book?



I happened to of been processing Sulphides, if you know what Sulphides do in Aqua Regia you would know what i'm talking about.
I am just a newbie but it worked well for me when I was learning how to do Aqua Regia and yes I used it over and over and dropped gold everytime out of my solution.

As far as assaying I think the reason you would use flux when you assay is to avoid getting copper,iron and other stuff in your smelt as your just trying to get your lead oxide to attach to your gold and silver if that's what your processing. I don't know seemed to work well for me . Remember I am just a newbie but there is more than one way to skin a cat and there are alot of different methods of Aqua Regia and Assaying I just tried to be the most effecient I could when processing stuff as I am only a hobbyist and worked a regular job and didn't have much time for processing. You would probally have a fit when you heard how I removed the silver from my Aqua Regia I just used tap water and it turned into silver chloride and then I filtered off then melted. Then would proceed back to the gold chloride and drop that with a mystery metal. Actually worked pretty well considering I was processing gold sulphide ore and would get around 10 grams ( 2 grams gold 8 grams silver) of precious metal out of 200 or so grams of ore. There was alot of copper and nickel in the ore and was able to remove in Aqua Regia and just filter off then drop my silver and gold chloride. How do you do it?


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## butcher

If you process sulfide ore, you need to remove the sulfide before processing, a good roasting procedure, will break down the sulfide to SO2 gas and sulfur, the sulfur will help fuel the roast, (sometimes adding free iron to the roast can also help to break the sulfide bond), leaching the sulfide ore without roasting the ore much of your gold would be locked up in the sulfide bond, and then leach would not get to the values, roasting the ore you will not have the sulfide to deal with.

I would not use aqua regia on sulfide ore, even after roasting, there are cheaper leaches that would work just as well to remove base metals from the ore, as most of what you would leach primarily from the ore would be base metals, like iron or copper depending on the ore, the iron and base metals would have to be leached out first (the gold would primarily be last be leached as the base metals replaced gold in solution), (unless your leach was more specific for gold), if leaching tons of ore for a very small amount of gold per ton of ore, using gold aqua regia would be a terribly expensive way to leach iron from your ore. 

Free gold concentrate, or placer gold is a little different story where the gold is much higher percentage of material, but even these I would consider what they consisted of before choosing a pretreatment, leach or other process to recover the gold, before using aqua regia to refine the gold.


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## TheGoldenChild

butcher said:


> if you process sulfide ore, you need to remove the sulfide before processing a good roasting proceedure, will break down the sulfide to SO2 gas ans sulfur, the sulfur will help fuel the roast, without roasting the ore much of your gold would be bound to the sulfide and the leach would not get to it.



Don't like roasting it and is why I used Aqua Regia, The Sulphides in the ore will actually boost your acid level up but takes a long time for it to work in my experience. I just let it sit for a week or so mixing the solution every couple of days. I may be very confused but it all worked for me and I was trying to be the most environmentally friendly as possible.


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## butcher

H2S hydrogen sulfide gas (arsenic and other gases) does not sound very enviromentally friendly.

If you wanted to be enviromentally friendly make sulfuric acid from the sulfide roasting process of your ore, use the dilute sulfuric you produce to leach base metals from the ore.


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## Pantherlikher

Irons said:


> There comes a point where extracting values becomes uneconomical. The problem is how to deal with these materials without spending a fortune.
> On another thread, there was a discussion of using a commercial polysulphide compound to recover values but it precipitates everything. It's what it was designed to do.
> 
> If you have to pay to dispose of hazardous waste, the trick is to reduce the volume to where the cost per ton is economical.
> 
> Precipitation as sulphides works well in this respect. If done properly, there is little odor involved and the effluent is clean enough to recycle or dispose of in municipal waste streams.
> 
> one trick I use to reduce volume is store the liquids until winter and as they freeze, the ice pushes the salts to the bottom, leaving a very concentrated solution. The nice thing about it is I don't have to expend any energy to evaporate the solutions. All I have to do is leave a loop of rope in the top of the solution so that I have a handle to pull out the block of ice.
> 
> everything but the squeal.




My question is:
Does 1 metal replace another in spent solutions?
For instance AL will drop CU.
If so, can you use spent solutions to dissolve another? Dropping the metal farther up the reaction list? My thinking is using it to seperate the different metals 1 by 1 untill the solution is as non toxic as we can make it while collecting the different scrap metals?
There's alot of containers involved, each removing a different metal, but is it even a possibility?
Just a newby's thought on what to do with waste. If even to remove tin and solder.


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## qst42know

To stair step this one metal at a time I would expect most often you would consume metals of value to cement metal powders of little value.

Interesting idea for an experiment but I don't see your plan as cost effective for recovery of anything outside of the specific steps described on the forum.


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## BJL1984

ask around at your local scrap yards, Most will take your copper powders, the Company I work with up here in new hampshire, Assays my precious metals and also allowed me to make a deal with them that they buy the copper in powder form less then clean (#1) price and in bar from clean or less depending on how it works up under the x-ray test, It my be a nominal amount, i am no getting rich of the copper but it almost always pays for the gas on the 45 minute ride to get there, So in theory making the whole process a little more cost effective, just some food for thought, for those who are looking to do something with the left over bits


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