First Mistakes

[lysdexic]

To paraphrase my father, there's no use being an idiot if there's no one there to see it. Well if he's able to look down and see this I'm sure he's chuckling. After 6 months of reading, gathering, reading, dismantling, reading... I had to DO something and of course made MANY mistakes.

#1 - I don't have a "Lab Journal/Notebook" I'm old fashioned and need to write and read notes in order to learn and retain. All those "steps" seem to slip my mind and running to the computer every 5 seconds doesn't work.

#2 - Start with small experimental batches. Well that was the plan. I had about 8oz. of assorted pins and other gold plated contacts, different types, some with solder, some clean. When I realized I should have at least kept the tin bearing pins separate it was too late. I figured there would be enough gold to make my first bb anyway and if I screwed up and lost values it wouldn't be as bad as if it was 8oz. of fingers. So I poured all 8oz. into a 2 liter jar and filled it 1/3 full of 32% HCl .

#3 #4 & #5 - I didn't measure how much acid, so I didn't know exactly how much peroxide to add to start the AP (copper chloride) leach. Apparently the hydrogen peroxide I was going to use went to college with my daughter so instead of 3% I had 20% H2O2 used for bleaching hair (at least it didn't have any mystery ingredients according to the label). I didn't do a conversion. Going just from memory (see mistake #1) I thought it was about 2 cups H2O2 per 1/2 gal of HCl on Steve's video processing fingers. So I added a couple cap fulls (about a teaspoon). Watched and waited... nothing. 2 more cap fulls... nothing. So I poured in about a half fluid oz. Flash of dark green then the entire solution turned light green.

For the next couple days I had the reaction vessel in a warm water bath while I was outside and left it at ambient temp when I wasn't around. The solution got darker and many tiny foil flakes were suspended in the solution.

#6 & #7 Beginners always use too much (acid, peroxide etc.) No bubbler so no and then add a few more drops of peroxide and a little more hcl. There's a reason for decanting verses just filtering. There's a reason to be patient and let the process run to completion. I didn't research the AP process enough to really understand that it was the copper chloride doing the digesting and not the acid alone. So... to add fresh acid (being impatient) I had to pour off what was already there... instead of pouring it off and letting it settle I poured it through a filter. A couple hours later I have a small amount of gold flakes in a small jar covered with a few ounces of rinse water and several filters with visible values embedded in them.

There's more... the thing is, none of it had to go the way it did. All of you have given me the steps and the answers to questions I don't even have yet. I need to learn by doing as well as reading, until then it's just theory, a dream. And a computer screen just doesn't do it. When I finally started to get a bit of Hoke it was because I printed out the book and read it with a notebook beside me and took notes. That notebook was just placed in front of my monitor, old school... works for me. As I said there's plenty more if you'd like a laugh. The only values I definitely lost is when I tried to incinerate this little pile of hard won treasure, the ceramic pan I used is fine, the large purple stain on the bottom and the yellow stains on the sides give it a very distinct look. (I can almost hear butcher explaining the yellow being from AuCl and the purple from a SnCl & AuCl reaction as they were vaporized even though I don't know if that did or could happen) Thank you all for your time and patience. I wasn't going to start a topic ever without a need and haven't found the need yet. I'm just too tired to search and read right now.

Doug

 

[Pantherlikher]

Everyone cringes while reading as it's always the same. Everyone makes these kinds of booboos before the light bulb gets brighter.

Anything with tin needs to be soaked in hot HCL, then rinsed. Does not get all the tin but helps. AP needs oxygen for the copper to digest copper. Air bubbles or more peroxide. The peroxide though will dissolve gold and drop it out when copper replaces it.

And yes, decanting all fluids before filtering. Less trapped in the filter to get out later. I have about 20 filters with almost nothing in them.

And finally here, several rinses before trying to incinerate. Gets rid of any tin left as well as any other base metals.

Doing a google search on AP will give more then enough reading on the steps so of course....DO IT...

Good luck and let us know what you do to fix it all

B.S.

 

[lysdexic]

Everyone cringes while reading as it's always the same. Everyone makes these kinds of booboos before the light bulb gets brighter.

Anything with tin needs to be soaked in hot HCL, then rinsed. Does not get all the tin but helps. AP needs oxygen for the copper to digest copper. Air bubbles or more peroxide. The peroxide though will dissolve gold and drop it out when copper replaces it.

And yes, decanting all fluids before filtering. Less trapped in the filter to get out later. I have about 20 filters with almost nothing in them.

And finally here, several rinses before trying to incinerate. Gets rid of any tin left as well as any other base metals.

Doing a google search on AP will give more then enough reading on the steps so of course....DO IT...

Good luck and let us know what you do to fix it all

B.S.

Thank you and so far the last suggestion was the first thing I did... well, after the STOP WHAT YOU'RE DOING until you know what you're doing!, that I have also read many many times here. I gained a better understanding of the AP (copper chloride) process. I read numerous posts about incineration and found Harold's post explaining about it and butcher explaining how and why to wash the recovered PMs first. Those two member's posts stick in my mind but there were many others and I am grateful to all of you. I am ashamed to admit it but I also did the same thing (at the same time) with some circuit boards with gold plating. Including some cell boards I couldn't fully depopulate (those at least I soaked in warm hcl until the stubborn components came free). So far:

I took my fouled, filtered copper chloride solutions dumped them in a plastic pail and added clean copper and let it sit. A week or so later it was dark brown. I carefully decanted the solution til I saw particulate matter. I set the poured off solution aside to let it settle some more. I rinsed off and removed the copper leaving some fine black powder and a few surface mounted components that snuck by. The wash turned a pale blue (very dilute whatever it is). It's sitting untouched in the pail.

The pins I left in the jar. I poured some fresh hcl over them the day before yesterday, today the solution is a beautiful emerald green clouded with a lot of gold sparkles when stired. It's going to sit and wait for my aquarium pump. (It's busy doing 4 oz of fingers (step by step according to steve's video except I bought and put into use the air pump instead of more peroxide).

The small amount of recovered gold that I didn't vaporize I washed with water then hcl then water again as per the thread on 100 oz of pins. Without proper set up I was afraid of incineration so I digested with hcl/clorox (too much acid, too much clorox of course). I let it sit a couple days. I finally had what I was looking for a known gold bearing solution. I could not find tin antimony solder anywhere. Silver bearing I had was 95% tin 4.7% copper and .3% silver silver and copper are lower on the reactivity series so I wondered if it would work. The resulting hcl, cornflaked solder solution was crystal clear. No positive on the copper chloride (tin of course renders the test meaningless), but dipping a q-tip in the gold solution and putting a drop of the suspect testing solution yielded a purpleish stain that's still there. I don't want to rely on this testing solution, but it seems to work for now.

The filtered auric chloride I evaporated a bit (not enough to measure the volume just until there was no chlorine fumes) to drive off excess chlorine and precipitated with SMB (my scale only measures in grams or ounces so I used WAY too much SMB). The result after 3 days is a fine brown powder (not very much, but something). The solution still appears to have a brown tint starting half way down. Not sure if it's a reflection or more suspended powder. It's going to sit until I have more to process.

The mess of filter papers and other potential gold bearing mess are going to hang around waiting for a means to properly incinerate.

Knowing and dreaming about a thing are never the same as doing. I knew I would have to go off and forget everything I learned and screw something up. I would have liked to have made a first bb I could keep. Instead it's all going to end up in one button (or a big bb). That will always remind me to stop, think, be very sure of the steps, do it right the first time. I can be trained... eventually. Thanks again.

Doug

(edited to remove redundant word)

 

[lysdexic]

I do have an actual question if anyone would be willing to offer advice. A few years back on a scrap metal run I picked up some scrap and in a box of assorted junk was a brown mailing envelope which contained a roll of silver brazing alloy wire. I believe the post mark was from 1958. It still had the tag on it... Engelhard Industries, American Platinum and Silver Div Grade E 301 .025 dia. (it weighs 10.4 oz). This was one of the main things that sent me on a search of how to refine PMs. It's sat hanging on a spike in the garage for years driving me nuts. Engelhard sold the platinum and silver division long ago, they were nice enough to give me contact info for the new owners but they never responded to my inquiries. I used some once to rebuild contacts in my starter solenoid (an hours work and a tiny amount of gas compared to much longer running around AND doing about the same amount of work plus the $100+ for a rebuilt starter... anyway). I am of course concerned about cadmium but also unwilling to throw away a couple (+ or -) oz of silver. I took a small piece of the wire, rolled it up and placed it in a small glass jar which I covered with hcl. The tarnish vanished almost immediately, the solution turned a light yellow and everything stopped. I have some suspicions about why it may have stopped reacting but no idea why it turned yellow. Any thoughts, comments, concerns?

 

[Ian_B]

If it were me, and because of the amount you have I would:
Cut off a sample of the wire. say 10 grams.
In a beaker add 15ml's of distilled water,
Add 10-15ml of 68% nitric (or equivalent total volume) giving you a solution of about 25-30ml of 30% nitric acid (always add acid to water not water to acid)
Then add your sample of wire to the beaker,
Cover with a damp filter paper,
You can heat on a hot plate or leave in a safe area until all the wire has been dissolved.

If any wire or residue is left and no further reaction occurs decant the solution (pour the solution off of the residue through a filter rinse the residue 3 times with distilled water pouring all solution through a filter into the same container.

If no visible residue or wire is remaining I would still pour the solution through a filter and rinse the beaker once with distilled water.

add a flat piece of copper to the solution and wait until the reaction of of the silver nitrate converting to copper nitrate has finished leaving you a precipitate of Silver metal in the bottom of your container.

decant solution, rinse and decant 3 times. test solution for any other PM's also test the residue for any other PM's. If no PM's are present dispose of them in a safe and proper manner.

rinse the silver powder one more time and then drain through a filter.

Dry the filter and weigh the silver powder and this will give you an idea of how much silver you have in that wire.

 

[jason_recliner]

Doug, as I read your notes, it's like you were watching me and wrote down almost everything I did.

I am in a very similar predicament. Despite also reading heaps here for several weeks before starting (but not with the benefit of CM Hoke), I made the same mistakes and am still similarly slowly going through my light blue stuff, my light green stuff and the yellow stuff.

Good luck mate.

 

[Geo]

Safety-Silv could have just about any other metal as an alloy http://www.harrisproductsgroup.com/en/Products/Alloys/Brazing.aspx look at the high silver index.

 

[lysdexic]

Geo, thank you for the link, the thought looking up such alloys to see what they're made of and the effort of finding and posting the link. Cu, Zn, Sn and Ni all possibly present. Being made in 1958 Cd and who knows what else could still be there. It was very windy the only time I used any of it and I do remember white smoke (Zn fumes?) but no way I'm melting more to see if Cd's distinctive fumes form.

By the way I've read many and gained much from your posts (and videos). The way you make things work with what's available reminds me of myself

Ian, thank you for detailing your approach. It sounds very much along the lines of all the other step by step processes I've read here. Each step preparing for the next in reaching the goal of recovery. Safety pointers are always welcome, the very first question should always be is it safe or how can it be done safely. Safety needs to be so ingrained that it is always thought of first and always mentioned no matter how well we all think we practice being safe. I forget too that others read this who have no idea of the risks and how to avoid them (danger to self, others, the environment and property).

I have no nitric at the moment and no source for it except to make it myself. I'm not set up yet to do that or comfortable and competent enough working with these dangerous chemicals to attempt that process... but I will get there. That wire has sat for years, it can wait a few more months. I'll keep your instruction handy and that will be my first use of nitric acid. Thank you again.

(edit) Something turned the solution yellow. So I wondered if the silver content could possibly be high enough to shut any reaction down... knowing how low carat gold behaves with acids. I'm not a chemist at all, but a light bulb went of (dim as it may have been.) (/edit)

Jason Thank you. I knew I was not alone and part of the reason I posted my blunder was hoping someone else would see it and think twice. Yesterday I read a post by Gold and Silver Pro (I think it was) pointing out the dangers (safety and loss of values) of letting gold fever run the show. For myself anyway, I'm very compulsive-addictive. Knowing that and always looking out for it is the only way for me to control it. Tunnel vision of the treasure can range from death to loss of values. Is it safe? How can it be done safely? What steps need to be taken to accomplish the goal with minimal loss (or pollution/wastes). One thing you said does kind of bother me.

Despite also reading heaps here for several weeks before starting (but not with the benefit of CM Hoke)

Why without the benefit of C.M. Hoke? The very first thing I learned here was to take the cotton from my ears (well... eyes), stuff it in my mouth (...keyboard) and keep it that way until Hoke was read and understood. The wealth of information here is worth way more than any PMs I will ever recover/refine and being cast out would be the worst possible "loss of values" I can think of.

Good luck to you as well. We can call this a learning experience to nurse the bruised ego.

 

[nickvc]

If your in no hurry with the wire keep it for when you have nitric and other silver to process, chances are you will over do the nitric and the wire could be used to consume any extra before cementation with copper. At the price many have to pay and the difficulty in obtaining nitric it's not wise to waste it.

 

[lysdexic]

Thanks Nick, no more hurries. I'll add that to the tool kit. Yes I have a 5 oz nugget of assorted purer silver and some contacts I melted years ago and all the silver bearing escrap I'm acquiring. If I couple your suggestion with Ian's (use the data from Ian's test to calculate how much silver was consumed to kill the nitric) I could use up all the nitric and still get a rough idea of yields on whatever I processed by keeping track of how much wire goes into solution and I'll have a reference as to what should be left over when the wire is completely digested. (sorry just thinking aloud)

Doug

 

[goldsilverpro]

Re: First Mistakes

When I was a bare beginner, I was dissolving about 1/4 bucket full of gold plated stuff with AR. It was for a guy that owned a scrapyard and I was doing it outside, behind his building. I had no catch basin under the bucket. I pre-mixed the AR (I knew no better at the time) and covered the material with it. It just sat there for awhile and then, all of a sudden, whoosh, it was violent and overflowing the bucket. By the time I got it calmed down, about 1/2 of it was soaked into the ground.

I never did that again. Screw-ups are much better teachers than when everything goes smoothly.

 

[lysdexic]

I never did that again. Screw-ups are much better teachers than when everything goes smoothly.

Most definitely. It's much like the difference between something hard won and something handed over on a silver platter.

I cringed at your story and had no problem imagining myself having done that. Thank you, at least I only lost for sure what went up in smoke the rest is somewhere in the mess. No recovering what went into the ground however. (I hate to admit it but very next project for me is setting up a catch basin).

Doug

 

[steyr223]

Gsp thats funny
Well not the actuall event but to hear one of the
Top dogs say it ..

I did the exact same thing
Filled a 2liter beaker with watches,rings,bracelets,etc
Not Ar but 50/50 Hno3 ,i put over 1 liter of acid :lol:
I never got it under control ,there was gold running down
My driveway over the grass and sidewalk and into the street
The worst part was the guy whos gold it was ,was standing next to me

That was the only time i made that particular mistake

There were many more,i will bet you could pull an ounce or more from that front yard :lol:

At least now since i found this form they are few and controlled where i can always recover and the most important note they are much safer to me the neighbors
And the world we live in.
Steyr223 rob

 

[goldsilverpro]

The worst part was the guy whos gold it was ,was standing next to me

I was lucky, I guess. I was all alone and I'm embarrassed to admit this, but I didn't tell the owner what happened. I should have. He ended up with about half and probably thought I was stealing from him. This is one of those dozens of crappy things that I've done, especially early in my life, that I wish I could go back and change. For some reason, in my advanced years, they now all keep cropping up in my mind. I think someone is trying to tell me something and I think I know who it is.

 

[Geo]

I lost over a half ounce of gold due to steam explosions while force drying gold powder. I set up my hotplate on my work table and set up a visionware casserole to dry powder and placed the wet powder in it and turn on the heat and left. I obviously set the heat too high because when I got back there were craters in the now dry powder and wet powder all over the place. I remember finding some on an old satellite dish about fifteen feet from the table. At least it was my gold but it was a horrible mistake for me and about made me sick.

 

[jason_recliner]

One thing you said does kind of bother me.

Despite also reading heaps here for several weeks before starting (but not with the benefit of CM Hoke)

Why without the benefit of C.M. Hoke?

Too many internet videos promising how easy it all is. I like think I had just enough foresight to at least try to understand what I thought was the entire process before starting, and I'd read a fair bit around this site which, at the time, confirmed the junk > fingers > goodbye copper > gold flakes > solution > powder > melt process I had in my head, but was not a member and therefore had no access to download files. And it appeared clear enough that I wouldn't need it. WRONG!!

Naturally, my case was not absolutely identical to what I'd seen and so it all went rather differently. Especially when I was too impatient, and put in too much HCl. And NaNO3. Ooh, it's not dissolving immediately. I must need more NaNO3.
I didn't even realise the HCl/Peroxide (before Copper Chloride starts its magic) was dissolving gold until this week; something the interweb vids promised wouldn't happen until nitrate got its teeth into it.

As you say, it's a far better education to get your hands dirty... which of course in this hobby is something I strive to avoid.

I'm still trying to recover my mistakes and still I make new ones. I made one yesterday while processing a large jar of waste acid. A very black powder sat at the bottom while new copper was still being eaten up, so I thought it should be worth collecting. Took a week to get it all out. I do not know what it is, but it's less obviously reactive than copper. Then I dumped fresh HCl on it to see whether it would stay solid, and put it on my coffee maker. It stunk of sulphur dioxide fumes (SMB) but stayed black suspension. It's only after I dropped my hot acid into water and the jar went basically clear that I realised: @#$%, I forgot to incinerate it and it's probably still nitrated. It's largely settling today, and I still don't know what it is. But it's a mix of black with almost lilac.

 

[nickvc]

I think most refiners have disasters at some point but it does teach you not to the same thing again.
GSP I'd have to call that bucket disaster an honest mistake, not done with intent to deceive so I'd not worry too much we all mess up and sometimes don't know how to put things right.

 

[lysdexic]

I see a glimmer of hope! Knowing that some of those I consider the experts (who I'm trying to learn from) have sometimes found the right path the hard way is encouraging.

Too many internet videos promising how easy it all is. I like think I had just enough foresight to at least try to understand what I thought was the entire process before starting, and I'd read a fair bit around this site which, at the time, confirmed the junk > fingers > goodbye copper > gold flakes > solution > powder > melt process I had in my head, but was not a member and therefore had no access to download files. And it appeared clear enough that I wouldn't need it. WRONG!!

The roll of silver brazing wire is what led me here. I too found web sites and videos on how to recover the silver, but for lack of a better description, they all left me with a feeling the process was on the "sketchy" side. When I landed here and started reading, I joined then and there and forgot about the sketchy stuff I read. This forum immediately "felt" built on solid ground. (I have to admit Harold scared the heck out of me, but in a very positive way. The message I got was this is serious and very dangerous, take safety and the processes seriously, communicate clearly. The knowledge is free but you have to be willing to learn and able to feed yourself, no one wants to spoon feed you. If you can't have the common courtesy to follow some simple rules or respect those trying to help you ...you're gone!)

Naturally, my case was not absolutely identical to what I'd seen and so it all went rather differently. Especially when I was too impatient, and put in too much HCl. And NaNO3. Ooh, it's not dissolving immediately. I must need more NaNO3.
I didn't even realise the HCl/Peroxide (before Copper Chloride starts its magic) was dissolving gold until this week; something the interweb vids promised wouldn't happen until nitrate got its teeth into it.

I figured the AP (copper chloride) process and the HCl chlorox (sodium hyperchlorite?) process were the least dangerous and not quite as complicated so a good place for me to start. (I forgot also an HCl leach to remove tin) I chose the least valuable of my material to start with. I'm not ready to add nitrates, nitric or sulfuric acids to the mix just yet. At the very least I want to establish sound lab practices first. Already a number of times I've decided to check on a reaction and grabbed say the strainer bucket my gold fingers are being processed in. I'm just checking I don't need gloves right? Copper chloride solution can't be good for your hands or any other part of your body. If I were that stupid with some of the other processes ...well we know what could happen.

As you say, it's a far better education to get your hands dirty... which of course in this hobby is something I strive to avoid.

...see copper chloride comments above

I'm still trying to recover my mistakes and still I make new ones. I made one yesterday while processing a large jar of waste acid. A very black powder sat at the bottom while new copper was still being eaten up, so I thought it should be worth collecting. Took a week to get it all out. I do not know what it is, but it's less obviously reactive than copper. Then I dumped fresh HCl on it to see whether it would stay solid, and put it on my coffee maker. It stunk of sulphur dioxide fumes (SMB) but stayed black suspension. It's only after I dropped my hot acid into water and the jar went basically clear that I realised: @#$%, I forgot to incinerate it and it's probably still nitrated. It's largely settling today, and I still don't know what it is. But it's a mix of black with almost lilac.

I'm a little confused and I don't mean to sound like someone who knows what they are doing because I'm not. I'm just barely to the point where I just might be able to pursue being a beginner, not even an apprentice. You're processing waste acid with copper to cement values there's SMB and possibly Nitrates along with a black powder precipitate? Is this left over poor man's nitric (edit... I meant poor man's AR) that you dissolved gold in? Was it tested? Did any gold drop? Does free sodium nitrate mean there's still nitric acid that should be neutralized before gold can be dropped? I haven't really looked into the process because I don't plan on using it. I purchased 5 gal. of battery fluid (35%? {would have to go look} sulfuric acid) and intend to concentrate it to 98% and use Steve's formula for cold nitric which I plan to distill afterwards. That's still beyond my currant capabilities, so it'll be a while.

I used the AP process on 8 oz of pins (some with solder) and an undermined amount of cell and other boards with gold plating (and solder) + some cell boards that I used an HCl bath to remove components I couldn't remove manually. I had an unknown/untested stannus chloride and when I tested the solutions I didn't trust the results. After my incinerating fiasco with the gold foils I filtered from my two solutions, I did manage to make about 50 ml of dilute gold chloride which tested positive for gold with my suspect stannus chloride (I still consider it suspect but it is at least some light in the dark). My chloride solutions I used on the pins and boards I combined and placed in a 5 gal plastic pail (it still tested negative for PMs BUT it has to have tin from the solder and I was almost positive it had dissolved gold as well) and added a 3# coffee container full of clean (I should say degreased with NaOH and rinsed several times, there was a little surface discoloration on the copper) heavy pure copper pieces to the contaminated copper chloride solution. After about a week I carefully decanted the copper chloride solution (and a container of rinse waters) leaving me with some fine black powder still sitting in about a qt/l of water/solution (it has a very faint blue tint). I had to explain all of that to make clear where the black powder I have came from before I can ask for help dealing with it. In my case there could be gold in it. There could be whatever surface contamination the copper had on it. There could be any number things I know nothing about. If I decided to proceed with what I think I know I would gather and wash the powder (to remove as much chlorides as possible) incinerate (cringe) wash with water, wash in HCl, wash in water (to make sure I got rid of anything I could that is soluble in hcl or water. I don't think I'd try to melt it, I think I'd attempt HCl/bleach leach (?) and see what happened. I don't know that's what to do and haven't found any postings that deal with my situation (yet, still looking). I could just ask even though it IS here somewhere. I could just take the powders and call it the start of my stock pot. It can wait, I'll keep looking and I have a batch of fingers that yesterday were starting to give up their gold foils. There's no need to force the issue... baby steps.

Doug

 

[Geo]

This is still a good ways from you but well worth the trip. http://greenwayproductsinc.com/ is in Knoxville Tn. and sell nitric acid in all sizes. If I remember right, you get the 15 gallon keg, the initial cost is around $250 because of the keg but every refill is less than $30. That's less than $2 a gallon. If you have an Approved container, you can transfer the acid and not have to pay the drum deposit. They will sell to anyone during regular business hours. You can purchase the acid and pay drum deposit and leave their lot and find a good spot to transfer the acid and take their drum right back to them. DO NOT USE AN UNAPPROVED CONTAINER. It would be best to consider the first purchase and deposit as one purchase and just return the drum for a refill.

 

[lysdexic]

Thank you Geo. I have family in Rossville GA/Chattanooga TN. Now I have another reason to visit. I don't have anything I would want to transport it that far in even if it were considered approved. So if your price is right it's less than $5/l drum included (if I did the math right).