Kinetics of Alkaline Decomposition and Cyaniding of Argentian Rubidium Jarosite in NaOH Medium

ENZ, ELEAZAR SALINAS RODRIGUEZ, EDUARDO CERECEDO SA O CARDONA, MARIUS RAMIREZ, FRANCISCO PATIN REZ LABRA and MIGUEL PE The alkaline decomposition of Argentian rubidium jarosite in NaOH media is characterized by an induction period and a progressive conversion period in which the sulfate and rubidium ions pass to the solution, leaving an amorphous iron hydroxide residue. The process is chemically controlled and the order of reaction with respect to hydroxide concentration in the range of 1.75 and 20.4 mol OH m3 is 0.94, while activation energy in the range of temperatures of 298 K to 328 K (25 C to 55 C) is 91.3 kJ mol1. Cyaniding of Argentian rubidium jarosite in NaOH media presents a reaction order of 0 with respect to NaCN concentration (in the range of 5 to 41 mol m3) and an order of reaction of 0.62 with respect to hydroxide concentration, in the range of 1.1 and 30 mol [OH] m3. In this case, the cyaniding process can be described, as in other jarosites, as the following two-step process: (1) a step (slow) of alkaline decomposition that controls the overall process followed by (2) a fast step of silver complexation. The activation energy during cyaniding in the range of temperatures of 298 K to 333 K (25 C to 60 C) is 43.5 kJ mol1, which is characteristic of a process controlled by chemical reaction. These results are quite similar to that observed for several synthetic jarosites and that precipitated in a xico, San Luis Potosi). zinc hydrometallurgical plant (Industrial Minera Me DOI: 10.1007/s11663-012-9697-4 The Minerals, Metals & Materials Society and ASM International 2012

I.

INTRODUCTION

THE family of jarosite type compounds is represented by the following formula: M Fe3 (SO4)2 (OH)6, where M can include some of the following cations: H3O+, Na+ K+, Rb+, Ag+, NH4+, Tl+, Pb2+, or Hg2+. Jarosite-type compounds are of interest to mineralogists and to metallurgists devoted to extractive metallurgy. Although nine jarosites have been synthesized, only six of these have been recognized in nature as mineral species, while the remaining three are rubidium jarosite, thallium jarosite, and mercury jarosite, which only have been obtained by way of synthesis.[1] Chemical names are used to label synthetic products, and mineral names are reserved to jarosites found in nature. For the case presented in this study, Argentian rubidium jarosite[2,3] has no analogous equivalent that is found in nature, and it is, therefore, called by its chemical name. Jarosite mineralsprincipally natrojarosite, potassium jarosite, argentian jarosite and plumbojarosite have a long and impressive history as a source of silver. Historically, humans had the rst contact with these types of minerals at around 1200 B.C. in the Spanish southeast, where it was rst found in the Jaroso Ravine
ELEAZAR SALINAS RODRIGUEZ, EDUARDO CERECEDO ENZ, MARIUS RAMIREZ, FRANCISCO PATIN O CARDONA, SA REZ LABRA, Professors, are with the Universidad and MIGUEL PE rea Acade noma del Estado de Hidalgo, A mica de Ciencias de la Auto xico. Contact e-mail: salinasr@ Tierra y Materiales, Hidalgo 42184, Me uaeh.edu.mx Manuscript submitted January 10, 2012. Article published online July 19, 2012.
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in the Almagrera Sierra. This is where its name came from.[4,5] Minerals from Spanish Gossan were formed by a natural leaching in situ of pyritic ores, leading a gradual substitution of original iron sulfurs by iron oxides with (among other elements) some contents of silver, gold, lead, and arsenic.[6] In Mexico, it is known that jarosites occurred by meteorization processes, with principal deposit sites of jarosites noted in Hidalgo,[7] Zacatecas, Durango, and Chihuahua. On the other hand, it is known that the application of conventional cyaniding of these minerals for silver extraction presents some problems, as this process yields erratic and sometimes problematic recoveries of silver. Rubidium jarosite was rst synthesized in 1975, in Dutrizac and Kaiman[2]; at this time, rubidium was also rst characterized. Moreover, Dutrizac and Kaiman obtained it as a jarositic product of precipitation from an aqueous solution using the technique of slow addition. Dutrizac and Kaiman concluded that hydonium ion (H3O+) is substituted in part for the alkaline metal, and therefore, the resulting jarosite is hexagonal (R3m). This analysis was done by thermal gravimetric analysis. Some researchers have discussed their work pertaining to jarosites synthesized in Mexico. For instance, Patin o et al.,[8] who have worked with both synthetic jarosites and with jarosites generated in the zinc hydrometallurgy industry, found in all cases that decomposition and cyaniding in alkaline media is a two-step process: (1) a step of alkaline decomposition that controls the overall process followed by (2) a fast step of silver complexation.
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Due to its nature and due to the fact that the jarositic compounds are capable of precipitating iron from leaching solutions, some important eorts were carried out to incorporate the jarositic process as a media in the middle of the 1970s. The purpose of this process was to eliminate iron (III) in the hydrometallurgical circuits, principally within the zinc industry. In addition to its ability to eliminate iron (III) and another impurities, this process permits developers to obtain and adequately control sulfates and alkali in the system, resulting in relatively low losses of divalent metals such as Zn, Ni, and Co. Furthermore, this system also allows for an easy and simplied process by which to lter and laud residues, creating great eciencies in the electrolytic zinc recovery process.[9,10] According the above points, this article is part of a wide alkaline study of reactivity of several synthetic jarosites carried out to determine the best cyaniding conditions of these compounds in order to develop an adequate process of silver recovery of jarosites precipitated at the electrolytic zinc plants.

Ag in cyaniding by atomic absorption spectrometry. Variations in the mass balance due to the sampling and reagent addition were corrected. The eect of particle size was carried out with particle families of 56 to 40, 40 to 36, 36 to 25, and 25 to 20 lm. Solids obtained at dierent conversion values were characterized by XRD, SEM, and EDS to observe their evolution during the processes of decomposition and cyaniding.

III.

RESULTS AND DISCUSSION

A. Materials Characterization The characterization performed by XRD, SEM, and EDS conrmed that the jarosite obtained consists of an Argentian rubidium jarosite, with some contents of H3O+ and Ag+ noted in the alkaline site. This produced a solid solution of a combination of rubidium jarosite, argentojarosite, and hydroniumjarosite. The chemical composition obtained for this compound is shown in Table I. For simplicity, the formula of this jarosites-type compound is normalized to SO4 = 2, Fe = 3, and OH = 6. The alkaline site is normalized to 1 and occupied by Rb+, Ag+, and H3O+. Hydronium is calculated by the dierence of these compounds. The resulting formula for the jarosite is Rb0:82 H3 O0:17 Ag0:000039 Fe3 SO4 2 OH6 The morphology observed is consistent with that found in several synthetic and industrial compounds,[1015] consisting of rhombohedral crystals (1 to 2 lm), which are interconnected with each other in a compact structure (Figure 1). Particle size distribution (Table II) was found between 20 and 80 lm in accordance with the RosinRammler model[16] F3 d 1 expd=42:63:5 1

II.

MATERIALS AND EXPERIMENTAL PROCEDURE

A. Materials For the kinetics study, samples of synthetic rubidium jarosite were prepared using the methods employed by Dutrizac and Kaiman[3] as well as Patin o et al.[1,8] These methods consisted of the heating of a solution containing 0.3 M of Fe2(SO4), 0.3 M of Rb2SO4, and 61 mg/L Ag2SO4 in an volume of 1 L at 367.5 K (94.5 C) during a 24-hour period, adjusting pH to 1.2 while adding H2SO4. At the end of each synthesis experience, the solution was ltered and washed to eliminate residual iron and silver. The resulting solids were then dried and weight in order to be characterized. All obtained samples were characterized by chemical analysis, X-ray diraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDS), and size distribution analysis. B. Experimental Procedure The experimental procedure was quite similar to that used in several previous investigations.[1015] For the alkaline decomposition and cyaniding study in NaOH media, 0.3 g jarosite (30.5 5.5 lm) at an initial volume of 0.5 L at 500 minutes1 and 303 K (30 C) was used, except for experiments in which the eect of particle size, temperature, or stirring rate was determined. The pH was kept constant by addition of small amounts of saturated NaOH solution. The OH concentration was calculated according the pH solution, and the ionization constant of water was retained at the working temperature. The progress status of extraction reaction was followed by taking samples of the solution throughout the experiment and testing for S in the alkaline decomposition study by way of emission spectrometry using inductively coupled plasma (ICP), or through testing for
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where F3(d) is the distribution function. Figure 2 shows particle families of limited size (25 to 36 lm) used for the kinetics studies. B. Decomposition of Rubidium Jarosite in NaOH Medium 1. Nature of the reaction One experiment was carried out according to the following experimental conditions: 0.3 g jarosite (30.5

Table I. Element Rb Fe SO4 Ag H3O + OH

Chemical Analysis of the Jarosite of Rubidium Silver Bearing Pct Weight 13.5 29.1 37.2 0.00557 20.2

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5.5 lm) at an initial volume of 0.5 L [NaOH] = 1.0 9 102 M (pH = 11.81), at 500 minutes1 and 303 K (30 C). This experiment was done to determine the elimination of sulfates by way of solution testing for S by ICP. The results obtained were treated according to the shrinking core model for chemical control.[1618] 1 1 x1=3 kexp t where kexp VM kq cn A r0 3 2

In this case, x is the fraction reacted, VM is the molar volume of the solid, cA is the concentration of reactant, kq is the kinetic coecient, r0 is the initial radius of particle, kexp is the chemical constant, and n is the order of reaction. Figure 3 is an S type plot showing a short induction period followed by a progressive conversion, and at the end, a stabilization zone during alkaline decomposition of rubidium jarosites is shown. On the other hand, Figure 4 shows that these results in the experimental conditions employed seem to t well (r2 = 0.997) with the model of spherical particles with a decreasing core[1015] and chemical control (Eq. [2]) showing a kexp = 3.6 9 102 (seconds1).

The process shows an induction period with a value of h = 80 seconds according to the chemical control model. This induction period has already been included in the decomposition process of other synthetic jarosites.[8,1015] During this period, there were no morphological and chemical changes in the solid surface (SEM-EDS). The analysis of XRD (Figure 5) of the evolution of decomposition in NaOH media reveals that increasing reaction time aected the resulting residue loss in the medias crystalline structure, and it then arrived to an amorphous form at the end of decomposition (20 minutes). This was observed in all of the jarosites studied in previous works.[1015] Figure 6 illustrates a SEM-EDS image of a partially decomposed particle of rubidium jarosite: The original jarosite (core) is compact and without porosity. Figure 7(a) shows an EDS spectrum corresponding to the original rubidium jarosite, in which the Ka lines of S and Rb, and the Ka and Kb lines of Fe appear with high intensity. In Figure 7(b), the EDS spectrum corresponding to the decomposition products (ash layer) can be observed, in which the lines of S and Rb have almost disappeared, while the lines for Fe remain. According to the observed ndings, during the process of alkaline decomposition, the sulfate and rubidium ions passed together through the solution, and so an amorphous residue of iron and silver hydroxides remained.

Fig. 1Image of individual crystals of jarosite of rubidium silver bearing (SEM, secondary electrons).

Fig. 2General image of a family of sizes of particle (25 to 36 lm) of the jarosite of rubidium silver bearing (SEM, secondary electrons).

Table II. Partial Weight (pct) 8.2 25.3 31.3 34.5 0.2 0.5

Analysis of the Distribution of Sizes of Particle (Wet Sieve) Rosin-Rammler

d (lm) 22.5 30.5 38.0 56.5 69.0 82.5

Accumulative Weight (pct) 8.2 33.5 64.8 99.3 99.5 100.0

F3(d) 0.082 0.335 0.648 0.993 0.005 1

ln d 3.11 3.42 3.64 4.20 4.23 4.41

Ln[ln(1 F3(d)] 2.45 0.90 0.04 1.60 1.67

Regression (r) 1.00 0.99 0.98 0.98

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Fig. 3Graph of the curve type S showing the period of induction and that of progressive conversion.

Fig. 5X-ray diraction spectrums of decomposed jarosite of rubidium silver bearing to several times of decomposition.

Fig. 4Alkaline decomposition of the jarosite of rubidium silver bearing. Model of shrinking core and chemical control.

Thus, the stoichiometry of the process across all the conditions studied can be expressed as follows: Rb0:82 H3 O0:17 Ag0:000039 Fe3 SO4 2 OH6s
2 3OH aq ! 2SO4aq 0:82Rb 0:000039AgOH 3FeOH3 s:amorphous

Fig. 6Image of a particle of jarosite of rubidium silver bearing partially decomposed. (a) Core without reacting and (b) cap of ashes. (SEM, secondary electrons).

0:25H2 Ol

2. Kinetics study of decomposition of rubidium jarosite in NaOH medium The study of alkaline decomposition of Argentian rubidium jarosite in NaOH media was executed to determine the inuence of (OH) concentration, temperature, particle size, and stirring rate on the overall reaction rate. The eect of (OH) concentration on the alkaline decomposition rate is shown in Figure 8. The order of reaction was 0.94 and fell in the range between 1.75 and 20.4 mol OH m3. In the same gure, it is noted that below the concentration of 1.75 mol OH
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m3 there was a change of order of reaction, reaching a value of 0, which means that at this particular point there was a change in reaction mechanisms. The eect of temperature is shown in Figure 9. The activation energy obtained was 91.3 kJ mol1, which fell in the range of 298 K to 328 K (25 C to 55 C). The plot represents the experimental rate constants as measured against the inverse of diameter of particles. The overall trend is linear and passes through the point origin: Moreover, the eect of stirring rate over the constant factor of experimental rate gave an order of n = 0, which is indicative that diusion in boundary layers has no eect and that the reaction is carried out by way of chemical control. All the above facts and the activation energy obtained are consistent with the spherical particle model, which necessitates decreasing core and chemical control in the experimental conditions employed.
METALLURGICAL AND MATERIALS TRANSACTIONS B

According to the results found, the kinetic expression in NaOH media is h i r0 =VM 1 1 X1=3 1:96 1012 exp91290=RT OH 0:94 t 5

boundary layer has no eect, and the reaction is, therefore, carried out by chemical control during cyaniding.

where VM = 355.7 9 106 m3 mol1, R = 8.31 J mol1 K1, r0 in m, T is in degrees Kelvin, [OH] is in mol m3, and t is in seconds. C. Kinetics Study of Cyaniding of Rubidium Jarosite in NaOH Medium The study of cyaniding of Argentian rubidium jarosite in NaOH media was carried out to determine of the inuence of [CN], [OH], and temperature over experimental rate constant of cyaniding. Also, the eects of particle size and stirring rate were studied to conrm the degree of control of the cyaniding process. In all experiences, reaction products are amorphous. The eect of cyanide concentration is presented in Figure 10. The reaction order is 0 with respect to cyanide, and the range of concentration fell between 5 and 41 mol m3. The eect of [OH] concentration was studied using a cyanide concentration of 20.4 mol m3. Figure 11 shows the results found. As in the previous study of the eect of cyanide concentration, values of experimental constants exhibited a similar behavior; however, here the order of reaction obtained was n = 0.62 and fell in the range between 1.1 and 30 mol [OH] m3. This result is indicative of a chemical control of the process. The eect of temperature is shown in Figure 12. This eect was also studied with a cyanide concentration of 20.4 mol m3. The activation energy obtained was 43.5 kJ mol1 and was in the range of 298 K to 333 K (25 C to 60 C). As was the case in the study of decomposition in the NaOH media, the plot of the experimental rate constants against the inverse of particle diameter is linear and passes through the point of origin. Finally, the eect of stirring rate over the experimental rate constants gave again an order of ration of n = 0, which is indicative that diusion in

Fig. 8Alkaline decomposition: eect of (OH)s concentration.

Fig. 9Alkaline decomposition: eect of the temperature.

Fig. 7(a) EDS spectrum of the original jarosite (core without reacting). (b) EDS spectrum of the products of decomposition (cap of ashes).
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Fig. 10Cyaniding: eect of (CN)s concentration. Fig. 12Cyaniding: eect of the temperature.

Fig. 11Cyaniding: eect of (OH)s concentration. Fig. 13Plot of the rate constants (Kcalc) calculated vs the rate constants (Kexp) determined experimentally.

According to all these results, chemical control seems to t well in the cyaniding process of Argentian rubidium jarosite in NaOH for the experimental conditions studied. In addition, these results can give the following kinetic expression for cyaniding of Argentian rubidium jarosite in NaOH media: h i r0 =VM 1 1 X1=3 18 10 exp
3 43450=RT

described are in satisfactory agreement with the experimental results.

IV.

CONCLUSIONS

OH

0:62

where VM = 355.7 9 106 m3 mol1, R = 8.31 J mol1 K1, r0 is in m, T is in degrees Kelvin, [OH] in mol m3, and t is in seconds. These results allow us to conclude that the cyaniding process can be described as a two-step process: a rst slow step of decomposition that controls the overall process followed by a second fast step with complexation of the decomposition products (Ag) by means of cyanide. Figure 13 is a plot of the ln (kcalc) (calculated) vs ln (kexp) (experimental) from the equations corresponding to all the experimental points obtained. According to these results, we can conclude that the equations
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The synthesis of Argentian rubidium jarosite results in a compound with the following formula: [Rb0.82 (H3O)0.17 Ag0.000039] Fe3 (SO4)2 (OH)6, as conrmed by chemical analysis. This compound consists of semispheroid aggregates of rhombohedral crystals between 1 and 2 lm, and these are interconnected in a compact structure. The size distribution is between the sizes of 20 and 80 lm, and it ts well with the Rosin-Rammler model, as exemplied by m = 3.5 and = 42.6. The alkaline decomposition and the cyaniding processes present an induction period, during which any changes were detected in the jarosite surface. The progressive conversion period is characterized by the liberation of sulfate and rubidium ions to the solution. It is
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important to note that during cyaniding, silver also passes through the solution where it is complexed by cyanide. The residues of alkaline decomposition and cyaniding are amorphous in nature and are formed by iron hydroxide. For the alkaline decomposition of jarosite in NaOH media, the process is of 0.94 order (OH concentration), the activation energy is 91.3 kJ mol1, and the plot of experimental rate constants against the inverse of particle diameter is linear and passes through the point of origin. This behavior is consistent with the spherical particle model, with decreasing core and chemical control evidenced in the experimental conditions studied. During cyaniding in the NaOH media, the reaction order is 0 (CN concentration). For OH concentration, the order of reaction was found to be 0.62, while the activation energy was 43.5 kJ mol1, and the plot of experimental rate constants against the inverse of particle diameter is linear and passes through the point of origin. According these results, the cyaniding process is also controlled by chemical reaction and can be described as a two-step process that follows this sequential order: a rst, slow, decomposition step that controls the overall process, followed by second a fast step of complexation of the Ag products by cyanide. In both studies, the eect of stirring rate over experimental rate constants was examined. In both cases, these processes yielded an order of reaction of n = 0, which is indicative that diusion in the boundary layer has no eect, indicating that reaction is clearly carried out by way of chemical control.

VM CA kq r0 n h R T Ea m

molar volume of the solid (m3 mol1) concentration of reactant (mol m3) kinetic coecient initial radius of particle (m) order of reaction induction period (s) gas constant, 8.314 J mol1 K1 absolute temperature (K) activation energy (kJ mol1) pendant for linear regression in Rosin-Ramler model constant of Rosin-Rammler model

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1. I.A. Reyes, F. Patin o, I. Rivera, M.U. Flores, M. Reyes, and ndez: J. Braz. Chem. Soc., 2011, vol. 22 (12), pp. 226067. J. Herna 2. J.E. Dutrizac and S. Kaiman: Hydrometallurgy, 1975, vol. 1, pp. 5159. 3. J.E. Dutrizac and S. Kaiman: Can. Mineral., 1976, vol. 14, pp. 15158. 4. J. Dutrizac, J.L. Jambor, and J.B. OReilly: CIM Bull., 1993, vol. 76, pp. 7881. 5. C. Nun ez y A. Roca: Rev. Met. Madrid, 1984, vol. 20 (3), pp. 17584. 6. C. Nu n ez and A. Roca: Can. Metall. Q., 1984, vol. 23, pp. 39397. 7. A.R. Geyne, C. Fries, Jr., K. Segerstrom, R.F. Black, and I.F. Wilson: Geologa y yacimientos minerales del Distrito Minero de Pachuca- Real del Monte, Estado de Hidalgo, Mexico., 1st ed., xico, 1963, Consejo de Recursos Naturales no Renovables, Me pp. 14647, 16569. vila, I. Rivera, J. M. 8. F. Patin o. E. Salinas. J.J. Canales, P. A Gonzalez, and M. Reyes: European Metallurgy Conference 2007 Proceedings, vol. 3, GDMB, Du sseldorf Germany, 2007, pp. 1209 20. 9. J.E. Dutrizac and J.L. Jambor: Appl. Mineral., 1984, pp. 50730. 10. A. Roca, F. Patin o, J. Vin als, and C. Nun ez: Hydrometallurgy, 1993, vol. 33, pp. 34158. 11. F. Patin o, J. Vin als, A. Roca, and C. Nun ez: Hydrometallurgy, 1994, vol. 34, pp. 27991. 12. F. Patin o, E. Salinas, M. Cruells, and A. Roca: Hydrometallurgy, 1998, vol. 49, pp. 32326. 13. M. Cruells, A. Roca, F. Patin o, E. Salinas, and I. Rivera: Hydrometallurgy, 2000, vol. 55, pp. 15363. 14. E. Salinas, A. Roca, M. Cruells, F. Patin o, and D.A. Cordoba: Hydrometallurgy, 2001, vol. 60, pp. 23746. 15. F. Patin o, M. Cruells, A. Roca, E. Salinas, and M. Perez: Hydrometallurgy, 2003, vol. 70, pp. 15361. 16. H.Y. Sohn and M.E. Wadsworth: Cinetica De Los Procesos De La Metalurgia Extractiva, Ed. Trillas, Mexico 1986, pp. 14148. 17. H.H. Haung: Unit Processes in Extractive Metallurgy. Montana College of Mineral Science and Technology, Modul 2, National Science Foundation, Washington, DC, 1989. 18. A. Ballester, L.F. Verdeja, and J. Sancho: Metalurgia Extractiva, Fundamentos, Editorial S ntesis, Madrid, Spain, 2000, vol. I, pp. 18289.

ACKNOWLEDGMENTS The authors want to thank the CONACyT of the xico Government for their nancial support. Me noma del Estado Thanks also go to Universidad Auto de Hidalgo, especially to the Materials and Metallurgy Research Center.

NOMENCLATURE F3(d) d kexp t X distribution function for particle sizes average particle size in lm experimental rate constant (s1) time (s) fraction of reacted solid

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