Discussion - Modeling of natural cyanide attenuation in tailings impoundments (Paper originally published November 2000, Vol. 17, No. 4)

Botz, M. M. ; DeVries, F. W. ; Mudder, T. I.
Organization: Society for Mining, Metallurgy & Exploration
Pages: 2
Publication Date: Jan 1, 2002
Discussion by F.W. DeVries Comments on natural cyanide attenuation. The paper by Botz and Mudder in the November 2000 issue of Minerals and Metallurgical Processing had one disappointing aspect. Table 1 (p. 229) failed to include a significant species - neutral copper cyanide (CuCN). This compound has been most trouble-some in many plant-scale cyanide cleanup processes, includ- ing acidification-volatilization- reneutralization (AVR), hy- drogen peroxide cleanup and air/SO2 cleanup. It has also plagued many pilot efforts to use ion-exchange (IX) resin technology. This author elucidated the concept that, under some conditions, copper cyanide failed to precipitate out of treated effluents and appeared to exist as a filterable colloid that reported as copper and cyanide, with the latter measured as WAD (weak-acid-dissociable) cyanide in that analytical method. The concentrations measured were very near the levels of 0.2 ppm, often the regulatory limit for WAD cyanide. The copper concentration, using the 1 : 1 ratio for this com- pound, would then be more than 0.4 ppm, which could also be unacceptable. We discovered that it was unsafe to assume that the Cu(CN),- would surrender both cyanide ions simultaneously and allow cupric copper to be removed subsequently as, say, cupric ferrocyanide (Hatchett's Brown). This compound could be ignored as safely as the "iron blues," as essentially an inert solid, stable in geologic time if not exposed to sunlight. Under poorly controlled oxidation of the cyanocuprite ions (copper with four, three or two cyanides complexed to the copper), CuCN could well be formed and could not be assumed to precipitate out as a solid. The authors of the paper, by failing to include the CuCN species in their model, may have left users of the model prone to ignore the possible occurrence of the colloidal(?) form in the discharge, thus finding an effluent that failed to meet regulatory limits. (See addendum below.) This somewhat ephemeral material may well have been responsible for some large-scale failures of cyanide destruction technology to succeed at sites in North America and elsewhere. Two specific references alluding to this occurrence may be found: Griffiths et al., 1987, "The detoxification of gold-mill tailings with hydrogen peroxide," Journal of the South African Institute of Mining and Metallurgy, September, p. 282. DeVries, 1989, "Improved understanding in detoxification of cyanide leach liquors using peroxide" Rand01 Gold Conference, Sacramento CA, p. 15 1. It is advisable for workers in this area of cyanide removal or recycle to avoid assuming that CuCN will, with certainty, precipitate out of solution, or that the dicyanocuprite ion will part simultaneously with both cyanide ions and allow cupric copper to be dealt with by other reactions. One further piece of work may be incomplete. That is, a definitive study of the long-term behavior of CuCN that does precipitate when exposed to other compounds present in neutralized tailings. Addendum. The extremely complex reaction of cupric ion on cyanide- which, of course, results in oxidation of cyanide to cyanate, probably through the intermediate stage of forming cyanogen [(CN)2] from oxidation of HCN with its hydrolysis to cyanate and cyanide ion - involves two cyanide moieties and the reduction of the cupric ion back again to the cuprous state. This, then, can form the CuCN potential "solid" that was already the undesirable species. In cyanide cleanup, with either air/SO2 or hydrogen peroxide, copper is generally employed as the catalyst, so it is unclear what happens when the CU(CN)2-1 is ultimately exhausted. Certainly, the field evidence is quite clear that all
Full Article Download:
(158 kb)