NurdRage - 2020-11-22
In this video we Efficiently Recover Nitric Acid and Copper Metal From Copper Nitrate Wastes by reacting copper nitrate wastes with sulfuric acid to generate nitric acid and copper sulfate. Then we electrolyze the copper sulfate to recovery copper metal and sulfuric acid. Related videos: Production of nitric acid by thermal decomposition of copper nitrate: https://youtu.be/hmB5x0LYfSE Purification and concentration of nitric acid: https://youtu.be/88gbfCnrV8o Donate to NurdRage! Through Patreon (preferred): https://www.patreon.com/NurdRage Through Youtube Memberships: https://www.youtube.com/channel/UCIgKGGJkt1MrNmhq3vRibYA/join Through Bitcoin: 1NurdRAge7PNR4ULrbrpcYvc9RC4LDp9pS Glassware generously provided by http://www.alchemylabsupply.com/ Use the discount code "nurdrage" for a 5% discount. Twitter: https://twitter.com/NurdRage Reddit: https://www.reddit.com/r/NurdRage/ Instagram: https://www.instagram.com/nurdrageyoutube/
Been watching Nurdrage for 10 years, never seem to get enough of it. still get excited when I see a new video, otherwise I’ll just watch one of the old ones.
Been watching him since, I think, 2006, when he destroyed that barbie ken puppet.
Next video will probably be on chemical resistance of palladium metal.
Trying to civilize the wild west of precious metals refining, eh? About time. Tired of watching DIYers dissolving and precipitating precious metal solutions in an endless loop, trying to squeeze out the last bits of metal, doing everything by rote, eyeball, and guesswork. What you've done here is refreshingly straightforward and waste free (by "waste" I mean usage of vast quantities of metal, acids, bleaches, peroxides, etc. thorough inefficient processing, not necessarily waste the way chemists usually mean.) I want my chemistry porn to be cleaner!
GOOD
@sreetips will thank you when he sees this message. Should give him some ideas I hope. Thanks for the excellent videos. Much appreciated.
is there a book you got all this info from, like the mA per cm2 stuff or the theory of the processes. i guess maybe im just asking for excellent book recommendations in general for a chemist like yourself
Dear Mr. NR, I am an Indonesian, can you teach me how to make metafitamins? Please reply to my email sir NR. Thanks in advance
This is a great video. Considering that dilute nitric acid is fine for a number of refining processes, it might not even be necessary to concentrate it further. Considering that nitric acid is by far the most expensive chemical used for basic gold refining, getting a fair amount of it back using equipment most would already have (well maybe they'd need to pick up a condenser) is pretty useful.
I have heard that bubbling nitrogen dioxide through 3% hydrogen peroxide works very well.
Also, reducing the copper FIRST with iron yields metallic copper and iron nitrate, which decomposes at a much lower temperature that copper nitrate: only 80C, well below water's boiling point. Your waste afterward is just iron oxide mud, which is totally nontoxic,
Dude! I hadn't thought of doing this but it's so elegant of a solution! I just so happen to have some copper nitrate waste and now I know exactly how I am going to process it. Thank you! :)
This is immensely useful information for those of us getting into precious metal recovery and trying to plan ahead to minimize wastes.
It's great you sharing your vast knowledge with all that would like to learn. For me. I most likely will never use this knowledge you represent in your video's. But just having the opportunity to see these things in action is great. I never had the opportunity to go to much higher learning institutions, so YouTube was really it for me, and man the things I've seen. My eyes were opened and my mind expanded way beyond what would've been if these platforms didn't exist. Thank you again for sharing your knowledge with me. I do hope you can continue the program.
Man, for real though. I have been watching your videos for years and even though YouTube has changed throughout the years your videos have continued to be amazingly informative and really top notch quality. Thank for everything man, always.
why thank you! I appreciate that!
Would be interesting to see what a large scale set up would look like.
I do precious-metals recovery. And I have learnt so much from your show, I really appreciate what you have done. You are very intelligent man
This is one of the most cost saving video I have seen. I have been trying to find a way to recycle my byproducts in refining since I started. Thank you!
If you have a lot of copper oxide powder, it's easy to smelt.
Just mix in finely powdered carbon in excess and hit it with a reducing flame. Same as reducing lead oxide to metallic lead.
It works so well, I was even able to get reduction in my first experiment with a steel spoon filled with carbon-copper oxide over a hot candle flame. Ended up with clean, red copper metal powder that polished up when rubbed between two smooth stainless steel surfaces (which is how I test powders to see if they're metal or not. If they take a polish, it's at least partly metallic. If not, it's mostly salts and oxides.)
Thanks for this, Dr.! As it happens, I have ~1/2gal of Cu(NO3)2 solut just sitting in my chemical waste stash pile, & I’ve been pondering what I should do with it. I think that being able to recover HNO3 from it is my best option, & I’ll certainly be doing this the next chance I get to play in my lab.
I do have a question however; I am lacking any form of Pt to use as an electrode, and I’m probably the poorest viewer you have 😂, thus I lack any funds to purchase any. So, my only options are to use materials I already have on-hand, which are either a Ti electrode, or I can make some graphite substrate lead dioxide ones. Do you think titanium would hold up to being electrolyzed in a solution of H2SO4? I’ve never tried, but I’m >99% certain they’ll quickly degrade, leaving Ti sulfate interspersed with my CuSO4. So between my 2 options, do you agree that Pb dioxide would be my best bet? I have used them for ClO3 cells, & they withstood the chlorate splendidly. And to the best of my knowledge, chlorate is a stronger oxidizer than sulfuric acid, hence my hypothesis that they’ll work for this application. However, I’m merely a 100% self-taught amateur chemist, and I immensely value the opinion of professionals such as yourself, hence my asking your advice in this instance.
If you could reply whenever it’s convenient for you to do so, it’d be greatly appreciated. Thanks again for the great content.
if you already have a lead dioxide electrode that's been thoroughly washed and cleaned then you can use that. Obviously be careful of lead particles since lead is toxic.
@NurdRage I would need to make some more. Currently, I just have the carbon rods I hacked from a 6v battery. But I’m glad to know that they should be suitable as my anode here. Thank you for your reply.
Excellent video to retain used copper & sulphuric acid. Will definitely help metal extraction industry .
You are doing a great research on nitric acid, and ‘tis one of my favourites.
I suggest you to research on Flourine-Cesium and Inert gases theories..
Also you could do good in proving wrong theories.
Good luck for your future videos!!
Hey Nurdrage, there's an interesting reaction Im trying to figure out. Involves plating copper onto aluminum. It's in a hackaday article called Soldering on aluminum. Using ferric chloride, copper sulphate and salt somehow causes the copper to bond onto aluminum. I think there is somehow etching going on, iron is somehow deposited and then copper binds to the iron. might be an interesting video.
copper sulfate would likely react with aluminium to produce copper and aluminum sulfate.
To speed up the electrolysis, you can do a time lapse :)
And use NileRed's time lapse music!
Oh man, there is a whole world of precious metal youtube out there. Sreetips is so interesting to watch him dissolve metals, and then get super high purity metals.
@andybaldman You're welcome.
@Vinicius Cordeiro In my opinion he could reduce all that chemistry to 1 step and use electrolysis to dissolve the raw input stock in hydrochloric acid. The silver would precipitate as AgCl, and the other metals would go into solution, and plate out on the cathode. In this 1 step, he would get the silver separated and the other metals in non-hazardous form, without consuming significant acid. Silver would be recovered with standard NaOH/sugar reaction.
@Vinicius Cordeiro Actually, when sreetips refines silver he first dissolves in nitric, expending it. Then he precipitates the silver as silver chloride using hydrochloric acid. This immediately forms new nitric acid, but I dont think he realizes... I sent a message about this in his last video where he builds a small kiln from kaowool. He replied but didnt seem to get the point. So I explained some more but no more reply... I think many refiners could benefit from the process in this excellent nurdrage video, but also from realizing nitric acid is formed by adding hydrochloric acid to silver nitrate.
@MegaFrankels That's only when he have to refine silver from silver chloride, which he avoids as much as he can. Usually he just adds pieces of copper on silver nitrate solution, which directly precipitates metallic silver.
@Vinicius Cordeiro True... most of the time he uses copper to cement out the silver... then you could use this nurdrage process to regenerate the nitric from the copper nitrate. But distilling nitric is not for everyone and you need a distillation setup. Choosing to use hydrochloric acid to precipitate silverchloride and regenerate nitric acid may be cheaper/ easier/ less labor intensive than cementing out the silver and either regenerating nitric with sulfuric acid or straight up buying new nitric. Of course with silver chloride then you need lye and sugar as well... I guess it comes down to how cheap you can source the materials/equipment and how efficient/big your setup is. And how valuable you deem your time. I dont know enough to be able to estimate what would be cheaper/ more efficient. But its definitely an alternative.
I watched Cody's metal refining videos like 5 or 6 years ago now and every time I think about all those big buckets of waste copper nitrate he had, I can't resist coming back to watch this video. This process is just so frickin' cool... sssso cool...
Great video! Its cool to think how many people this will actually help
I've been re-watching the whole "make/recover nitric acid" series and one I would love to see would be making nitric acid using urea. Not sure if it is even possible but if so I think it would be rather interesting.
That was hella awesome
Would love to see you recover the base metals as well
(Seriously not sure why im so enamoured by metal based chemistry when i am a molecular biologist)
The good thing is expanding your interest is other fields can suggest unconventional approaches to unsolved questions in your own field
Another interesting biochemical process, is the industrial use of archaea and pyrite to harvest metals, via the sulfuric acid they produce, it could even be used during recycling of pcbs and e-waste.
However, the size of the reaction vessels used, are often quite large, as it is only useful for processing large amounts, ie tons of ore or electronic wastes.
Copper Nitrate is such a beautiful shade of blue...
Could you produce the copper and nitric acid directly if you used a cation exchange membrane to prevent the nitric acid from reacting with the produced copper metal?
A very useful and practical application of chemistry. Love this video as is gives me more routes to make copper sulfate.
From an amateur precious metals refiner, thank you for the video!
Can you avoid spongy deposits by ramping down the current at the end of the run, or perhaps even matching the current throughout the entire run with the measured impedance of the solution? May be worth doing for larger scale batches, for just for the science of it.
You could ramp down the current, but then the process becomes VERY slow. the first 90% is quick and takes a few days, but if you keep ramping down to match the copper potential, the last 10% can take weeks. So it's best just to stop when the solid copper sulfate is gone.
If your intent is to just recover as much copper as you can because you're going to smelt it all down at the end, it being spongy and weakly deposited shouldn't matter all that much. Otherwise, like NurdRage said, should just stop when it gets near the end since the copper left in solution will just feed forward with further use (just dedicate that volume to use for metal refining only).
@Kain Yusanagi Many years ago I ran the computer graphics lab for a professional photography lab, back in the chemical photography days, and they had this big tank with electrodes that they stored their waste in. Very large, but chunky, crystals of silver would build up on the electrodes, I just wondered what sort of methods could have been behind that metal recovery unit.
Do you have any recommendations on brands/supply outlets/things to look for when purchasing a platinized electrode? I’m looking for something that can handle potassium hydroxide & electrolysis (for Hydrogen Torch applications).
Thank you for sharing this amazing process. I can't believe you were contacted by metal refiners with chemists on staff, thst did not know. That is what defines brilliance. )
You seem to have a knack for electrochemistry. Can you demonstrate making solid Mg/Ca carbonate (or one of its precursors like CaO or CaOH) from feldspars or silicate minerals using water or sea water? We will need negative emissions to stay below 1.5C warming. There's a paper: "Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production" by Rau et al but I think the concept can be taken further.
Hello from France NurdRage. Really nice your video and chemistry lesson, like all times ! Can you tell us if it is possible to do the same job ( making sulfuric acdid ) with others sulfates like Iron sulfate or potassium sulfate, any sulfates maybe? Thanks NurdRage.
i totally <3 your e-chem videos, every time again it is a interesting topic.
could you show to us how to make a diaphragm cell for organic e-chem from easy to get materials??
Could you use mixed metal oxide instead of a platinum electrode?
As always an excellent video! Thank you very much!
Extremely informative video. I have couple of questions: 1) Is dilute sulfuric acid is OK for this purpose? (as long as the stoichiometric amount of H2SO4 is large enough)? 2) Do all metal nitrate salts react similarly (with reasonable speed) with dilute sulfuric acid to form metal sulfate and nitric acid? I have read that many metal chlorides react very slowly with sulfuric acid, which would cause problems in similar process for recovering HCl and Cu from dirty CuCl2 solution. 3) How do you calculate/estimate the surface area of such mesh platinum anode? (it is a 3D structure, exact surface area calculation requires taking several accurate measurements around the holes)
1) Dilute sulfuric acid is fine, but it might be annoying if it's very dilute since you're handling dilute solutions and need to distill large amounts of water. Then it becomes annoying again when you need fractionally distill the resulting dilute nitric acid.
If your sulfuric acid VERY dilute, like 10% or less, then i recommend distilling off some water from that first. Get it up to around 30% before using it (you can determine concentration by checking the density and consulting a density table). It's optional, but it's saves a lot of annoyance and time.
2) some metal nitrates will immediately precipitate insoluble sulfates, like calcium or silver nitrates. This will ruin the subsequent electrolytic step as the insoluble sulfates will interfere with deposition of metal. This is why i said you should displace all precious metals like silver using copper metal before starting. But if you have metals that aren't an issue, then the reaction with sulfuric acid is straightforward and the distillation will not be an issue. The distillation will concentrate the sulfuric acid and force forward the nitric acid production so even dilute sulfuric acid can be used.
3) A rule of thumb is that expanded mesh electrodes are 30% of the surface area of the solid electrode. So if you measure 30 square centimeters (including the holes) you actually have 10 square centimeters. but you'll need to read up the actual electrode specifications if they are available. If not, you'll need to measure and calculate the area yourself.
@NurdRage Thanks for the answers! I was thinking of car battery acid (around 35%), since that is easily available.
Couple of additional questions: If the waste copper nitrate solution is very dilute, would it make sense to try distill water out from it before this recovery process, or is it more efficient to do slow fractional distillation of the resulting distilled nitric acid?
Another question is actually more related to your old informative video: https://www.youtube.com/watch?v=FjEoRidvgYE.
If the CuCl2 solution fed to that process contains other metal chlorides, my understanding is that these will happen as long as HCl is distilled away:
ZnCl2(sq) + H2SO4(aq) → ZnSO4(aq) + 2HCl(aq)
BeCl2(aq) + H2SO4(aq) → BeSO4(aq) + 2HCl(aq)
But I have not been able to fully figure out the behaviour of SnCl2, SnCl4, NiCl2, FeCl2, FeCl3 contaminants in this process. (many references tell that reactions of these with sulfuric acid are very slow and require concentrated sulfuric acid)
Are there any risks that Sn would coplate with copper on the cathode and contaminate the recovered copper? (Sn is closest to copper on the reactivity series)
@Foo Bar 1) if you distill off too much water from the copper nitrate, you can accidentally thermally decompose it, lowering your yields of nitric acid. If you know what you're doing then go for it. But if you don't know how much copper nitrate you have i reccomend erring on the side of caution and fractionally distill the dilute nitric acid later.
2) the sulfuric acid will concentrate anyway as you distill it, so the reactions will still be driven forward.
3) not really sure about tin. But i think that would indeed be a danger. Nonetheless, i reccomend doing it anyway and then casting your copper and testing it, if it has significant tin, perform an electrorefining process.
Great video, been looking to solve this exact problem!
What a legend.
This channel deserves a million subs.
I think im going to blitz social media this week and try to make it happen.
Gudluck kid
@Cosmic Rider i was liking your comments kido:)
I have been binge watching sreetips doing metal refining and I always wince at all the toxic gas it produces during inquartation and was wondering if it is possible to easily capture that gas to make pure nitric acid. When you dissolve the reddish NO2 gas into water, is that nitric acid??
Lol. A few years after I asked, but better late than never :P Now if I can ever get my recovery lab put together....
I’ve learnt so much from you.....Thankyou your content is purely Awesome.
Thank you for your wonderful content!
I would like to see you repeat the thermal decomposition video and this video with actual refining waste. I would even send you a jug of it just to see how this would work with waste products and any contamination they may contain.
Can you do some videos on fluorine reacting with various highly stable metals?
Hi NurdRage .cool video.how can I separate the copper zinc and tin from brass? I want learn more about this process?
Thanks
Noor
No need for Pt electrode, lead metal will work just fine (only in sulfuric acid media of course) !
@ropersonline Lead is not going to be consumed at all, look how lead acid batteries work, electrodes stand for decade in such environment. Only small amount s of lead dioxide is expected to pile off over time and even that is in insoluble form.
@papanyanz yeah but lead sulfate is soluble and lethal if touched or inhaled
Hii I wanted to know how we can calculate the current densities for anode and cathode. Could you please hel
@Mia Lauren Current density is current (in Amperes) divided by surface area of the electrode. You'd need some school geometry to calculate that.
Just want to say your wisdom has been infinitely helpful... These tips you mention along the way... Beautiful.
Hi NR. Would this be feasible on an industrial scale? I imagine the energy bill could be high.
This is basically what chip fabs do. That copper waste is very valuable.
The copper oxide recovery also applies to sludge I get in my acidified copper sulfate electroforming tank. I put ingots in felt bags and after 4 five runs they are half full of goo. I have about 20 pounds of it. The tank is a low acid recipe.
Ceviri ekle
I hope you some day may be do whole series of all impurities cleaning process from any liquid form. Meaning most used preferred, so example there is little to no use remove astatine or radioactive elements cause there is almost none of them in commercial products, but all solids that may be in solution like most of the metals, post transaction metals and non metals solids. Its interesting to think process that you can take all of these in good use just knowing how to.
bormisha - 2020-11-22
This is what happens to processes of hobby refiners when the real science comes in! Thanks NurdRage, you are the real professional!
lazersteve - 2020-11-22
I've been recycling my copper nitrate for years...I first posted on the GRF about recycling copper solution over 10 years ago. If you plan on doing any serious refining, recycling your waste is not only the right thing to do environmentally, but also economically. That being said, NR has a very special way of presenting material that makes it understandable even to the layman. He is a valuable resource for everyone in the refining community. Steve
bormisha - 2021-11-08
@lazersteve How do you recycle your sulfuric acid that is contaminated with base metals?
bormisha - 2021-11-09
@lazersteve Thank you for such an elaborated answer. It sounds very complicated to not bother in most cases, but as a matter of principle it is nice to know that the purification could be done.
lazersteve - 2021-11-09
@bormisha it's no more complicated than any other salt chemistry. Key points to know are solubilities of the various salts, ions present, and which ion combinations precipitate which salt. Temperature plays an important role in these parameters as with any chemical reaction. I usually convert my alkali sulfates to nitrates then use the dissolved nitrate as a solution in my refining work forming nitric acid in situ.