hydrometallurgy

ELSEVIER Hydrometallurgy 47 (1998) 217-229

Cementation kinetics of an industrial solution of Ag(CN) ] with granular spherical zinc in a vibrating reactor
Jorge Ornelas a,*, Miguel Marquez a, Juan Genesca b
" Facultad Ingenieria, Universidad Nacional Autdnoma de Mgxico (UNAM), Ciudad Uniuersitaria, 04510 Mdxico D.F., Mexico b Departamento Ingenieria Metal~rgica, Facultad Quimica, UNAM, Ciudad UniLersitaria. 04510 Mdxico D.F., Mexico

Received 12 August 1996; accepted 14 July 1997

Abstract
The kinetic behavior of the cementation of an industrial solution of Ag(CN) 2 with granulated spherical zinc in a vibrating reactor was investigated. The influence of parameters such as vibratory amplitude and frequency, cyanide and oxygen concentration, pH and temperature were studied in an intermittent state. The reaction rate was analyzed in a continuous run. Some of the significant results are the following: (1) the process takes place in two steps, the first one consisting of an instantaneous cementation in which silver concentration in solution was reduced by 54% to 78% and the second, a slower one, with a reaction order of one; (2) in batch tests, it was possible to perform the cementation at a rate of 2.49 10 4 mg cm -2 s - ~ with an oxygen concentration of 8 mg 1 I (2.5 X 10 -4 M); (3) the critical effect of the cyanide concentration on the reaction kinetics, found with different techniques in other investigations, was not observed in this study; (4) the granulated zinc was not passivated in the 77.5 rain of the continuous test. 1998 Elsevier Science B.V.

1. Introduction

In 1890 the r e c o v e r y o f g o l d a n d silver f r o m a clarified c y a n i d e s o l u t i o n was c a r r i e d o u t b y a c e m e n t a t i o n p r o c e s s w i t h zinc s h a v i n g s . In 1897 Merrill i m p r o v e d the p r o c e s s

* Corresponding author. 0304-386X/98/$19.00 1998 Elsevier Science B.V. All rights reserved. PII S 0 3 0 4 - 3 8 6 X ( 9 7 ) 0 0 0 4 6 - 7

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by using zinc powder, and in 1918 Crowe made another improvement by eliminating dissolved oxygen before adding the powder [1]. The Merrill-Crowe process has undergone few changes to date, although now the operation is carried out under computer control [2]. Since the introduction of the cementation process for gold and silver with zinc, there have been some attempts to change the process. For example, at the beginning of this century McArthur and Hutton used a fixed zinc bed made of sheets through which the solution passed. The process was employed in a small plant [1]. Wiewiorowski and Mollere [3] patented a process in which leaching and cementation of precious metals took place in the same reactor. They used shavings or sheets of several reducing metals such as cadmium, copper, iron, lead, molybdenum, tin and zinc and affirmed that the process could function with different reactors and leaching agents. However, two important disadvantages of this process are: (1) it is efficient only with carbonaceous minerals and (2) increased temperatures are required. Esna Ashari et al. [4,5] investigated a vibrating reactor to diminish the reaction time and consumption of the reducing agent. They studied copper cementation with scrap iron and the purification of a zinc electrolyte with granular zinc. Nissen et al. [6] patented a method for cementation of a metal from solution by the addition of a finely divided cementation medium. The cementation reaction was carried out in a reaction chamber located in an oscillating reactor partially filled with agitated bodies inert with respect to the reaction. The purpose of this was to transmit the oscillations of the reactor into the reaction chamber. Merrill [U.S. pat. No. 684 578] describes the addition of pulverized silica, emery, corundum or other abrasive material to zinc, when the last-named is used as a reducer of gold or silver in cyanide solutions. The function of the pulverized material is to keep the surfaces of the zinc particles mechanically clean, thus avoiding passivating layers on the zinc particles. These pulverized materials have the disadvantage of mixing with the cement material and are difficult to remove by conventional means during the refining process. The aim of the investigation in the vibrating reactor was to study the cementation of silver from an industrial solution of Ag(CN) 2 by using zinc granulates, in order to increase the cementation rate, as the friction removes passivating layers on the zinc granulates thus allowing it to be a more powerful reducing agent. The inert bodies or abrasive particles used by Nissen et al., and Merrill to separate the passive layer on the reducing agent are not needed when zinc granules themselves act as their own autogenous abrasive material. This is possible with granular zinc but not with zinc powder.

2. Experimental
Fig. 1 describes the vibrating reactor. It has a cylindrical shape with a length of 65 cm, a diameter of 11.3 cm and a free volume of 3.75 1. The granulated pure zinc (99.995%) occupied 60% (2.25 1) of the volume and the solution (1.5 1) occupied the remaining part.

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Fig. 1. Components of the vibrating reactor. 1 = motor (1.5 HP), 2 = pulley system, 3 = eccentric wheel, 4 = vibrating reactor, 5 = granulated zinc and solution feed, 6 = sample valve and exit of the Barren solution. In this reactor twelve batch cementations were performed. In each test an industrial cyanide solution (1.5 1) with 141 mg 1 1 (1.31 10 3 M) of silver and 200 mg 1 (4.08 10 -3 M) of free NaCN, and 9 kg of granulated spherical zinc with a diameter of 7 m m were used. All experiments (except 2) were carried out at room temperature (25C). At the beginning of the test, the frequency and the amplitude were fixed. Prior to each test and before adding the zinc granules, the electrolyte was deaerated by using nitrogen. Only in one test was the solution not deaerated. This was done with the purpose of studying the effect of oxygen on the cementation rate of silver. After being washed with dilute sulfuric acid to remove any oxidation product, the granules were charged to the reactor. During the test a 10 ml sample was taken every 15 s for the first 4 min. and then every 30 s for 2 min. and finally every 60 s for the last 2 min. Samples were filtered and analyzed in an atomic absorption spectrophotometer for silver, zinc and copper. The solution pH was also measured at room temperature. One continuous test was carried out to study whether passivation of the zinc granules could take place. For this purpose a peristaltic pump was used to feed the solution into the reactor continuously. When the test finished, the zinc granules with silver were removed from the reactor. During the test a 10 ml sample was taken every 30 s for the first 6.5 min, then every 60 s for 11 min. and finally every 5 rain. for the last 60 rain. The samples were processed as in the case of the batch tests.

3. Discussion
3.1. Batch tests

The results were analyzed with the following relation: log C~o / C( i) = ( - KA / 2.303 V ) t (1)

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proposed by Miller [7] and used by Oo and Tran [8], in their study of gold cementation, where: Cd), Cu) = initial and final concentrations at time t; K = rate constant (cm s- ~); A, V = reaction surface (cm 2) and volume of the reactor (cm3); t = time (s). The variation of the logarithmic ratio of silver concentration in solution at a given time divided by the initial concentration (log Cu)/Cti )) as a function of time follows a linear behavior. However, the lines do not start at the origin. Thus indicating that silver cementation takes place in two stages. The first stage consists of an early instantaneous cementation of silver on the zinc surface. The amount of silver cemented from solution was estimated to be 54% to 78% of the total silver in solution. This value was obtained from the difference between the initial concentration of the solution C(i) and that obtained by extrapolation of the above mentioned lines to t = 0. The second stage consists of a first order reaction that appears to take place when the Ag(CN)~- ion diffuses through a film of Zn(OH) 2, which is quickly formed on the surface of zinc. This appears to occur despite the presence of a relatively large free cyanide concentration of 106 mg 1-~ (4.1 10 3 M) to 160 mg 1-~ (7.7 10 3 M), which could neutralize the hydroxide ions as follows [9]: Zn + 2 O H - = Zn(OH)2 + 2e Zn(OH)2 + 4CN = Z n ( C N ) ] Zn + 4 C N - = Zn(CN)42 + 2OH+ 2e (2)

In the vibrating reactor, 10 tests were performed at an initial pH of 11. In the first 15 s the pH decreases to a value near 10. In the experiment performed at an initial pH of 10, the pH decreases within the first 15 s to 9.5 while in the experiment which began at an initial pH of 8, it increases to 9 (probably due to cyanide hydrolysis). The bulk pH
Table 1 Percentage of instantaneous cemented silver, rate constant for the second stage and overall cementation rate for each intermittent test Test number Test type Percentage of instantaneously cemented silver 75 66 62 68 78 64 76 54 57 63 64 61 Rate constant x 103 (cm/s) 3.01 3.66 4.71 3.52 4.38 2.81 4.75 3.08 3.27 1.11 2.90 3.34 Rate during the initial 75 s X 104

(mg/cm2/s)
2.57 2.59 2.65 2.59 2.55 2.49 2.67 2.48 2.51 2.17 2.51 2.51

1 2 3 4 5 6 7 8 9 10 11 12

standard (900 rpm, 5 mm,O 2 conc. = 1 mg/1, pH = 11, free CN = 106 mg/1, 24C) frequency 1300 rpm frequency 1700 rpm amplitude 3 mm amplitude 7 mm oxygen conc. = 8 m g / l pH = 8 pH = 10 cyanide conc. 132 mg/1 cyanide conc. 160 m g / l temperature = 33C temperature = 43C

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decreases because Zn(OH) 2 is formed and the hydroxide concentration in solution is lowered. Barin et al. [9], in their study of gold cementation, assumed that gold deposition occurs on Zn(OH) 2 when free KCN concentrations smaller than 91 mg 1 l (3.5 10 -3 M) are reached. When a higher KCN concentration is present, the influence of the hydroxide ions disappears for the same reason mentioned above. The rate constant of the second stage for each test is obtained from the corresponding slope of the line and considering Eq. (1). The percentage of instantaneously cemented silver, the rate constant and reaction rate for each test are shown in Table 1.
3.2. First stage o f cementation rate

The amount of instantaneously cemented silver increases as the frequency is decreased (from 1700 to 900 rpm), the amplitude is increased (from 3 to 7 mm), the oxygen concentration is decreased (from 8 to 1 mg ! 1) and the temperature is decreased (from 43 to 24C). A correlation between the percentage of instantaneously cemented silver and the pH or free cyanide concentration could not be found. When the frequency decreases, the turbulence within the reactor diminishes. Miller [7] has shown that hydrodynamics can affect the nature of the superficial deposits obtained during the cementation. He affirms that when the Reynolds numbers (Re) are small, the deposit is rough (dendritic or botryoidal), but when Re are large, deposits tend to be terse. In the vibratory reactor, at low frequencies, the silver deposits are more intensive and could be very rough. If the amplitude increases, then the granules move 'as a whole' with many contacts among them, thus increasing the probability of charge transfer. At an oxygen concentration of 1 mg 1-~ (3.1 10 5 M) more silver is cemented than at 8 mg 1-~ (2.5 10-4). Oxygen facilitates zinc dissolution by cyanide as described by the following reactions [10]: Zn + 1 / 2 0 2 + 4 C N - + H 2 0 = Zn(CN)] Zn + 1 / 2 0 2 + H 2 0 = HZnO 2 + H + + 2OH(3) (4)

The presence of oxygen at the interface could decrease the electrochemically active surface area, which, in other circumstances, would be available for silver cementation. The apparent increase in silver cementation at low temperature is possibly due to a decrease in silver redissolution by cyanide and residual oxygen. Hydroxide, as in the case of oxygen, could also occupy sites on the zinc surface. Insoluble Zn(OH) 2 or soluble zinc-hydroxy complexes such as Zn(OH) 2- and possibly mixed hydroxy-cyanide complexes can form [11]. This may be the reason why at a pH of 8 the amount of silver removed was the highest measured (76%). A larger percentage of silver cements at a relatively small concentration of free cyanide of 106 mg 1-1 (4.1 10 -3 M). This is probably due to the direct transfer of the cyanide ions from Ag(CN)y to zinc, as indicated in the following reactions: 2Ag(CN)2 + Zn = Zn(CN)24 - + 2Ag 2Ag(CN)2 + Zn = Zn(CN)2 + 2 a g + 2CN(5) (6)

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The Zn(CN)42- ion may separate into Zn(CN) 2 and 2 C N - when there is a low free cyanide concentration [1,12]. The intermediate reactants or products such as H20, CN , O H - and H 2 are not necessary. Thus silver could cement on zinc even without free cyanide in solution. Nicol et al. [11] assumed that free cyanide is necessary only when oxidants, different from Ag(CN) 2, such as oxygen and ferricyanide, are present in solution.

3.3. Second stage of cementation rate (first order reaction)

Figs. 2 - 7 show changes in the logarithmic dimensionless concentration ratio as a function of time for different experimental conditions. Silver cements faster when the frequency increases. The cementation rate is independent of oxygen concentration. There is no evident correlation between the cementation rate and pH, amplitude, free cyanide concentration or temperature. The increase of frequency produces more turbulence which could enhance the diffusion of Ag(CN)~] ions to the zinc surface; this counteracts the passivating effect of the Zn(OH) 2 film and increases the cementation rate. In other studies of gold or silver cementation from cyanide solutions, it was found that diffusion of the precious metal complex to the zinc surface (under specific conditions) controls the reaction rate [7-9,11,13,14]. Miller and Oo [7,8,14] mention that the reaction follows first order kinetics. There is hardly any difference in the rate constants obtained in the tests performed with 1 and 8 mg 1-1 o f O 2 (3.01 X 10 -3 and 2.81 10 3 cm s 1, respectively). If zinc dust is utilized as a reducer, it is not possible to prevent its passivation by oxygen [2,15]. When the cementation kinetics of gold or silver by zinc (at relatively low free cyanide concentration and without additives) are studied by using classic techniques [7-9,11,13,14], gaseous nitrogen is always employed to extract oxygen from the solution

Time (s) 0 o -0.2 -o.4 ~-o.6 o

o/)

15

30

45

60

75

-0.8 -1 -1.2 -1.4 -1.6

Fig. 2. Effect of vibratory frequency on cementation rate.

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223

T~ne (s)
0 15 30 45 60 75

-0.2 -0.4 -0.6 r,.) -0.8 ~ -1 -1.2 -1.4 -1.6 -1.8 . Amplitude 3mm Amplitude 5 mm Amplitude 7 mm
!~:..~ :~"

Fig. 3. Effect of vibratory amplitude on cementation rate.

and prevent passivation. The large cementation rate obtained at pH 8 could be due to the formation (from the first stage) of a thinner or inconsistent film of Zn(OH) 2 on the granulated zinc. At initial pH values of 10 and 11 pH decreases because of the Zn(OH) 2 formation. At an initial pH of 8 as the hydroxide concentration increases, less Zn(OH) 2 is produced. After the second stage the pH of each test increases slightly. In addition some silver

Time(s)
0 0 -0.2 -0.4 -0.6
I.i ~

15

30

45

60

75

-0.8 -1 -1.2 -1.4 Conc. of oxygen I mg/l [] Conc. of oxygen 8 mg/l Fig. 4. Effect of oxygen concentration on cementation rate.

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Time (s) 0 0 -0.2 -0.4 -0.6 -0.8 -1 -1.2

- 1.4

15
u

30
u

45
i

60

75

t5
e~

-1.6 -1.8 *pH=8 pH=10 ApH=II

Fig. 5. Effect of pH on cementation rate.

starts to redissolve mainly because of presence of the free cyanide and residual oxygen. The following reaction takes place [16,17]: 4Ag + 02 + 8 C N - + 2H20 = 4OH + 4Ag(CN)2 (7)

Cyanide hydrolysis at pH 8 diminishes the concentration cyanide and may contribute to the increase of the cementation rate.

Time (s) 0 0 -0.2 -0.4 -0.6 -0.8 -1 -1.2 -1.4 Cyanide conc. 106 mg/l Cyanide conc. 132 mg/l Cyanide conc. 160 mg/l Fig. 6. Effect of free cyanide on cementation rate. 15
I

30
I

45
I

60

75

J. Ornelas et al. / Hydrometallurgy 47 (1998) 217-229

225 75

r~ne (s) 0 0 -0.2 -0.4 -0.6

-0.8

15
i

30

45
i

60

-1 -1.2 -1.4 Temperature24C Temperature 33 C Temperature 43 C

Fig. 7. Effect of temperature on cementation rate.

On the basis of the above analysis it may be proposed that the free cyanide retards the cementation rate because: (1) it can produce hydroxide ions that react with zinc, (2) it reacts directly with zinc without necessarily reducing silver, and (3) it causes redissolution of silver if oxygen is present. Zn(OH) 2 can still be formed at an initial pH of 8. Cyanide hydrolysis produces hydroxide ions and decreases the flee cyanide concentration. Therefore, if the free cyanide concentration is zero and at the same time the pH is near 7, a thinner Zn(OH) 2 film will be formed and the zinc extracts cyanide from the silver complex. This results in a maximum cementation rate and a minimum quantity of oxidized zinc. As the granules move 'as a whole', they may contact more solution (there is a large displacement of them). For this reason, at an amplitude of 7 mm the rate is higher. Cementation rate results at different initial free cyanide concentration suggest the existence of an optimum cyanide concentration, in this case 132 mg 1-1 (5.08 10-3 M). It was previously mentioned that Barin et al. [9] found that below a critical cyanide concentration of 91 mg 1-1 (3.5 10 3 M), gold cementation and Zn(OH) 2 formation occur simultaneously. They affirm that free cyanide inhibits the formation of Zn(OH) 2. Nevertheless, it is possible to observe that 75% of the silver cements during the first stage with a free cyanide concentration of 106 mg l- 1. The residual silver (25%) is little, resulting in a smaller rate for the second stage. At 132 and 160 mg 1-I of free initial cyanide the residual silver, after the first stage, was 43 and 37%, respectively. Nicol et al. [1 l] (as well as Barin et al. [9]) found a critical flee cyanide concentration equal to 52 mg 1-l (0.002 M). They proposed that the diffusion of free cyanide to the zinc surface controls the cementation rate. On the basis of the results of silver cementation in the vibrating reactor, it is possible to affirm that, in this case, there is no a critical value of initial free cyanide concentra-

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tion below which the surface is passivated. In addition, if the free cyanide concentration increases, the rate diminishes. This effect may be produced by the direct reaction of cyanide with zinc, thus producing a decrease of reacting surface or by a simultaneous redissolution of silver by cyanide. The following reaction can take place when the cementation rate increases because of the decrease of cyanide: 2Ag(CN)~ + Zn = Zn(CN)2 + 2Ag + 2 C N (8) In each test, small quantities a gray amorphous precipitate are formed. The precipitate formation is intense at the beginning and this contains Zn(CN) 2. If there is more free cyanide, then the reduction of silver takes place according to the following equation: 2Ag(CN)2 + Zn = Z n ( C N ) ] - + 2Ag (9)

Temperature had little effect on the cementation rate, as may be observed in Fig. 7 or from the values of the rate constants of the corresponding tests (Table 1). This is because the process is controlled by diffusion.
3.4. Continuous test

The results of the continuous test are shown in Fig. 8 , where the changes in the concentration of silver are plotted as a function of time. Within the first 15 s of the test, the silver concentration decreases from 111 to 16 mg 1-] . Afterwards, it increases gradually to a maximum of 20 mg 1- ~ at approximately 4.5 min. and finally drops to 6 mg 1- ] at 6 min. This concentration value was observed until the end of the test. As in the batch tests, the pH decreases suddenly when the continuous test starts, in spite of the presence of a high free cyanide concentration (160 mg 1-~). The results obtained in this test validate the hypothesis of the formation of a Zn(OH) z film. The film is separated by the friction of the granules after about six min. of reaction. For this reason, silver cements efficiently after this time all the way to the end of the

120 100 80

Ag initial concentration = 111 mg/1 Amplitude = 5mm CN" initial conc.= 160 mg/l Initial temperature = 21C

60

.~

4o
20
M i i ~ i i i i i i i i i i

4 Time (rain)

Fig. 8. Silver concentration in bulk electrolyte during continuous test.

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Table 2 Comparison of rate constants and the cementation rates of different procedures Technique Rotating cylinder, Au, Barin [9] Rotating cylinder, Ag, Miller [7] Rotating disk, Ag, Miller [7] Rotating disk, Au, Nicol [11] Suspended zinc particles, mesh size 150 200, Au, Miller [14] Vibrating reactor, second cementation stage, Ag Rate constant (cm s - l ) 8.3X 10 3 8.9)< 10 3 1.41X 10-~ 1.8X 10 2 3.4X 10 3 2.32X 10 ~) Cementation rate (tool g c m - 2s - t ) 1.35 10 9

227

test. The presence of oxygen (5 mg l - J) did not stop the cementation, but it is possible that it could have caused a higher consumption of zinc (the zinc concentration starts at 100 mg 1-~ and increases to 160 mg 1-i). The residence time given for the solution throughout the test is t r = V/L, = 1.5 1/0.645 1 min- ~ = 2.32 min (V is the volume of the reactor and ~, the flow rate of the solution). This is possibly larger than necessary. In almost all the batch tests the two stages of cementation took place in less than 75 s. A shorter residence time may be sufficient in the continuous tests, after which the film of Zn(OH) z disappears. Chemical analysis and electron probe microanalysis of the silver content on the granulated zinc showed that most of the cemented silver firmly adheres to the zinc (this adherence was not measured). Despite the presence of this silver layer, silver cementation continues during the rest of the test (77.5 min long). Nicol et al. [11] found that the presence of gold on the zinc surface had little effect on the dissolution of the same even after a cementation time of 90 rain. The barren solution of the continuous test contains a zinc concentration 57% larger than that predicted by stoichiometry to reduce silver and copper from the solution. This excess is probably caused by the high oxygen content of 5 mg 1 i and the free cyanide of 160 mg 1 J. The formation of Zn(OH) z also takes place at the beginning of test, but after six rain, it probably disappears because of both the collisions of the granulated zinc, and the large quantity of free cyanide in the solution. In summary, the reactions of reduction of silver during the first stage of cementation could be: Zn + 2 O H - = Zn(OH)2 + 2e 2Ag(CN)2 + 2e- = 2Ag + 4CN (a) Zn + 2Ag(CN)2 + 2OH = 2Ag + Zn(OH)2 + 4CN(b) 2Ag(CN)2 + Zn = 2Ag + Zn(CN)2 + 2CN and during the second stage of cementation: (a) with a low concentration of free cyanide, 2Ag(CN)2 + Zn = 2Ag + Zn(CN)2 + 2CN-

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(b) with a high concentration of free cyanide, 2Ag(CN)2 + Zn = 2Ag + Zn(CN)J Table 2 describes some values of the rate constant and cementation rates reported in the literature for gold and silver, with the purpose of correlating them with that of the vibrating process.

4. Conclusions Silver cementation with granulated zinc in a vibrating reactor takes place in three stages: (1) instantaneous cementation on elemental zinc, (2) slower silver cementation reaction of first order across a film of Zn(OH) 2, and (3) a silver redissolution stage. It is possible to prevent or counteract the redissolution stage in the batch tests by decreasing the pH or increasing free cyanide concentration. In continuous tests redissolution disappears within a few minutes of experimentation due to the friction that eliminates the passivated film on the granulated zinc. The total silver cementation rate at 75 s (time at which the first order stage is complete in almost all of the intermittent tests) has a value near 2.56 10 4 mg cm 2 s - 1. This value is practically independent of the conditions in these experiments. If the pH or free cyanide concentrations are low during the first two cementation stages, the cementation rates in both stages are large. If the pH and the free cyanide concentrations are simultaneously lowered, the formation of the hydroxide ion is prevented and zinc is complexed by C N - transfer from the Ag(CN)~- ions. With this, a maximum cementation rate and a minimum consumption of cyanide and alkali, and less zinc oxidation could result. The vibrating process is successful with up to 8 mg 1-~ of oxygen in solution, without affecting the rate and recovery in comparison with the concentration of 1 mg 1-1 , which is the maximum permitted in the Merrill-Crowe process. A recovery of as much as 98.6% of silver in a maximum time of 1.5 min. is obtained in the batch tests. In the continuous test recovery is 90% after 12.5 rain. once stable conditions are obtained. Cementation is controlled by diffusion during the second stage. For this reason, the cementation rate increases when the frequency increases, thus counteracting the effect of the passivated film. An increase in temperature does not affect the cementation rate at any stage because, in the first stage, temperature favors silver redissolution and, in the second stage, the process is controlled by diffusion, which is less affected by temperature. The possibility of an industrial application of the vibrating process exists. This also may be considered a technique to effect other kinetic studies of cementation or dissolution. This method presents advantages over others, such as the rotary disc and cylinder; for example, the larger reaction surface which permits a better simulation of the industrial conditions.

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Acknowledgements
The authors wish to acknowledge Dra. G.T. Lapidus of the Universidad Autrnoma Metropolitana (UAM-I) for the revision of this study. They are also indebted to G. Contreras Ordaz and C.E. Mfirquez Herrera who carried out the chemical analyses. They appreciate the financial support from Consejo Nacional de Ciencia y Tecnologfa (CONACYT) and Direcci6n General de Asuntos del Personal Acadrmico, (DGAPA) of the Universidad Nacional Aut6noma de Mrxico.

References
[1] E.H. Schulz, in: G. Gili (Ed.), Enciclopedia de Qulmica Industrial, Barcelona, vol. 7(IV), part 11, 1932, pp. 595-600. [2] R.M. Van Zyl, Computer controlled Merrill-Crowe processing, Eng. Miner. J. 184 (4) (1983) 58-59. [3] K.T. Wiewiorowski, D.P. Mollere, U.S. Pat., 4384889, 1983. [4] M. Esna-Ashari, E. Kausel, R. Nissen, P. Paschen, Schwingmtihle als hochleistungsreaktor ffir kupferzementation, Erzmetall 30 (6) (1977) 262-266. [5] M. Esna-Ashari, R. Nissen, Einsatz des schwingreaktor in der zinklaugenreinigung, Erzmetall 3t (4) (1978) 170-175. [6] R. Nissen, R. Graf, U.S. Pat. 4309215, 1982. [7] J.D. Miller, in: H.Y. Sohn, M.E. Wadsworth (Eds.), Cin~tica de los Procesos de la Metalurgia Extractiva. Editorial Trillas, M~xico, 1986, pp. 274-285. [8] M.T. Oo, T. Tran, The effect of lead on the cementation of gold by zinc, Hydrometallurgy 26 (1991) 61-74. [9] I. Barin, H. Barth, A. Yaman, Electrochemical investigations of the kinetics of Au cementation by Zn from cyanide solutions, Erzmetall 33 (7-8) (1980) 399-403. [10] M.G. Potter, B.R. Bhappu, The Chemistry of Gold and Silver Recovery from Natural Resources, in: M.C. Kuhn (Ed.), Procces and Fundamental Considerations of Selected Hydrometallurgical Systems, AIME. Tucson, Arizona, 1981, pp. 27-35. [11] M.J. Nicol, E. Schalch, P. Balestra, H. Hegedus, A Modern Study of the Kinetics and Mechanism of the Cementation of Gold, J. South Afr. Inst. Min. Met., February, 1979, pp. 191-198. [12] V.N. Alexeiev, Semi-microanfilisis Quimico Cualitativo. editorial MIR, URSS, 1975, p. 570. [13] J.R. Parga, J.D. Miller, in: S.S. Aguayo, O.L. AlmazS.n (Eds.), Avances en Metalurgia Extractiva no Ferrosa, Universidad de Sonora, Hermosillo, M~xico, 1988, pp. 132-152. [14] J.D. Miller, R.Y. Wan, J.R. Parga, Characterization and electrochemical analysis of gold cementation from alkaline cyanide solution by suspended zinc particles, Hydrometallurgy 24 (1990) 373-392. [15] G.M. Potter, Merrill-Crowe Precipitation of Precious Metals by Zinc Dust, Proceedings of Arizona Conference, AIME, Tucson, Arizona, May, 1980, pp. 1-7. [16] J. Libaude, El Tratamiento de los Minerales de Oro. Mundo Cientffico (La Recherche), vol. 14(148). editorial Fontalba, Barcelona, 1984, pp. 556-664. [17] F. Habashi, Kinetics and Mechanism of Gold and Silver Dissolution in Cyanide Solution. State of Montana Bureau of Mines and Geology, Bulletin 59, Butte, Montana, 1967, pp. 1-42.