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topic 12375

HOW TO ELECTROWIN COPPER


A discussion started in 2004 & continuing through 2016 and beyond.

(2002)

Q. I just wanted to know whether only copper can be taken out from rota cat which is dissolved in sulphuric acid or rota cat can also be used to recover metals like nickel in hydrofluoric acid, chromium in hydrofluoric acid, iron in hydrofluoric acid, zinc in sulphuric acid?

Would be delighted to have an answer.

VIDU GOYAL
METAL WORKS - Rewari, Haryana


(2002)

A. I assume by the term "rota cat" that you are referring generically to a rotating cathode system, and not a particular system commercially sold as a Rota-CatTM. They are two entirely different concepts.

The rotating cathode design (normally a rotating metal cylinder onto which metal is electrodeposited) is useful for a variety of electrowinning applications. The caveat here is that you need to have a proper design on the other side of the reaction -- the anode -- to allow electrowinning from these types of solutions that you mention. Sulfuric acid based electrolytes are amenable to most electrode designs, however caution must be used on ionic strengths. More is not necessarily better.

The use of any type of anode in a HF environment is severely limited due to the materials of construction and the cost. You would at a minimum require a niobium substrate and platinum catalyst coating. Normally, this has to be either a hot dipped platinum coating (i.e the patented "DeGussa Process", or the platinum could be clad onto niobium in small sheets and slit and expanded to get larger geometries. Depending on how much surface area that you need, you are likely to pay several tens of thousand dollars for anodes in a system such as these -- and they might not last 3-6 months time.

There has been some limited success in the use of ion specific membranes to envelope the anodes. This requires a separate electrolyte solution to promote conductivity between the membranes and the electrodes. Fluoride, being a very small ion, will permeate the membrane over time, and you will have to deal with the issues it causes.

I would stay away from any precious metal oxide based electrodes, as these are micro-cracked coatings and will allow free fluoride attack on the substrate, which will dissolve, and the coating will literally fall off in a process called exfoliation.

As far as the actual process goes (electrode issues aside) the strength of the acids and such will determine the efficiency of the process. You have to be your own gauge on whether the costs to operate the unit, including power, man-hours to maintain and remove deposits, and replacement parts have a positive value as compared to the recovered value of the metals. Zinc and tin are the least likely to be economical, copper fluctuates, and nickel is usually a positive to break-even consideration. I am not aware of anyone who has successfully electrowon iron from solutions on a commercial scale.

You need to be prepared to run an electrowinning unit much the same as a plating bath, which means additives, buffers, and other things will be required in the case of some metals, such as nickel. Also, remember that deposit integrity is a must - you're trying to get a thick deposit, and EVERY inconsistency in the deposit will be magnified, which usually means dendrites, and low quality plating.

Lastly, I would tend to stay away from any electrowinning cell that requires the use of raw media (other than reusable substrates like stainless steel or titanium) to plate on to operate. In some cases, they might tell you that you need copper shot as a starting media. It might have a value of US$3.00/kg, but as soon as you put in the cell and use it, its value drops to type 1 scrap or less - which means you lose money right from the start. Titanium makes for an excellent cathode, and if polished and used correctly, will give you almost immediate release of the reclaimed metals. I have seen too many cells where cathode prep was non-existent, and they use air chisels to try to remove the metal deposits.

tom baker
Tom Baker
   wastewater treatment specialist
Warminster, Pennsylvania



thumbs up sign Super informative posting, Tom. Thanks!

Regards,

Ted Mooney, finishing.com Teds signature
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey



October 3, 2011

Q. Hello,

I am electrowinning copper chloride with a membrane. In an older post in this forum, I read that chlorides stress the deposit and consequently, it grows doing trees and dendrites and takes a lot of space on the cathode for a few grams ... and that is my problem.

I am would like to know if there is some bath additive that can reduce considerably the formation of dendrites?

Thanks,

Pedro Torres
metal technician - Bogota, Colombia


October 6, 2011

A. Try adding some gelatin, coumarin or naphthalene trisulphonic acid. I have never done it with electrowinning, but try about 1 g/litre.

trevor crichton
Trevor Crichton
R&D practical scientist
Chesham, Bucks, UK


October 8, 2011

Q. Thanks, I will give a try to gelatin. Do you recommend a special one? from pig? or other?

The solution contains about 10 g/liter of copper. I reduced it first to get only Cu+ chloride complex, else the solution etches my cathode. pH is adjusted to 2. Chloride concentration is about 20 g/L.

Regards,

Pedro Torres [returning]
- Bogota, Colombia



July 16, 2012

Q. Hello,

I am electrowinning copper from chloride media.

I succeeded once to get a thick, compact and adherent deposit until 1 g/L Cu but now I am suffering to get the good conditions again. My solution has around 15 g/L cuprous chloride (not cupric). I use gelatin as additive. The solution has 2 g/L Zn and 1 g/L Ni, lots of Cl-, Na+, [SO4]2-.

At the beginning of my new attempt, I got brownish and dendritic copper with 0.3 M H+.

I cleaned the cathode to remove the dendrites then I raised solution acidity to 1M H+. The new deposit was compact and adherent but my deposit has still some brownish areas in the top part the cathode. I don't see hydrogen evolution but I suppose this could be the origin of the brownish color. Electrolyte flow is 5.7 m^3/hr which is already quite high but necessary considering low copper concentration.

Why my copper deposit gets a brownish or reddish color instead of the sweet pink copper color ? should I raise acidity ? or improve circulation ?

Thanks,

Pedro Torres [returning]
metal technician - Bogota, Colombia


July 18, 2012

A. As the copper concentration decreases, you will need to do one or more of the following.

Reduce current density, and/or
Increase agitation, and/or
Use a high surface area cathode (which is the same effect as reducing current density).

Lyle Kirman
consultant - Cleveland, Ohio


July 19, 2012

thumbs up signDear Lyle,

I think I figured out what happened. My solution had more impurities than previously, especially Ni. Increasing the acidity made the impurities less active at the cathode surface. My flow rate is around 10 m/h (m^3/h per m2 cathode) and I got nodular but compact deposit which is enough for my application.
Pedro T.

Pedro Torres [returning]
- Bogota, Colombia



Copper electrowinning parameters

August 25, 2014 -- this entry appended to this thread by editor in lieu of spawning a duplicative thread

Q. Hello everyone,

I'm currently working on electrowinning of copper from copper sulphate solution.

The initial specifications for the copper sulphate solution are:
Copper content: 21000 ppm
pH: 1

I used the following parameters for my electrowinning of copper
Temperature: 38 °C
pH: Adjusted to 2 using ammonia hydroxide of 1M
Boric acid of 30 g/L
Cathode: Stainless steel 316L
Anode: Titanium coated with platinum
Current density of 400 A/m2

However after 5 hours of plating and maintaining the pH to less than 2, I realise dark brown powder coated onto the cathode. I assume that is copper but I don't understand why is it not adhering to the cathode. I'm expecting it to be plated out like a sheet of copper.

Can anyone enlighten me if I have done anything wrong or change any of my parameters?

Thank You

Yan Jun Jie
- Singapore


August 28, 2014

A. Hi Yan

Many things in your question suggest that you are not an experienced plater or chemist and it would be interesting to know how you arrived at your starting conditions but I will try to point you in a more productive direction.

It is important to know what you mean by electrowinning. It usually applies to a method of extracting copper from ore or a crude copper anode e.g what you might get from melting electronic scrap. In that case, your objective is to obtain as pure a deposit as possible and the appearance does not matter because it will be melted down. Therefore you would plate onto a copper plate and avoid additives. The cathode plate is either stripped or, more usually, smelted with the deposit. Electrowinning is a crude large scale operation using impure materials with very little control of the plating conditions.

The term is sometimes used to describe extracting metals from rinse waters.

Firstly, if I have counted all those zeros correctly, you have about 21 g/l of copper, which is rather low. In a practical electrowinning situation, you would want it as high as possible to allow more current to pass and speed up the process.

You should aim for about 100 g/l of sulphuric acid. Unless you have very specialised equipment and knowledge, pH values under about 3 are meaningless.

I have no idea why you are adding ammonia. It is a very bad idea as it will complex with the copper and cause endless problems.

Similarly, boric acid has no use here.

If you really must have a fine grain deposit, the simplest additive is probably gelatin about 1-2 g/l but some will be in the deposit. It is rarely used in electrowinning

Current density is about 3-5 A/dmsq at room temperature (neither is critical).

geoff smith
Geoff Smith
Hampshire,
       England




Electro-won copper is fragile and only the density of a cookie

November 21, 2014

Q. Hey there...

I'm getting copper electrolyte from sea water leaching process, in which 01 Washing stage in SX, with not that high chlorine level in electrolyte.

I'm working in a copper sulphate electrolyte tank house and we tried to electro-win copper -- but it was very fragile & easy to rip out.

Conditions:
- Cu: 28 g/lt
- H+: 180 g/lt
- Cl: 40 ppm
- T: 25 °C
- Amp: 6000 Amp
- Density 45 A/m2

What's the reason for the "cookie" density copper?
Thanks

mikel manchego
- Sta Rosalia, BCS, mexico



Electrowinning Research: Copper is turning black during electrowinning

December 14, 2014

Q. I am working on a project for extracting copper from powder-form raw material which is a waste from brass industries, containing 7-15% copper, 20% zinc and around 10% iron.
I have taken 3 samples of 25 grams and dissolved in mild H2SO4, HCl and CH3COOH in three beakers. I tried to apply direct DC current using Carbon Cathodes^Anodes (+) to pass electricity as the copper is already dissolved in the solution and a Copper anode^cathode (-) to accumulate extracted copper. But the thing is when I switch on the electricity some bubbles start to form and copper anode^cathode suddenly turns black. In this experiment the main target is to extract copper from raw material (not finishing).
Please help. I have no clue what is exactly happening in my cell. And please give some suggestions.
Thank you.

Apurva Patel
M.Tech Chemical Engineering student - Kadi, Gujarat, India


December 2014

A. Hi Apurva. Your nomenclature is reversed. The negative pole where you are accumulating your plated-out material is the cathode, and your carbon positive pole is the anode. I am assuming that you succeeded in dissolving the powder into the acids before you started trying to plate it out?

You haven't given us any details on pH, current density, etc., but from your description of bubbles and "suddenly turns black", it sounds like the current is far too high. What you probably need to do as a first step is to maintain a current density so low that copper plates out preferentially to iron, nickel, and hydrogen.

Good luck.

Regards,

Ted Mooney, finishing.com
Teds signature
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey


December 20, 2014

Q. Thank you so much for your reply. It helped a lot. I have used hydrogen peroxide to increase leaching but as it is strong oxidant; I suppose that's why I get black copper. I am using 20% sulfuric acid for leaching and electroplating in same cell. I am using 5V 0.4A DC source for plating. My raw material is smelter slag containing copper, zinc, and iron in major part. So I am directly mixing 25 grams of sample in 20% sulphuric acid and apply electroplating in same cell. My main target is to recover copper and zinc from the raw material. Please guide me in right direction. Am I doing it right?

My questions are:

1. At what voltage I can only get copper from the produced mixture of copper sulphate, zinc sulphate and iron sulphate.
2. Should I use different solvent to increase electroplating efficiency?
3. I have heard about some organic chemicals that can separate copper sulphate and make it float over the solution. Is it true? If it is then suggest some names.
4. Can I recycle electrolyte?
5. Can I recover zinc and copper both from the same solution? What changes should I apply.
6. Can I use iridium oxide coated titanium anodes for this application to eliminate anode corrosion? Or to provide better anode.

Thank you so much for helping.
I guess you are my only hope.

Thank you.

Apurva Patel [returning]
- Kadi, Gujarat, India.


December 2014

A. Hi Apurva. I'm sorry to hear we're your only hope :-)

My experience is in electroplating, and while there are certain similarities, I can't help you very much in the details of differential electrowinning ...

Yes, a strong oxidizing agent like peroxide can wreak havoc on electrodeposition -- hopefully there is little of it remaining by the time you do the plating. Bubbling the solution should help it escape.

1. Copper is more noble than iron or zinc and will selectively plate out if you keep the voltage below the voltage needed to plate those other metals out. But it's not quite as easy as looking up the potentials in the galvanic series because it depends on concentration. 5V sounds way too high unless the anode is quite far from the cathode so there is over 4V of solution resistance.
2 & 3. I have not heard of such in my limited experience.
4. Recycling may be possible to some extent, but the acidity is consumed whenever hydrogen bubbles are released from the process. 2H20 => H2^ + 2OH
5. In practice I doubt that you will be able to recover the zinc. Zinc electroplaters generate tons of zinc-rich sludges, and even in their more favorable position of having solutions richer in zinc and lower in other metals, practical zinc recovery escapes us.
6. Yes, I think iridium oxide coated titanium anodes would be fine. Good luck.

Regards,

Ted Mooney, finishing.com
Teds signature
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey

----
Ed. note: Readers, please see letter 14472 "Electro-refining of copper" for additional discussion on this topic.



May 16, 2016 -- this entry appended to this thread by editor in lieu of spawning a duplicative thread

Q. In our company dealing with copper cathode and rod production, we have cathode nodulation problems. How we can solve this issue?

Khagani Asadli
- Baku, Azerbaijan


May 2016

A. Hi Khagani. We appended your inquiry to a similar thread to give you some food for thought. Please get back to us with additional detail or your comments on the solutions proposed. Thanks.

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"


May 18, 2016

A. Nodulation is normal on thick deposits, especially in high current density areas. Are the nodules in just one area of the part or all over? Is it possible that your current density is too high?

Lyle Kirman
- Cleveland, Ohio USA



September 21, 2016

This is a wonderful effort by a group of experts worldwide with a view to finding out minor faults in operation. Appreciate all your work.

We, at Jay Somnath Industries, are having a melting unit with a rotary furnace for melting of brass residues and recover copper ingots (98.5% Cu) along with collecting zinc oxide (80%+ ZnO). We are thinking of further refining copper to a high-grade copper ingot and zinc ingots from 80% Zinc Oxide powder via electrowinning.

Specification of copper ingot:
Weight - 60 kg
Length- 20 inch
Width- 8 inch
height- 5 inch

Avg. spectro result of Copper:
Zn: 0.028 %
Pb: 1.077 %
Sn: 0.114 %
P: 0.00 %
Mn: 0.0106 %
Fe: 0.027 %
Ni: 0.391 %
Al: 0.009 %
Si: <0.005 %
Ag: 0.043 %
Co: 0.003 %
Cu: 98.298 %

First of all; Is it possible to purify such ingots with electrowinning? If it so, then we can operate with existing ingot size or should we have to change the size that fits with the requirement?

Secondly, does zinc oxide has some future with electrowinning?

Please enlighten to concepts with your life long experience.

Regards,

Vasu Patel
Jay Somnath Industries - Gujaratr, India



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