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Kinetic and equilibrium effects in

gold ore cyanidation
M.I. Brittan
Head consulting metallurgist, Gold Fields, International Development Projects, Englewood, Colorado

Cyanide leaching of two West African gold ores was studied in multiple laboratories to provide process-engineering
data for plant design purposes. Unusually slow leach extraction kinetics were observed using routine cyanide
leach test procedures with pregnant solution monitoring. Carbon-in-leach testing, however, showed normal rapid
kinetic behavior, with the same ultimate gold extractions being reached in much shorter elapsed times. Kinetic
curves based on washed solids assays also exhibited more typical leaching characteristics. The results bore all
the hallmarks of some equilibrium inhibition of the leaching. It was surmised that ore gangue components were
responsible for weakly adsorbing gold-cyanide complex reaction product, thereby holding up soluble gold in
the solid phase. The term “preg-borrowing” was coined to describe the reversible phenomenon and distinguish
it from irreversible preg-robbing. The two ores investigated may represent an extreme form of a more general
effect that in most instances might pass unnoticed. The effect can lead to misinterpretation of kinetic leach curve
data and underestimation of calculated ore head grades.
Key words: Gold Processing, Cyanide leaching, Carbon-in-leach, Kinetics, Equilibrium

Introduction commissioned in late 2004. The mill is now undergoing
A project was launched in 2002 to determine the best expansion to 12 Mt/a (13 million stpy).
processing option to expand production at Gold Fields’ The subject of this paper was prompted by some curious
Tarkwa Mine in Ghana. The open pit operation was started metallurgical behavior that was observed in the course of
in 1998 with 100% heap leach production. By 2002, the the test work.
question at issue was whether to expand the heap leach or
to install a mill to process the harder ore of lower porosity Gold ore leaching kinetics
that would be encountered at depth in the pits. Metallurgical extraction reactions involving low-grade
Test work was initiated at McClelland Laboratories comminuted ores typically exhibit highly nonlinear kinet-
in Sparks, Nevada. In due course, further extensive ics. The reaction is normally very rapid to begin with, but the
work was conducted on Tarkwa ore and other samples rate tails off markedly as high extractions are approached.
from West Africa at the Tarkwa Mine Laboratory; at the This behavior is largely caused by progressive changes in
SGS-Lakefield Laboratory (SGS) in Johannesburg, South the rate-controlling step (Brittan, 1975). The initial reaction
Africa; at Kappes, Cassiday & Associates (KCA) in Reno, may be governed by chemical reactions at the surfaces
Nevada; and at the Advanced Mineral Technology Labo- of exposed gold particles, or diffusion through boundary
ratory (AMTEL) in London, Ontario, Canada. The test layers if pulp agitation is not adequately vigorous.
work involved extensive programs geared to providing Chemical equilibrium effects do not normally restrict
flowsheets and plant design parameters for engineering gold leaching. The Elsner equation governing the gold
purposes. Results reported here represent a focused se- leaching reaction (Marsden and House, 2006) is essen-
lection from a large body of data to illustrate specific ore tially irreversible, so that even though gold builds up in
leaching characteristics. The Tarkwa project culminated the solution as the reaction proceeds, it would not inhibit
in a 4.2 Mt/a (4.6 million stpy) mill that was eventually the leaching of additional gold.

Paper number MMP-08-011. Original manuscript submitted March 2008. Revised manuscript accepted for publication May
2008. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept.
prior to Feb. 28, 2009. Copyright 2008, Society for Mining, Metallurgy, and Exploration, Inc.

MINERALS & METALLURGICAL PROCESSING 117 Vol. 25, No. 3 • August 2008

mmp_117_122.indd 117 7/14/08 3:29:15 PM

It was observed that a sample that required 72 typically washed before drying and splitting out an aliquot hours to reach 97% extraction in a kinetic leach test (i. reaction of some sort appeared to be in play. It was (Tarkwa ore. the cyanide leach time. It was similarly through pores in ore particles (Brittan. column extraction rates drop and the rate of extraction per pass may be low enough to compromise accurate measurement of the incremental gold in solution at a daily frequency. 2. Once cyanide starvation had been eliminated as a possible cause. and the gold-cyanide complex product will be In these tests. the solution leaving the bottom of the column may be returned directly to the top of the column.. as noted above. The standard milled-ore kinetic leach test conducted by of the reverse reaction and thus speed up the overall extraction many laboratories involves taking small intermediate solution kinetics.indd 118 7/14/08 3:29:15 PM . test. 25 No. the long tail on the the weekly circulation periods. These data are shown in Fig. Tarkwa Laboratory). needed to compensate for evaporation and sample volumes so as to maintain the original solution volume and the specified Further observations at SGS-Lakefield leaching conditions. gold particles. The gold in solution is implicitly assumed A second test program was initiated at SGS-Lakefield in 2002 to represent all the gold that has leached from the ore. and pH and cyanide concentration (sometime dis. stirred vessel) to follow the course of the gold extraction. the activated carbon in the CIL test would perhaps agglomerated) ore. and/or of gold-cyanide complex. thereby keeping the concentration bottom of the column may typically be passed through a bed to a low level. For example. For plant design purposes. Any gold that may be washed from build-up of gold in solution and intermediate solution sampling) the solids over and above pregnant solution entrained values required only 24 hours in a bottle roll carbon-in-leach (CIL) would not be accounted for. to provide design data for the Tarkwa mill option. Accordingly. in certain cases. Could this increase in concentration in the solution solution. It was observed that the low- Figure 1 — Dilution effect on leach extraction kinetics porosity ore appeared to be leaching particularly slowly. a means to supplement the column testing. In the case of a column leach test carried out on crushed (and In this case. The observations made in the course of studying the two If in fact some equilibrium was being established between West African ores suggest that effects other than classical gold in solution and gold in solids. with (or aliquots) for fire assay. the Tarkwa Laboratory was requested to samples from the leach reactor (usually a rolling bottle or a run kinetic bottle roll tests on a sample at three dilutions: 1:1. gold would be building up in solution as the test diffusing away from the surfaces via the interstices to the bulk progressed. with appropriate adjustments to maintain the cyanide strength and the pH. Under these circumstances. pregnant leach solution leaving the adsorb the gold in solution. it was apparent that the slowdown was commensurate with the build-up of gold in solution during Unless caused by large gold particles.e. 3 118 MINERALS & METALLURGICAL PROCESSING mmp_117_122. Bottle roll At the end of the test. gold concentration in the intermediate solution samples is Figure 1 shows that the rate of gold extraction does in fact measured. the leaching of gold from ores is August 2008 • Vol. also noted that when the columns were switched from daily solution monitoring and circulation through carbon to weekly circulation without carbon. along with reagents as may be larly at higher extractions. another reversible equilibrium desired extraction. extraction curve is usually a reflection of the slow diffusion of Bottle roll cyanidation tests on crushed ore were used as cyanide and oxygen reagents. and therefore the tank capacity. The solution grade would As mentioned above. If the hypothesis were correct. the pregnant solution is sampled for and stirred leach testing of milled Tarkwa ore samples were gold and reagent concentrations. this scenario appeared to promote of activated carbon to remove the gold in solution before being much higher rates of extraction. 1. and the filtered solids are carried out. there was a marked drop in the gold extraction rate. Initial test work observations Initial column cyanide leach testing of crushed and agglomer- ated Tarkwa ore was carried out at McClelland Laboratories for heap leach design purposes. The reagents observed that these tests also required excessively long leach will be diffusing to the surfaces of residual partially occluded times. The 2:1 and 3:1 (liquid:solids). particu- added back to the leach vessel. 1975). Once again. returned to the top of the column. a bottle roll test conducted with a higher liquid:solids ratio would yield lower soluble gold concentra- Laboratory leaching procedures tions in solution. Allowing the gold in solution to build up over several days or a week before monitoring reduces the labor requirement. it might be expected that chemical and mass transport phenomena may. it is generally this long be responsible for inhibition of further gold extraction from tail on the leach curve that dictates the cyanidation residence the solid phase? Because. bypassing the activated carbon. while accumulating sufficient soluble gold to assist analytical accuracy. With extended leach times. running tests at different dilutions would influence the extraction contribute to the form of the gold leach curve. curve. the law of A few words on test work procedures are appropriate at this mass action would dictate that this should reduce the kinetics point. increase with dilution such that longer times are required to solved oxygen as well) usually checked. normally be monitored on a daily basis while the extraction rate is reasonably rapid. Makeup solution is reach the same gold extraction with less dilute pulps. required to achieve the reaction itself is non-reversible. The results are given in Fig.

therefore. in the test. the adsorption expect to have experienced this manifestation of gold leaching experienced in this case was reversible. typical kinetic leach test procedures con- ducted by metallurgical laboratories allow for solids residue washing ahead of drying and sampling of leach residues for fire assay. This gold rinses out easily Figure 3 — Solution vs. it was speculated at the time that perhaps the gold was actually leaching at the particle surface but that the gold-cyanide complex product was inhibited from finding its way to the bulk solution by the gold already in solution. has been extracted. 3 • August 2008 mmp_117_122. Given the unusual behavior experienced with the Tarkwa ores. already been solubilized and additional gold that could leach The fact that the gold is easily washed from the residue solids out of test residue solids during the washing stage. such as diffusion of reagents through boundary layers around ore particles and within pores and interstices in the particles to the surface of the gold. Similarly. on to gangue. Certainly. washed solids leaching kinetics and. Figure 3 shows that the solid phase is holding up a signifi- cant portion of soluble gold. where the gold is strongly adsorbed. behavior with many ores. filtration and washing of residues introduces a dose of fresh The ability of activated carbon to accelerate the apparent oxygen that. As noted above. with Tarkwa ores having certain gangue constituents that the gold-cyanide complex in solution reduces the driving that might promote the adsorption. could lead kinetics is an indication that chemical control or depletion of to further leaching if oxygen starvation had been a problem cyanide and oxygen reagents were not issues in these tests. No. over all the test work programs. solids. bottle roll tests on clay fractions of ore samples showed periods when the gold concentration in solution actually dropped as time passed. This gold would not appear in the solution samples that are normally taken in the course of a kinetic cyanidation test. should be considered as part of the gold that (Tarkwa ore. the back-calculated head grade of the sample will be lowered accordingly. 2. the mass of gold in every product and sample would be accounted for. If this were the case. not just a simple matter of free gold particles in contact with cyanide and dissolved oxygen. CIL extraction kinetics (Tarkwa ore. removing the gold from solution (as in CIL) creates kinetic testing of gold ores in the industry over the last century a desorption driving force to keep the gold from adsorbing and more. there was a large MINERALS & METALLURGICAL PROCESSING 119 Vol. The results generally seemed more commensurate with “Preg-borrowing” weak. Other steps are involved. one would robbing. it is preferentially captured by activated charcoal in a CIL test. been noted during a heap drilling campaign at Tarkwa — it was found that substantial pockets of rinseable water-soluble gold existed in apparently spent areas of the heaps. Vacuum indicates that the adsorption bonds are indeed weak. As opposed to preg- the bulk solution. operating at greater dilution (higher liquid:solids ratio) will reduce the tendency to adsorb because 1 It is necessary here to distinguish between gold that has the solution concentration of the gold-cyanide complex is lower. with residual cyanide in the filter cake. however. The term “preg-borrowing” force for diffusion of complex out of the ore particles into was coined to describe the phenomenon. Figure 3 is an example of the results. particularly given the widespread Thus. To explain the test work observations. If this were the case. The gold in residue washings is not normally measured. Similarly. 1975). reversible adsorption of the complex onto gangue par- One possible hypothesis to explain the observations could be ticles. It should also be noted that if the soluble gold in the final residue is not accounted for. along with similar diffusion of reac- tion products away from the surface to the bulk solution. Thus. 25. There should also be residual solubilized gold remaining in the Figure 2 — Leach vs.indd 119 7/14/08 3:29:15 PM . an amount greater than would be accounted for by simple entrainment. Some indication of such gold hold-up in ore had already SGS Laboratory).1 As was seen. It is generally these solid-phase diffusion steps associated with partially occluded gold particles that determine the ultimate leaching time required for commercial CIL or CIP plant opera- tion (Brittan. a revised laboratory test work procedure was specified in which solids residues were to be washed twice with specified aliquots of water and the gold in the washings accounted for as part of a total material balance for the test. as suggested by Fig. SGS Laboratory). it could well be that the gold concentration in the solution was not a good measure of the potential extraction kinetics.

large nature of the adsorption bond means that any sample preparation gold particles were not the sole contributing factor. are recognized adsorbers of gold. as illus- trated in Fig. In any event. Here it can be seen that the ore still appears to be leaching at a significant rate after 48 hours. but in Figure 5 — Whole ore leaching kinetics (West African ore. for example. 7. However. of course. 7 it can be seen that CIL leaching of whole ore is leach tests on the sample and found behavior similar to that a lot faster than cyanidation in the absence of activated carbon. species could be responsible for the weak adsorption of the be lower for gravity tails with reduced leach feed grades gold. An attempt was made to determine which of the gangue The leach solution gold concentrations would. Metallurgical testing for this project was initially carried out by Kappes. Oxide ores in this deposit typically contained major quartz with some muscovite and minor go- ethite and kaolinite. Table 1 — Mineralogical composition of Tarkwa sample.2 Total: 100 Figure 4 — Solution vs. it should be noted that any time. 4. 6. few tests with limited sample is a tall order because the weak As further tests would show for the West African ore.1 K-feldspar 0 Na/Ca Plagioclase 0 Calcite 0 Dolomite 0 Pyrite 0 Kaolinite 0. however. The ores from this deposit displayed the same charac- teristics as had been observed with the Tarkwa material. CIL leach kinetics (Tarkwa ore. Gold Fields began an investigation of another ore deposit in West Africa. The difference in rates. as shown in Fig. much faster kinetics and maintain appropriate cyanide and oxygen concentrations was in evidence. appears to have leached fully after only 24 hours. A single CIL test at a 24-hour residence time once again duplicated the extraction achieved by washing of the solids. Cassiday & Associates and involved both column leach tests on crushed ore and bottle roll tests on milled ore samples. too dramatic for this to be the primary cause. as shown in Fig. 25 No. 5. The mineralogical composition of responsible for the faster kinetics of the other West African this sample is given in Table 1. 3T) 9. In Fig. 4. along with ankerite and muscovite and minor tourmaline and sulfides. The gold in gravity tails during leaching.indd 120 7/14/08 3:29:15 PM . % Quartz 86. ores with large free gold particles often exhibit slow quest to uncover the responsible gangue component in just a leaching behavior. washed solids vs.9 Muscovite (2M1. appeared Surface microanalysis of the clay fraction showed no evi. In keeping with the behav- sample of the Tarkwa ore tested by SGS was sent to AMTEL ior of the Tarkwa ores. Second ore from West Africa In 2005.8 Chlorite 0 Paragonite 3. reported by McClelland Laboratories and SGS. The same apparent slow leaching kinetics was observed when whole ore was subjected to kinetic leach tests. this case the results were exacerbated by a very strong nugget KCA Laboratory). AMTEL Laboratory). it could be speculated that this was in Canada for examination. Additional technique involving washing or drying of the cyanided solids samples for this prospect were tested at McClelland Labora- militates against the adsorbed species remaining intact. Primary ores contained major quartz and plagioclase. A than they would for whole ore. effect — the ore samples contained visible gold particles. tories. 3 120 MINERALS & METALLURGICAL PROCESSING mmp_117_122. Relevant results are shown in Fig. AMTEL carried out their own independent From Fig. At the same dence for preg-borrowing. August 2008 • Vol. When the same tests were repeated on gravity tails after a body of test work conducted (not reported here) to establish gravity concentrate had been removed. Clays. Mineral Concentration. ore gravity tails. the gold extraction based solely on solution samples is both lower and slower than that determined from washed solids.

For comparison. Consequently. sample of the West African ore in which caustic soda was used 2006) and have been observed in the analysis and optimiza.indd 121 7/14/08 3:29:15 PM . CIL case. Figure 7 also shows different pH levels were conducted in the original 2002 Mc- that with a gravity concentrate removed. Brittan and lime as the base. conventional cyanide leach kinetic tests at two appears to be at play in this case as well. The readily. CIL vs. Figure 8 shows somewhat faster kinetics at lower pH. Taschereau. it would not be possible to speed if pulp agitation is not adequately vigorous. Figure 6 — Gravity tails leaching kinetics (West African ore. Figure 8 — Effect of pH on leaching kinetics (Tarkwa ore. the same ultimate extraction being attained after 24 hours. 25. up the kinetics merely by having the gold in solution adsorb To determine whether pH may have an influence on this on to activated carbon. which might tend to inhibit mass transfer the leaching of large particles. and the gravity-with-tails-cyanidation case. are es. McClelland Laboratories). a test was car- pH could have an influence on leaching kinetics. two pH levels were tested with tion of gold plant operations (see. 2005). If the cyanidation extraction rate were being determined only by viscosity of the pulp. With this in mind. for example. A recent paper by Davidson and Sole (2007) has also ques- tioned whether the calcium ion associated with the lime used pH investigation for pH control may not in fact have adverse consequences for Early on in these test work programs. it was anticipated that gold cyanidation chemistry. because pH ried out at McClelland Laboratories in 2007 on a gravity tails effects are known in gold ore cyanidation (Marsden and House. One effect of increasing pH is to raise the The results again accord with a tendency for faster initial MINERALS & METALLURGICAL PROCESSING 121 Vol. the gravity tails leach Clelland Laboratory investigation on a Tarkwa sample. Whole-ore cyanidation. some preg-borrowing phenomenon. 9. No. on the other hand. but with sentially the same. gravity tails leaching (West Figure 9 — Effect of pH and alkaline reagent on initial leach- African ore. 8. requires 72 hours to reach the same extraction. The ultimate extraction in 36 hours for the whole ore results are given in Fig. McClelland Laboratories). McClelland Laboratories). for pH control. ing kinetics (West African ore. KCA Laboratory). The results are shown in Fig. Figure 7 — Whole ore vs. 3 • August 2008 mmp_117_122.

” because of its revers- for lime or the calcium ion.. Interpretation of the kinetic results in Figs. 2. 41-47. Society for Mining. “Improving cash flow at Gold Fields’ depletion in solution concentration. cedures used in the testing of gold ores and the interpretation agitation and reagent concentrations would have to be carried of test work results: out in combination with viscosity measurement to address these issues. therefore. components that promote a much higher degree of gold complex Davidson. pp. 107.. 2006.J. and House. (SME). of the characteristics of a reversible adsorption phenomenon. For most ores that one encounters. such as with leach tests left to run overnight. Inc. August 2008 • Vol. 2006) do not influence the results.. House.J. 2nd cannot be determined unequivocally from the limited data Edition. Cases have. inter alia.indd 122 7/14/08 3:29:15 PM . The exact mechanism of the “preg-borrowing” phenomenon Marsden. temperature. 3 122 MINERALS & METALLURGICAL PROCESSING mmp_117_122. In addition. Ghana with the aid of diagnostic process analysis. any testing of pH has to be rigorously have exhibited this behavior. lime can have a ible character. temperature. ores may well represent extreme cases of what could be a fairly • If a significant proportion of solubilized gold is held general phenomenon. M. leading to a small International Journal of Mineral Processing. however. thereby affecting rates of Nevertheless. Vol... • Kinetic testing with results based solely on solution samples and final washed residue assays may yield mis- Discussion and conclusions leading results. “preg-borrowing. J. 8 and 9 is not The “preg-borrowing” label is. “The major role played by calcium in gold adsorption than most run-of-the-mill ores one encounters.I. Metallurgy.. C. however. This could well accompany a drop in pulp using the total gold mass-balance concept.” more adsorption as the temperature drops. This can have gangue adsorption in the solids is relatively small so that the repercussions not only for metallurgical processing.” Journal of the South African Institute of Mining and Metal- lurgy. with caustic used available in the studies reported here. but preg-borrowing effect would not be noticeable. 2005. Vol. appropriate. and Sole.I. Brittan. should not be problematic for plant operation. been reported in kinetic cyanidation testing where • Any wet chemical leach assay method employed for grade the gold concentration in solution reaches a peak and then estimation purposes should be thoroughly investigated declines with time. and Exploration. and Taschereau. 2007. any equilibrium between gold in solution and gold References adsorbed on solids would be pushed slightly in the direction of Brittan. perhaps. C. As noted above. extraction kinetics at lower pH and. unequivocal. M. In this instance. for the plants designed by Gold Fields where ores mass transfer.O. “Variable activation energy model for leaching kinetics. This could affect. it is up in the solids and is not accounted for.” Mining The two West African ores studied may well have gangue Engineering. December 2005. preg-borrowing has constituted conducted to ensure that extraneous effects such as cyanide one reason for selecting CIL as the process of choice rather depletion (at lower pH) and competing reactions (Marsden and than leach-CIP. plant circuits.I.. 25 No. pp. negative influence on pulp viscosity. in establishing a definite chemical role In practical terms. the design The kinetic effects observed in the case of the two West African residence time specified for plant operation. but certainly has many for pH adjustment in place of lime. 463-468. M.A. this will lead conceivable that the quantity of solubilized gold held up by to an underestimation of ore head grade. R. This is beyond the scope of the present exercise. The Chemistry of Gold Extraction. also for ore reserve estimation and project valuation. Extensive testing under The phenomenon could well have implications for the pro- well-controlled conditions of sample homogeneity. 1975. pp. Damang Mill. 321-331.