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Mercury precipitation reagents were compared using pregnant cyanide leach solutions. Sodium polymeric thiocarbonate (NaPTC) was most efficient and selective reagent. Mercury occurs primarily as cinnabar (HgS) in some gold ores.
Mercury precipitation reagents were compared using pregnant cyanide leach solutions. Sodium polymeric thiocarbonate (NaPTC) was most efficient and selective reagent. Mercury occurs primarily as cinnabar (HgS) in some gold ores.
Mercury precipitation reagents were compared using pregnant cyanide leach solutions. Sodium polymeric thiocarbonate (NaPTC) was most efficient and selective reagent. Mercury occurs primarily as cinnabar (HgS) in some gold ores.
Principles of Green Chemistry provide useful guidance for sus-
tainable mineral process development. Laboratory bench scale test- ing was carried out using pregnant cyanide leach solutions, and a number of commercially available mercury precipitation reagents were compared using jar testing to determine the most efficient and selective reagents for mercury precipitation. The most efficient reagent identified was sodium polymeric thiocarbonate (NaPTC). Coagulation experiments with fine diatomaceous earth resulted in a stable precipitate, with good settling properties. On line monitoring of the mercury in solution is recommended for process implementation to conserve reagent removing approximately 90-95% of the mercury with minimal silver and negligible gold losses. INTRODUCTION Newmont Metallurgical Services has been involved in research and development efforts to control mercury concentrations in metal- lurgical processing circuits and for meeting discharge requirement for excess processing water for over a decade. Recent work has focused on the stepwise removal of mercury from the higher concen- tration gold bearing (pregnant) cyanide solutions (Bucknam 2001 and 2002), where it will be most beneficial from economic, industrial hygiene and environmental perspectives. The American Chemical Society (ACS) supports the use of the twelve Green Chemistry Principles (Anastas, P. T.; Warner, J. C., 1998), which are mostly related to chemical syntheses. Several of the principles, however, provide guidance for sustainable use of chemicals in metallurgical processing as follows: 1. prevention, 2. atom economy, 3. safer auxiliaries, and 4. real-time analysis for pollution prevention. This paper explores how these four green chemistry principles apply to the development of methods for removal of mercury from pregnant cyanide solutions. PREVENTION Use of low concentrations of cyanide for leaching of gold is by far the best preventative measure to be employed to keep the mer- cury present in the ore out of solution. Mercury occurs primarily as cinnabar (HgS) in some gold ores and, as a sulfide, typically requires higher concentrations of cyanide in solution to dissolve than does the elemental form of gold present in oxide gold deposits. Heap leach- ing of oxide deposits for gold may be operated efficiently by monitor- ing the concentration of cyanide in the pregnant solution by silver nitrate titration to make sure that there is still a measurable concen- tration of un-complexed cyanide leaving the heap, which indicates that the pregnant solution still has the ability to leach additional gold. Field tests were conducted to determine if addition of sodium hydrosulfide (NaSH) to leach solutions could be used to prevent mer- cury from dissolving from the ore. Dark sulfide precipitates were observed on the surface of the heap which re-dissolved in the leach solution, demonstrating the instability of inorganic mercury sulfide precipitates in cyanide leach solutions. Column tests were conducted at the University of Nevada Reno (UNR) using potassium dimethyldithiocarbamate (KDMDTC) to precipitate the mercury in the pregnant solution leaving the column vs. adding the reagent to the leach solution to prevent the mercury from leaching (Misra, Lorengo, Nanor and Bucknam, 1998). Results indicated that precipitation of the mercury leaving the column was much more efficient for mercury removal than adding the reagent to the leach solution, which indicates that the reagent was being con- sumed in the ore by mechanisms other than mercury precipitation. Mercury precipitation from pregnant cyanide solutions can be viewed as a preventative measure, however, since it can be used to control the mercury contamination in the downstream processed if properly managed. Research on preventing mercury from dissolving in cyanide leach solutions needs to focus on development of a reagent to selec- tively passivate the cinnabar in the ore from dissolving in cyanide. Work to date using reagents containing sulfide ligands indicate that they are most effective after the mercury is dissolved and in the absence of other reagent consuming solids. ATOM ECONOMY Conventional technology for the removal of mercury from preg- nant cyanide solutions relies on sulfide based inorganic and organic chemicals (Diaz, Cavero and Yataco 1999). From a cost perspective, inorganic sulfide chemicals are preferred, due to their low cost. From an atom economy perspective, however, inorganic sulfides do not perform well overall in cyanide circuits, due to their instability. A series of screening jar tests (Bucknam, 1997) was carried out to determine the relative efficiency of sulfide containing reagents for precipitation mercury from two different cyanide pregnant solutions. The active ingredient and concentrations of the reagent in the prod- uct was obtained from the manufacturers so that the reagents could be directly compared on an equivalent concentration basis. The active sulfide group in each reagent tested is shown in Table 1. Reagents tested included: 1. KDMDTC - Potassium Dimethyldithiocarbamate 2. NaCTA Sodium carbonotrithioic Acid 3. NaDBTDC Sodium dibutyldithiocarbamate 4. NaDEDTC - Sodium diethyldithiocarbamate 5. NaDMDTC Sodium dimethyldithiocarbamate 6. NaSH Sodium hydrosulfide 7. NaPDTC Sodium polymeric dithiocarbamate 8. NaPDAET Sodium pyridodiamidoethanethiol 9. NaPTC Sodium polymeric thiocarbonate 10. NaTMT Sodium trimercaptos-triazine SME Annual Meeting Feb. 24-26, Denver, Colorado PREPRINT 04-101 A GREEN CHEMISTRY APPROACH TO MERCURY CONTROL DURING CYANIDE LEACHING OF GOLD C. H. Bucknam Newmont Metallurgical Services Englewood, CO 1 Copyright 2003 by SME Figure 1. Comparison of Active Sulfide Groups for Mercury Removal Reagents Tested The inorganic hydrosulfide is the simplest functional sulfide ion, followed by the carbonotrithioic, mercaptotriazine, dithiocarbamate, polythiocarbonate and amidoethanethiol (Matlock, Howerton and Attwood, 2001) in order of increasing complexity. Some of the organ- ic sulfide active groups have different functional groups which affect their activity towards mercury removal from pregnant cyanide solu- tions. Jar testing of the reagents on the nominal 3 and 6 g Hg/t preg- nant cyanide solutions covered the range of 0-25 g reagent/t of preg- nant solution, starting from 1% stock solutions of the reagents, except for the NaPDAET, which was provided by the University of Kentucky as a nominal 15% solution in organic solvent and was added neat by micropipet. Initial screening eliminated NaTMT, NaCTA and NaDBTDC in the concentration range tested. Table 1 shows the relative rating of the reagents at 95% mercury removal. Table 1. Rating of Reagents for 95% Mercury Removal for Pregnant Cyanide Solutions 0.5-6 g Hg/t As can be seen from the reagent to mercury mole ratios, the NaPDAET designed reagent provides near stochiometric results, resulting in true atomic economy and as such should be designated as a green reagent for mercury removal. Many analytical problems were encountered during the screen- ing testing, which is a common problem for mercury studies. Best results were obtained after preserving samples with 1% bromide chloride solution and performing mercury analysis in the preserved pregnant solutions by inductively coupled plasma (ICP) emission at Newmont Metallurgical Services. The gold silver and mercury con- centrations of the pregnant cyanide solutions used in the screening testing is summarized in Table 2. Table 2. Summary of Gold, Silver and Mercury Concentrations in Heap Leach Pregnant Cyanide Solutions Used in Reagent Screening Testing SAFER AUXILARIES Screening studies identified the best candidate precipitation reagents for mercury removal from pregnant solutions from a chemi- cal perspective, but it left the question of how to efficiently remove the fine precipitated solids from the solution without affecting gold recov- ery. In the excess water treatment process, ferric chloride is used to co-precipitate arsenic, coagulate the fine solids with the aid of floccu- lants and lower the pH prior to discharge. A reactor clarifier is required for solid-liquid separation in this process. In the case of re-circulating pregnant solutions the simplest solution is to use the heap leach pad as a filter to remove the fine mercury precipitates. This concept was tested in the lab using fire assay to quantify the gold and silver losses in the fine precipitates. For the NaPDAET reagent, 95% mercury removal indicated about 9-12% silver losses and gold losses were not significant at <1%. For NaPTC the indicated silver losses at 95% mercury removal were 2-62% with gold losses <1%, indicating that a target mercury removal of 90-95% may be better to limit silver losses. It was recom- mended to set the mercury removal target where the amount of silver removed from solution equals the mercury concentration to optimize reagent use. Pilot testing for the use of NaPTC for the pregnant solution recir- culation application was recommended, since NaPDAET reagent is not available in commercial quantities. The test would simulate the time that the reagent would have to mix in the surge tank and during pumping back to the heap and verify that silver losses can be con- trolled and the gold losses will not be significant in production. In the case of treated pregnant solutions destined for gold recovery by Merrill-Crowe, it is desirable to remove the mercury pre- cipitate from solution prior to or in the clarifier filters. Preliminary plant trials using NaSH for mercury removal in pregnant solutions showed that clarifier filters could be easily plugged with fine mercury and silver precipitates in just a few minutes. Jar tests were carried out using a fine (-350 mesh) high surface area diatomaceous earth (DE) product with five minute reaction time were successful at 77% mercury removal with no gold and silver loss- es using 2 g NaPDAET/t in a 1.64 g Hg/t pregnant cyanide solution and 90% mercury removal was obtained in another pregnant cyanide solution with 6% silver and no significant gold loss. DE is a green SME Annual Meeting Feb. 24-26, Denver, Colorado 2 Copyright 2003 by SME auxiliary for gold heap leaching processes since it is pure silica, sim- ilar to the ore that is being leached. Tests were carried out using NaPTC at twice the NaPDAET dosage for the lower mercury concentration pregnant cyanide solu- tion and 1.5 times for the higher mercury concentration mercury preg- nant cyanide solution and comparable results were achieved. Fine DE was confirmed to be an effective green auxiliary reagent for use in solid liquid separation of the fine mercury from pregnant cyanide solutions. An equal weight of DE to mercury precipitate concentra- tion is recommended to effectively adsorb the fine precipitate from solution. REAL TIME ANALYSIS FOR POLLUTION PREVENTION At the completion of the preliminary DE testing, the research was refocused on treatment of pregnant eluant solution at an order of magnitude higher concentration of gold and mercury and higher tem- perature. The concentrations of gold, silver and mercury in the preg- nant eluant and intermediate eluate solutions used in the preliminary screening tests are shown in Table 3. These solutions were blended with the heap leach pregnant cyanide solutions at a ratio of about 1:100 parts, prior to Merrill-Crowe gold recovery. Table 3. Summary of Pregnant Eluate Gold, Silver and Mercury Concentrations Screening results eliminated NaPDAET as a suitable reagent for the pregnant eluate, probably due to hydrolysis of the complex molecule at the high cyanide concentrations and temperatures. Work proceeded using NaPTC, which showed excellent atom economy in development pilot studies carried out on-site by Pocock Industrial. Bulk sludge produced passed TCLP testing and is scheduled for long-term stability testing at NMS using water and cyanide solutions. Since the metals concentrations vary during the cycling of the carbon stripping process, it will be desirable to monitor the solution in real time, if the reagents are to be added directly to the holding tank. A survey was undertaken of analytical instrumentation that could be used to monitor the mercury concentrations for process control as a result, four instrumental methods were identified for real-time analy- sis of mercury concentrations in solution: 1. digestion-cold vapor atomic absorption (CVAAS), 2. digestion-cold vapor atomic fluorescence (CVAFS), 3. inductively coupled plasma emission spectroscopy (ICP), and 4. x-ray fluorescence (XRF). Do to the relatively high concentrations of mercury in solution and the relatively low cost of instrumentation, the XRF application was tested and appeared to give satisfactory results above 50 g Hg/t. Subsequent plant experience, however, has resulted in lower mercu- ry concentrations in the 50 g Hg/t range, eliminating that option. Two on-line CVAAS instruments have been ordered for use in pollution control in the excess water treatment plant to be installed in the Fall of 2003. Plant performance of these instruments will be eval- uated to see if they can be used for real-time control of mercury pre- cipitation for pollution prevention in the excess water treatment plant. CONCLUSIONS AND RECOMMENDATIONS Research and development efforts carried out by NMS on mer- cury removal from pregnant cyanide solutions have been reviewed according to four green chemistry principles to see if the implemen- tation of the technology for mercury removal from pregnant cyanide solutions can be used as a gauge of the technologys contribution to sustainable mineral development. In terms of prevention, use of low concentrations of cyanide in solution is probably the best option to prevent cinnabar dissolution. Use of sulfide precipitation chemicals does not prevent mercury dis- solution, but helps to manage the mercury concentrations in solution at the heap leach source, preventing mercury contamination in the processing plant.. Addition of the precipitants are most efficient as the pregnant cyanide leaves the heap. Addition of NaSH to the leach solution in ineffective due to dissolution and use of other organic sul- fide precipitants result in losses if added to the leach solution which do not contribute to mercury removal from solution. Research is needed to identify a reagent specific for passivation of cinnabar to dissolution by cyanide leach solutions. NaPDAET was shown to have the best atom economy for mer- cury removal in pregnant heap leach solutions and should be given preference for use if it can be made commercially available at a rea- sonable cost. NaPTC showed comparable atom economy in the pregnant eluate application and the efficiency was proven in pilot scale testing at site and provides a cost effective option for mercury control in metallurgical operations using cyanide solutions. Fine DE was shown to be a green auxiliary to assist in solid-liq- uid separation during mercury removal from pregnant cyanide solu- tions at a 1:1 ratio to the mercury precipitate. Sludge produced with DE and HgPTC during pilot testing was shown to be relatively non toxic, passing TCLP testing for mercury at relatively high mercury concentrations in the sludge. Long-term stability testing of this mate- rial is recommended prior to implementation of the process for mer- cury removal form pregnant cyanide solutions using NaPTC, fine DE and filtration. On-line analysis for pollution prevention is a critical component of the process for mercury removal from pregnant cyanide solutions. Mercury analysis and preservation procedures are problematic at best and real-time control is necessary to achieve sustainable use of reagents and control of metals losses. Mercury removal is best achieved by a number of carefully controlled stages to assure the optimum cost, industrial hygiene, environmental stewardship and sustainable mineral development goals are reached. ACKNOWLEDGMENTS The Author wishes to acknowledge the contributions of Brian Granger of NMS in carrying out the bench scale testing, Glenn Welch of Pocock Industrial for making the process work in the plant and John Huddle of NMS for all of the fire assays necessary to verify the insignificance of the gold losses during mercury precipitation testing. REFERENCES Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and Practice, Oxford University Press: New York, 1998, p.30 Bucknam, C. H., 1997, Cyanide Solution Detoxification Jar Tests, Global Exploitation of Heap Leach able Gold Deposits, TMS, Warrendale, PA, pp.191-204. Bucknam, C. H., 2001, Bench Scale Screening Test Results for Mercury Removal from Pregnant Solutions, MYSRL, Cajamarca, Peru, Newmont Metallurgical Services internal report. Bucknam, C. H., 2002, Final Bench Scale Testing Results for Mercury Removal from Pregnant Leach and Pregnant Eluate SME Annual Meeting Feb. 24-26, Denver, Colorado 3 Copyright 2003 by SME Solutions, MYSRL, Cajamarca, Peru, Newmont Metallurgical inter- nal report. Diaz, M., Cavero, A. and Yataco, D., Water Management at Minera Yanacocha, Presented at the SME Annual Meeting, February, 1999, Orlando, Florida. Matlock, M.M., Howerton, B. S., and Attwood, D. A., Irreversible Precipitation of Mercury and Lead, Journal of Hazardous Materials, B84, pp. 73-82, 2001. Misra, M., Lorengo, J., Nanor, J.B., and Bucknam, C. H., Removal of Mercury Cyanide Species form Solutions using Dimethyl Dithiocarbamates, Minerals & Metallurgical Processing, Vol. 15, No. 4 November 1998, pp. 60-64. Pocock Industrial, Inc., Mercury Precipitation on Yanacocha Carbon Stripping Eluate Using Sodium Polythiocarbonate, Report to Newmont Mining Corporation, September 2002. SME Annual Meeting Feb. 24-26, Denver, Colorado 4 Copyright 2003 by SME SME Annual Meeting Feb. 24-26, Denver, Colorado 5 Copyright 2003 by SME SME Annual Meeting Feb. 24-26, Denver, Colorado 6 Copyright 2003 by SME SME Annual Meeting Feb. 24-26, Denver, Colorado 7 Copyright 2003 by SME