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How to destroy Ferricyanide in Electroplating Wastewater

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Q. We have a kind of waste water that contains both Cyanide and Copper. We generally use bleach to pretreat it and Electrocoagulation system to treat it. However, the Ferricyanide is still there. I wonder if we have any better way to destroy or remove the Ferricyanide except put sodium metabisulfite in it.
Thanks.

Randy Guo
Waste Treatment - Vancouver, B.C. Canada


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A. We usually have from 1 to 11 ppm of ferrocyanide in our wastewater, and this process works to remove it:

Adjust pH to 11.3 with caustic, and pump in industrial strength bleach (12.5%) until the ORP reading is 500 to 600 (for our first couple batches, we went to only 450 to 500 and we found this inadequate, and ended up doing the entire batch over again). Going to 550 or 600 may be required to fully oxidize ferrocyanide to the cyanate. Allow to react for an hour.

Adding 40% sulfuric acid through a funnel attached to a 2' long hose, in order to introduce it well below the surface of the liquid, adjust pH to 8.75 (do this cautiously, and slowly, so as to not overshoot the pH target and release chlorine gas). Next, add more bleach until the ORP reading is 800 (this oxidizes cyanate to nitrogen and carbon dioxide). It is possible that you won't have to add much more bleach at all, if the ORP is found to be 800, after achieving pH 8.75. In this step, we have observed paradoxical behavior, so if adding bleach appears to lower the ORP, invest time, and bleach, and hope to eventually get there. Others have noted this paradoxical behavior in the first step, but we have not (we've seen it in this second step on some occasions). Allow to react 90 minutes beyond the time you achieve 800, or more if needed to do this oxidation step.

Next, pump in magnesium bisulfite solution a shot at a time, and instruct a second person to add caustic to keep the pH at about 8.2 to 9.2 (the goal is to keep pH at 8.75). The bisulfite will lower pH, and the task is to counter this with caustic adds, to maintain pH at 8.75. Good pH control is important to this and all steps. Go to a target ORP of 200. Sneak up on it toward the end, since once you reach 300 it will not require a lot more. This reduces bleach to just simply sodium chloride. Our local chemical distributor found the magnesium bisulfite at Hydrite Chemical in the midwest, available in plastic drums. Magnesium contributes to the efficacy of the process, so sodium bisulfite may not work at all.

We next add 7.6 ml per gal of wastewater, of a coagulant, as a 10% solution mixed into water, to the batch. We have found this product at Chemetall Oakite (Enprox 8412). Mix this for 15 min into the batch. Finally, adjust the pH to 10.6, or what is appropriate to the product next used. The batch needs to now have a flocculent added, at 3.8 ml/gal, also as a 10% solution. We have found this product at Oakite, too (Enprox 8440). Allow to mix for 15 minutes, and then settle the tank. We are getting total cyanide (e.g., ferrocyanide) at non-detect, in the supernate.

David H. Duncan
- Ponderay, Idaho, USA


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A. To the best of my knowledge, these iron cyanides are not amenable to chlorination. If your lab runs the cyanide test via distillation/colorimetric method, the sulfites you add will generate SO2 during the distillation. This passes over into the sparger solution along with the HCN. The first step of the colorimetric procedure is a chlorination with Chloramine 'T'. If there is enough sulfite in the sparger liquid to neutralize it all, a false negative results. I have personally been skunked by this on two occasions. Once, I got a really nasty surprise when the inspector came along and cited me because my "non-detect" effluent was in fact, in violation.
I developed a precipitative method for removing these complexes.

A careful technician will check the analytical prep after the Chloramine 'T' addition with KI starch paperamazoninfo, and add excess if required. Or, the finish could be run by ion selective probe, which is not subject to this interference.

Dave Wichern
- The Bronx, New York


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Yes, that's correct, iron cyanides are not amenable to removal by chlorination, as cyanide is. The procedure above uses bleach to oxidize ferrocyanide all the way to iron cyanate, which is then further oxidized to decompose the cyanate to elemental nitrogen and carbon dioxide. It does require a fair amount of bleach. Thanks for the tip on sample prep!

David H. Duncan
- Ponderay, Idaho, USA



February 13, 2014

Q. I am now one of the lab technicians at the company where David H. Duncan established this procedure for the removal of ferricyanide. Sadly, Dave passed away a few years ago but we still follow his procedure with the exception of us starting to use sodium bisulfite instead of the magnesium bisulfite in the process. We made this substitution due to us no longer being able to obtain the magnesium bisulfite from our chemical supplier.

I know Dave mentioned at the time of this post that this substitution "may not work at all" but we still have been achieving a total cyanide result of "non-detect" from our EPA approved outside testing lab and have been doing so for quite a few years now. Occasionally, the process needs to be repeated but it is very rare. Recently, during the ferricyanide removal processing of a waste water batch we added an excessive amount of sodium bisulfite due to a malfunctioning ORP meter. When a sample of that batch was sent out for analysis, the lab provided us with a positive result for ferricyanide at a level that is nearly impossible for the batch to achieve even without processing. We submitted a second sample for testing since we suspected that the excessive sodium bisulfite maybe causing interference with the analysis but the lab again provided us with a positive result. We would like to reprocess the batch but we're reluctant to make any further additions of sodium bisulfite and wondered if anyone had any suggestions to remove the sodium bisulfite from the batch before reprocessing.

Doug Marden
- Ponderay, Idaho United States of America


February 18, 2014

A. Make sure your lab, if they are running CN(t) by colorimetry, tests the sample prep after the chloramine 'T' addition. The sulfites come over in the distillation and if there's enough to neutralize all of the oxidizer you will get false negatives.

Dave Wichern
- The Bronx, New York

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