Waste Water Treatment for zinc electroplating(1995)
Q. Our company paints and Zinc plates automotive parts. We usually segregate the waste water from both the departments. But by accident, all the water got mixed up, and now we are having problems with the precipitation of Zinc. By the way, we use hydroxide precipitation to remove metals. We have been able to get down the Zinc concentration to 4 ppm using various chemicals, but not any lower than that. Our discharge limits are 2.61 (daily) and 1.48 (monthly).Various chemicals we tried : Caustic soda, Lime, Magnesium oxide, Ferrous sulfate, Calcium chloride, Sodium borohydride, Calcium polysulfide, two proprietary organometallic polymers. Any suggestions will be highly appreciated. Thanks in advance.prasad s [last name deleted for privacy by Editor]
A. I assume these values are after filtration, Prasad?
If not, your problem is easily solved -- you need to clarify or filter the wastewater.
My personal experience is that sulfide chemistry is often the most powerful precipitating method for zinc, like calcium polysulfide [adv: avail. from "Graus Chemicals], DTC (sodium diethyl dithiocarbamate) or Degussa's proprietary TMT15.
For this one-time troublesome batch, I suggest trying to lower the pH to about 5 and loading it up with your ferric chloride before raising the pH for the hydroxide precipitation. Filter out the precipitated zinc. Now treat the filtrate with the proprietary co-precipitant and the polysufide, DTC or TMT15. Naturally, do jar testing of this idea committing the whole batch. before Good luck.
Ted Mooney, P.E.
Pine Beach, New Jersey
Q. Dear Mr. Mooney :
Thank you for your reply. I forgot to mention, but we tried the carbamate too. Yes, we are filtering the effluent. Since my last letter, we had successfully precipitated out zinc using Magnesium Oxide and a proprietary organometallic polymer 326-C. But now we are having problem removing Nickel. This is not caused by 326-c. We had the problem with Nickel to start with. One more chemical we tried in the last couple of days is Ferric Chloride at around pH 8.0. Please suggest any chemicals to remove Nickel and at what pH, they work best. Thanks again for your reply. -Prasad.prasad s [returning]
A. Hi, Prasad.
1). When you describe all these things they you have tried, they hopefully were each tried on small samples of the waste. You should not attempt treating the whole batch without lab scale beaker tests first to verify that they work, or you will be faced with a large volume of witches' brew that already contains large amounts of a dozen different precipitants, and it just gets harder and harder to treat.
2). After some of the metal has precipitated out, you must get rid of it by filtering it before going on to deal with the remaining dissolved metal. If the precipitated metal remains in the batch you are working with, constantly ready to redissolve into equilibrium, you may never get there. The strong sulfur based precipitant will remove a molecule of zinc, but if the waste was not filtered, a molecule of formerly hydroxide precipitated zinc just goes back into solution to replace it. So you must hydroxide treat, filter it, and then sulfide treat only the remaining unprecipitated zinc and nickel.
3). In general, nickel precipitates best at high pH, about 10.5. When magnesium hydroxide is used for the treatment of nickel it has to be 'topped off' with caustic or another stronger alkali because magnesium hydroxide doesn't get the pH high enough. See letter 565 for starters.
4). You need a treatment sequence and strategy, not a hunt for a miracle precipitant. For example: lower the pH, add ferric chloride, raise the pH, add flocculant, and filter out most of the zinc. Now you take the clear effluent and raise the pH further to remove the nickel, and filter it. Now you are left with a few ppm of zinc or nickel still in solution, and you add a few ppm of a powerful sulfur based precipitant to precipitate it.
It may be unaffordable and environmentally hazardous to try to remove the bulk of the metal with strong sulfides like polysulfide or DTC! In America, the worst pollution incident in the history of the electroplating industry was not a discharge of untreated or under-treated waste, but a a gross over-discharge of the treatment chemical DTC (White River, Indiana).
Ted Mooney, P.E.
Pine Beach, New Jersey
May 2, 2013
A. Try 3 separate tanks, bring the pH to about 6.5 in the first tank while adding the ferric chloride; then in the second tank raise the pH to about 9.2-9.5 try aluminum sulfate in this tank; then in the 3rd tank (typically a smaller tank then the first 2) meter in the polymer and run through a clarifier/filter press. There are many things to take into consideration ... the flow of the water and how fast the coagulant/flocculant chemicals are feeding, I do not deal with nickel but our effluent numbers are usually below 1 mg/l.Jake Skinner
- Clinton, Iowa, U.S.
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