Hydrometallurgy 95 (2009) 247253

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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t

Kinetics of platinum extraction from spent reforming catalysts in aqua-regia solutions

Morteza Baghalha a,, Homa Khosravian Gh. a, Hamid Reza Mortaheb b
a b

Department of Chemical and Petroleum Engineering, Sharif University of Technology, Azadi St., Tehran, 11365-9465, Iran Chemistry and Chemical Engineering Research Center of Iran, Tehran, Iran

A R T I C L E

I N F O

A B S T R A C T
Platinum content of two commercial spent reforming catalysts were extracted in aqua-regia solutions under atmospheric pressure and at temperatures up to 100 C. Three factors, including presence of coke, catalyst particle size, and impeller agitation speed were rst tested to study the relative importance of mass-transfer resistances during Pt extraction reaction. Catalyst particle sizes b 100 m and agitation speeds N 700 rpm eliminated the internal and external mass-transfer resistances, respectively. The effect of other factors, including HNO3-to-HCl volume ratio, liquid-to-solid mass ratio, and the reaction temperature on the extraction rate of platinum were then examined. Pt extraction rate was signicantly increased by increasing liquid-to-solid mass ratio and the reaction temperature. Kinetic modeling using power-law rate equation for Pt extraction revealed that increasing liquid-to-solid mass ratio increases the acid concentration, as a major reactant. This quantitatively accounted for the increased Pt extraction rate. The effect of temperature on Pt extraction kinetics was studied using the Arrhenius equation. The activation energy for the platinum surface dissolution reaction was calculated as 72.1 kJ/mol. This large value indicates that Pt extraction in aqua-regia solution is controlled by surface chemical reaction. The reaction order was 1.5 for Pt concentration in solid and 1.3 for the hydrogen ion molarity in solution. 2008 Elsevier B.V. All rights reserved.

Article history: Received 1 March 2008 Received in revised form 7 June 2008 Accepted 8 June 2008 Available online 17 June 2008 Keywords: Kinetics Leaching Extraction Aqua-regia solution Reforming catalyst Platinum Reaction rate Power-law

1. Introduction Pt/alumina catalyst is widely used in rening and petrochemical industries for the catalytic reforming process. In this process, the low octane naphtha is upgraded to higher octane aromatic hydrocarbons. Usually rhenium is also added to these catalysts to improve its activity, selectivity and stability (Kluksdahl, 1971; McCoy and Munk, 1971). Due to the high price of platinum and rhenium, several researches have worked on the recovery of these precious metals from spent catalysts. Platinum recovery from spent reforming and isomerization catalysts has been studied by selective dissolution of base metals in 50% H2SO4 and treating the insoluble residue with aqua regia from which platinum was recovered (Jeliyaskova et al., 1982). Chen and Huang (2006) examined PGM extraction from spent auto catalysts by cyanidation. However, at room temperature and pressure, the reaction between sodium cyanide and platinum group metals proceeds slowly due to poor kinetics. As a result, the cyanide leaching of PGM must be performed at elevated temperatures and pressures. In addition to the high cost of operation at high temperatures and pressures, this process employs cyanide which is highly toxic. In fact, many major precious metals producers and research groups are actively develop-

Corresponding author. Tel.: +98 21 6616 4577; fax: +98 21 6616 4391. E-mail address: baghalha@sharif.edu (M. Baghalha). 0304-386X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2008.06.003

ing alternate processes to replace the cyanide process. In our group, for instance, hypochlorite/NaCl solution as a strong alternate lixiviant system has already been tested for gold extraction from ores (Baghalha, 2007). Matjie et al. (2005) considered different lixiviants such as sodium hydroxide, nitric acid, hydrochloric acid, sulphuric acid and aqua regia to extract platinum from FischerTropsch catalysts. They pointed out that platinum dissolves completely in an aqua regia medium but is not soluble enough in single mineral acid. de s Pinheiro et al. (2004) considered the solubility of Pt in HF, NaF, HCl, HNO3, H2O2 and binary mixture of them. They concluded that, except HNO3/HCl mixture (aqua-regia), platinum solubility in such mixtures is low. In two recent works, platinum was recovered from spent catalysts using aqua regia solution. In one work, the effects of some limited factors on maximum Pt leaching values was investigated (Barakat and Mahmoud, 2004). Another group examined microwave assisted leaching followed by chemical precipitation to recover platinum (Jafarifar et al., 2005). However, neither groups studied the extraction kinetics of platinum in aqua-regia solutions nor they offered a reaction kinetic model to quantitatively describe the effects of various parameters. In this work, we experimentally studied the effects of various parameters on Pt extraction kinetics and maximum platinum recovery. Furthermore, aluminum extraction from the catalyst matrix was also measured. Finally, a variety of reaction kinetic models were considered for the obtained Pt extraction data.

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2. Experimental Two types of spent naphtha reforming catalysts were supplied by a petroleum renery. The chemical compositions of the catalysts were obtained by X-ray uorescence (XRF) analysis. The platinum content was also veried by wet chemical analysis through long-term hot aqua-regia total dissolution and atomic absorption spectroscopy. Phase identication of the catalysts was performed by powder X-ray diffraction (XRD) analysis. The two types of the catalysts were separately ground, dried and screened into two different sizes, in order to examine the possible effect of particle size on the observed extraction kinetics. To investigate the effect of decoking on Pt leachability, some of the ne-ground used catalyst sample was decoked by heating in a furnace at 600 C for 4 h. The coke contents of the as received and decoked catalysts were measured by Leco analysis. Aqua regia was freshly prepared by mixing concentrated hydrochloric acid (37%) and concentrated nitric acid (65%) at a volume ratio of 3 HCl:1 HNO3. The batch reactor used in this work was a 1 liter glass container equipped with a thermometer, a mechanical turbine-type stirrer and a reux condenser. The condenser was used to recover and send back to the reactor as much vapor as possible. Any escaped gases (such as Cl2, NOCl, HCl, and NOx) at the exit of the condenser were scrubbed into a cold water container. The reactor was maintained at a desirable constant temperature by a controllable hot-plate heater. The reactor temperature was controlled with a precision of 2 C. For each run, 600 cm3 of aqua regia was rst charged into the reactor. Then, the system was quickly heated to the desired temperature under continuous stirring. When the temperature reached the pre-set value and remained stable, a certain amount of catalysts powder was added to the reactor. Next, the mixture of the reactants was intensively stirred at 700 rpm under atmospheric pressure. At appropriate time intervals during a run, approximately 15 mL of the sample was taken out and quickly centrifuged. The supernatant solution samples were then taken and analyzed by atomic absorption spectrometer (Perkin Elmer 1100 B) to determine its platinum and aluminum contents. A few verifying test solutions with aqua-regia matrix and known contents of Pt and Al were made and measured for those metals by Atomic absorption. The accuracy of Pt and Al measurements were found to be within 2% and 3%, respectively. The obtained solution samples were also analyzed for H+ ion concentration through neutralization titration with 0.1 N NaOH standard solutions. However, no masking agents such as F were used for Al3+ ions during NaOH titration. As a result, the consumed NaOH solution to reach a solution pH = 6 was due to both H+ ion neutralization and Al3+ ion precipitation to Al(OH)3. It will be shown later that the H+ ion concentration can be calculated by knowing the aluminum concentration in solution. 3. Results and discussion The main chemical compositions of the two different types of spent catalysts, as determined by XRF and wet chemical analysis for Pt,

Fig. 1. XRD pattern of the reforming catalysts C. The peaks marked with A represent gammaalumina phase.

are shown in Table 1. As expected, these results show that the main constituent of these two catalysts is alumina. The crystalline structure of alumina in the catalysts was identied as gammaalumina through powder XRD analysis (Fig. 1). The experimental conditions and the code name of the performed leaching tests are reported in Table 2. As seen from this table, the two catalysts are distinguished by their original shape, i.e., Spherical and Cylindrical. It is believed (Massucci et. al., 1999) that HNO3 and HCl in aquaregia undergo through the Reactions [I] and [II] to some small extent: HNO3 3HClNOCl Cl2 2H2 O NOCl H2 OHNO2 HCl I II

Dissolution of Pt from the catalyst is a redox reaction that undergoes according to Reaction [III]:
2 8H 8Cl 2NO 3 PtPtCl6 4H2 O 2NOCl

III

As Reaction [IV] shows, aluminum extraction from the alumina catalyst support is an acid-attack reaction. Al2 O3 6H 2Al3 3H2 O IV

Due to high acidity in solution, the produced Al3+ in Reaction [IV] does not hydrolyze into aluminum hydroxo species (Tagirov and Schott, 2001). The hydrolysis reactions may go forward only when the H+ concentration is low. Depending on such other factors as the aging time, mono-nuclear hydrolytic Al species (Tagirov and Schott, 2001) or poly-nuclear hydrolytic Al species (Bi et al., 2004) may then form at near neutral pHs.

Table 2 The experimental conditions of platinum leaching tests Catalyst type Spherical Test code name Decoking Temp. Liquid/solid HNO3/HCl Size m mL/mL C g/g 100 100 100 100 80 80 80 50 100 80 80 10 10 10 10 10 10 10 10 10 5 15 1/3 1/3 1/6 1/9 1/3 1/3 1/3 1/3 1/3 1/3 1/3 b 50 b 50 b 50 b 50 50 b size b 100 b 50 b 50 b 50 b 50 b 50 b 50

Table 1 Chemical composition of two S and C catalysts determined by XRF Component Al2O3 SiO2 SO3 Cl TiO2 Fe2O3 Re Pt LOI Spherical catalysts (S), wt.% 90.9 0.29 0.21 0.70 0.03 0.13 0.39 0.23 7.00 Cylindrical catalysts (C), wt.% 93.2 0.27 0.17 0.80 0.17 0.17 0.30 0.29 4.30

S1 Yes S2 No S3 No S4 No Cylindrical C1 No C2 No C3 (800 rpm) No C4 No C5 No C6 No C7 No

M. Baghalha et al. / Hydrometallurgy 95 (2009) 247253 Table 3 The results of NaOH titration (=[H+] + 3[Al3+]), Al3+ measurement and calculated [H+] molarities Catalyst type Spherical Test code name [H+] + 3[Al3+], Measured Calculated kobs [H+], molar [Al3+], molar molar 2.25 2.25 1.86 2.03 0.62 0.7 0.53 0.155 1.185 1.067 0.50 0.55 0.87 2.47 1.91 5.39 5.11 5.51 7.21 2.68 3.76 5.94 0.0698 0.0520 0.0048 0.0043 0.0148 0.0154 0.0160 0.0023 0.0229 0.0103 0.0187 ln(k) R2, goodness of t 0.95 0.93 0.96 0.89 0.96 0.96 0.95 0.95 0.99 0.93 0.99 6.30 8.84 4.92 6.30 6.30

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S1 7.30 S2 7.62 S3 8.05 S4 8.00 Cylindrical C1 7.25 C2 7.20 7.10 C3 (800 rpm) C4 7.68 C5 6.24 C6 6.96 C7 7.44

The tted values for kobs in Eq. (6) are also reported.

As mentioned in the Experimental section, the obtained solution samples were analyzed for H+ ion concentration through neutralization titration with 0.1 N NaOH standard solutions. However, no masking agents such as F were used for Al3+ ions during NaOH titration. Without masking agents, it is known that at solution pHs near 6 and at temperatures lower than 100 C, Al3+ ions precipitates into gibbsite (Tagirov and Schott, 2001) according to Reaction [V]. Al3 3OH AlOH3s V

As a result, the consumed NaOH solution during titration to reach a solution pH = 6 was due to both H+ ion neutralization and Al3+ precipitation to Al(OH)3; i.e., Consumed [OH] = [H+] + 3[Al3+]. The measured [H+] + 3[Al3+] molarities in the neutralization titration of the nal solution of all tests are reported in Table 3. The Al3+ concentrations of the nal solutions, as measured by Atomic Absorption, are also reported in Table 3. [H+] molarities were then calculated by the difference of the column 3 and 3 times of the column 4. The values of [H+] molarities, as reported in Table 3, have the same order of magnitude accuracy as the measured aluminum in solution, i.e., ~ 3%. The effects of six parameters, including state of coking, HNO3-toHCl volume ratio, agitation speed, particle size of the ground catalysts, liquid-to-solid mass ratio, and temperature on Pt extraction kinetics were investigated in the tests that are reported in Tables 2 and 3. 3.1. The effect of state of coking The effect of decoking on Pt extraction kinetics was examined in tests S1 and S2 (Table 2). The coke contents of the as received and decoked catalyst samples, as measured by Leco analysis, were 1.4% and 0.3%, respectively. The results of the S1 and S2 tests are compared in Fig. 2. The smooth curves in this gure are based on power-law kinetic modeling, as it will be discussed later. As seen in this gure, the extraction of as received and decoked samples are rather the same during the rst 15 minutes of the leaching tests. From then, Pt extraction of as received sample is visibly lower than the decoked sample. The nal extraction of platinum in decoked sample was about 3% higher than that in the other sample. Since, de-coking of the spent catalysts requires large amounts of energy for heating the catalyst to 600 C, the 3% higher Pt recovery may not justify the added cost of de-coking. As a result, the catalysts were tested as received (i.e., decoking was not performed) for the next leaching tests. 3.2. The effect of HNO3-to-HCl volume ratio Although the xed 1/3 volume ratio of HNO3-to-HCl is often applied in commercial labs for total dissolution of metals and minerals, it has been reported that the dissolution power of aqua-

Fig. 2. The effects of de-coking (S1 and S2) and HNO3/HCl ratio (S2, S3, and S4) on A: Pt extraction; B: Al extraction. The smooth curves for Pt %leached are based on powerlaw kinetics.

regia, in fact, depends on three factors; the metal being dissolved, aging of the prepared solution, and the ratio of HNO3 to HCl (Bonilla, 1932). The effect of HNO3-to-HCl volume ratio on Pt extraction kinetics was investigated in three tests (S2, S3, and S4) on the spherical catalyst. As reported in Table 2, all these tests were performed at 100 C and at a constant liquid/solid ratio of 10. The results of these tests are also shown in Fig. 2A for Pt and Fig. 2B for Al. For platinum extraction, the HNO3-to-HCl volume ratio of 1/3 produced the best results in terms of reactions rates and maximum recovery. The ORP (oxidation reduction potential) of the solution samples produced at the end of these tests were measured by a platinum electrode vs. the saturated Ag/AgCl reference electrode, as reported in Table 4. The data in this table shows that the solution sample containing HNO3-to-HCl volume ratio of 1/3 has the highest oxidation potential. The highest oxidation potential of the solution

Table 4 Obtained results of ORP electrode vs. the saturated Ag/AgCl reference electrode for different values of HNO3/HCl ratio Test code name S2 S3 S4 HNO3/HCl mL/Ml 1/3 1/6 1/9 ORP (mV) 951 939 922

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better performance of this test in Fig. 2A. As a result, in considering the effects of other parameters on Pt extraction kinetics, the HNO3-to-HCl volume ratio was xed at 1/3. For the aluminum extraction results in Fig. 2B, there is no signicant differences between these tests. As Reaction [IV] shows, aluminum extraction from the alumina catalyst support is an acidattack reaction. Hence, the Al extraction kinetics is only affected by the acid level which is rather the same (Table 3) in the three tests. 3.3. The effect of agitation speed To achieve faster kinetics and smaller reactor sizes, solid leaching processes require severe agitation to suspend solid particles and to preferentially eliminate the external mass-transfer resistances. As reported in Table 2, the conditions of tests C2 and C3 were exactly the same except that the agitation speed of test C3 was 800 rpm (for the test C2 it was the normal speed of 700 rpm). The obtained experimental Pt extraction results from these tests were virtually the same, Fig. 3. Hence, it was concluded that 700 rpm agitation was enough to eliminate the external particle mass-transfer resistances. 3.4. The effect of particle size of the ground catalysts The factor that impacts the internal particle mass-transfer resistances is the catalyst particle size. Two different catalysts sizes:

Fig. 3. The effects of particle size and agitation speed on Pt extraction. The smooth curves for Pt %leached are based on powerlaw kinetics.

corresponding to the HNO3-to-HCl ratio of 1/3 may, in fact, corresponds to the stoichiometry of Reaction [I] for maximum concentration of Cl2 (a very active oxidant). According to Reaction [III], higher redox potential of solution in test S2, in fact, explains the

Fig. 4. The effect of Liquid/Solid ratio on A: Pt extraction; B: Al extraction. The smooth curves for Pt %leached are based on powerlaw kinetics.

Fig. 5. The effect of reaction temperature on A: Pt extraction; B: Al extraction. The smooth curves for Pt %leached are based on powerlaw kinetics.

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smaller than 50 m (test C2) and between 50 and 100 m (test C1) were leached in otherwise exactly the same conditions. No measurable differences were observed between the Pt extraction kinetics of these two tests, as also shown in Fig. 3. Hence, it was concluded that if the catalyst particles are ground below 100 m sizes, no internal particle mass-transfer resistance would remain. This conclusion was consistent with the ndings of Barakat and Mahmoud (2004), who reported a critical size of 106 m below which the kinetics was not affected by the catalyst particle size. 3.5. The effect of liquid-to-solid mass ratio The liquid to solid mass ratio was the other major factor that was investigated. Three levels of 5, 10, and 15 liquid/solid ratios were examined in tests C6, C2, and C7, respectively. The temperature of all these three tests was constant at 80 C (see Table 2). The obtained extraction results for these experiments are presented in Fig. 4A for Pt and in Fig. 4B for Al. In both cases of Pt and Al, as the liquid/solid ratio increases, the extraction kinetics becomes faster. The data in Table 3 for tests C6, C2, and C7 reveals that as the liquid/solid ratio increases, [H+] molarity also increases. As Reactions [III] and [IV] for the extractions of Pt and Al suggest, H+ ion is a major reactant for those reactions. As a result, it is expected that higher acidity due to higher liquid/solid ratio produces faster kinetics. This is clearly observed in both cases of Pt and Al in Fig. 4A and B, respectively. 3.6. The effect of temperature The Pt and Al extraction kinetics were nally studied at three temperature levels of 50, 80, and 100 C in tests C4, C2, and C5, respectively. The other experimental conditions, such as liquid/solid ratio and HNO3/HCl ratio were the same for these three tests (see Table 2). The results of these tests for the extraction of Pt and Al are presented in Fig. 5A and B, respectively. These gures clearly show that increasing temperature greatly enhances the extraction kinetics and maximum recovery of both Pt and Al. This large temperature impact must be due to relatively high activation energies for the extraction reactions. 4. Kinetics modeling To predict the major N, Cl, and Pt species in concentrated HNO3/HCl solution (with the volume ratio of 1/3), HSC chemistry software (Outokumpu Research, Finland) was implemented. The Eh-pH diagram

Fig. 7. EhpH diagram of NClPt system at 100 C, drawn using HSC chemistry software (Outokompou Research, Finland): Chlorine species.

of this system at 100 C were produced and drawn in Figs. 68. The distribution of nitrogen species in Fig. 6 shows that at low pHs and in the presence of NO 3 in solution, the redox potential of solution must be close to 1.0 V (vs. the Standard Hydrogen Electrode). For the Eh value of 1.0 V and pHs close to zero, Fig. 7 shows that the major chlorine species is Cl and HCl. For the same conditions, Fig. 8 shows that the major platinum species are H2PtCl6 and PtCl2 6 . No NOCl was identied by the software as the major nitrogen/chlorine species. In heterogeneous soliduid reactions, at least, the following three sequential steps occur: (a) diffusion of reactants through the uid lm surrounding the solid, (b) diffusion of reactants through the solid matrix, and (c) chemical reaction on the internal areas of the solid. As explained in the previous section, the level of slurry agitation and the solid particle sizes were selected in such a way that diffusions of reactants in the uid lm and inside the particles were not the limiting steps (as conrmed by the leaching tests). Hence, it is assumed that the observed Pt extraction kinetics is solely governed by the surface chemical reactions. Two classical uidsolid reaction models, namely, homogeneous diffusion model (HDM) and shrinking core model (SCM) (Zhou et al., 2005; Lee et al., 2005; Levenspiel, 1999) and a newer adsorption kinetics model, namely, Elovich equation (Juang and Chen, 1997) did not produce meaningful results.

Fig. 6. EhpH diagram of NClPt system at 100 C, drawn using HSC chemistry software (Outokompou Research, Finland): Nitrogen species.

Fig. 8. EhpH diagram of NClPt system at 100 C, drawn using HSC chemistry software (Outokompou Research, Finland): Platinum species.

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assumed that Wsolids remains constant and was canceled from both sides of Eq. (2). Further, replacing Eq. (1) into Eq. (2) results in
1 n2 dwPt =dt kwn Pt mH

Since, platinum extraction data are conveniently reported in terms of percent extracted, Eq. (3) should be modied accordingly, using the relationship wPt w0 Pt 1X w0 Pt 4

is the platinum weight fraction in the ground catalyst Where feed and X is the fraction of platinum extracted. Thus, Eq. (3) reduces to: n11 n2 mH 1X n1 d1X =dt k w0 Pt
Fig. 9. Linear behavior of ln(kobs) vs. ln(mH+) for tests C2, C6, and C7 at constant temperature of 80 C.

The empirical powerlaw equation (Baghalha and Papangelakis, 1998a) has been successfully implemented to model the nickel extraction kinetics from solid particles in aqueous acid solutions. Assuming that the powerlaw rate equation can also predict the platinum extraction data at constant oxidizing power, i.e., constant HNO3/HCl ratio, the results from the C tests in Tables 2 and 3 were considered for the kinetics modeling. The powerlaw rate Eq. (1) describes the Pt extraction rate in terms of the concentrations of the reactants of Reaction [III].
1 n2 rPt kwn Pt mH

The total concentration of H+ was measured in each test during the 120 min of the leaching time. For all the tests, it was observed that H+ concentration in solution drops sharply during the rst 5 min of the test. Thereafter, it remained relatively constant until the end of each test. Therefore, by assuming mH+ to be approximately constant after the rst 5 minute of each test, Eq. (5) can be integrated from 5 min to any time (t). h i 1Xt 1n1 1X5 1n1 kobs t 5 Where, n11 n2 mH kobs kn1 1 w0 Pt 7 6

Where rPt is the observed rate of platinum extraction per unit mass of solids in the reactor, wPt is the weight fraction of platinum in solids, mH+ is the molarity of the hydrogen ion in solution, and n1 and n2 are the reaction orders. The parameter k is the overall reaction rate constant which is temperature dependent. This kind of rate equation, which involves solid concentrations of reactants, has been widely used for non-catalytic solidgas reactions (Froment and Bischoff, 1979; Doraiswamy and Kulkarni, 1987). In Reaction [III] for Pt extraction, the concentrations of the other two reactants, namely Cl and NO 3 are constant in all tests. As a result, their contribution in the powerlaw rate Eq. (1) is, in fact, included in the parameter k, i.e., the overall reaction rate constant. For highly non ideal systems such as concentrated electrolyte solutions, rate equations must be in terms of activities rather than concentrations (Carberry, 1976). Hence, in Eq. (1) the activity coefcient of H+ is needed to change its molarity to activity. Activity coefcients, however, are mostly inuenced by the total ionic strength, and the interaction parameters of the major species (Baghalha and Papangelakis, 1998b), which, in this case, are H+, Cl and NO 3 (refer to Figs. 6 and 7). These ions remained within the same order of magnitude in each test performed in the present work. Furthermore, due to the high initial concentration of the electrolytes in solution, the ionic strength also remains relatively constant. As a result, the hydrogen ion activity coefcient may be assumed to be a constant value in all the performed tests. Hence, its net effect on the rate is absorbed in parameter k of Eq. (1). Therefore, Eq. (1) was maintained in terms of H+ ion molarity. For a batch operation, a mass balance for platinum yields: rPt WSolids dwPt WSolids =dt 2

For each leaching test from t = 5 min to the end of the extraction, kobs is constant. To obtain the optimum value for n1, different values were tried to t platinum extraction data (from 5 to 120 min) to Eq. (6). After repeating this procedure for all the 11 sets of experimental data in Table 3, the optimum value for n1 was found to be 1.5. The values of kobs and the correlation coefcients for each test when n1 = 1.5 are reported in Table 3. The average goodness of t for the S and C catalyst runs was 0.93 and 0.96, respectively. The assumption of constant weight of solid is more valid for the C catalysts; hence, as expected, a better t for these catalysts was obtained. Although, this assumption is not quite valid for the S series tests, perhaps some unknown factors cancel out this error in such a way that Eq. (6) still represents a good mathematical t for those data.

Where, Wsolids is the total weight of the solids inside the reactor. Figs. 4B and 5B show that the extraction of aluminum for the alumina matrix remains between 5 and 45% during the tests. Hence, it was

Fig. 10. The Arrhenius effect of temperature on reaction rate constant k for tests C2, C4, and C5.

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To obtain the optimum value for n2, ln(kobs) can be plotted against ln(mH+), as Eq. (7) can be reduced to lnkobs lnk4 n2lnmH Where n11 k4 kn1 1 w0 Pt 9 8

indicates that Pt extraction in aqua-regia solution is controlled by the surface chemical reaction of platinum dissolution. Notations A Frequency factor of reaction rate constant E Surfacereaction activation energy, kJ/mol k Overall reaction rate constant kobs The observed reaction rate constant k The modied reaction rate constant as dened by Eq. (10) mH+ The molarity of the hydrogen ion in solution, mol/L n1 and n2 The reaction orders rPt The observed rate of platinum extraction per unit mass of solids in the reactor, mol/s kg R The universal gas constant (8.3145 10 3 kJ/K mol) T Reaction temperature, K wPt Weight fraction of platinum in solids w0 The initial platinum weight fraction in the ground catalyst Pt feed Wsolids Total weight of the solids inside the reactor, kg X Fraction of platinum extracted

The values of mH+ are reported in Table 3. As Eq. (9) shows, k is proportional to k, the overall reaction rate constant, which, in turn, is a function of temperature. To obtain a linear plot of ln(kobs) against ln (mH+), k must be constant; i.e., according to Eq. (9), using tests with the same constant temperature. To obtain the optimum value for n2, Fig. 9 was constructed for tests C2, C6, and C7 at constant temperature of 80 C. The optimum value for n2, as reported in the linear correlation in Fig. 9 was found to be 1.3. Tests C2, C4, and C5 have been performed at different temperatures. Hence, temperature-dependent parameters may be obtained through these experimental data. The modied reaction rate constant, k, maybe expressed according to Arrhenius Eq. (10) k4 A expE=RT 10

References Where A is the frequency factor, E is the surface-reaction activation energy in kJ/mol, R is the universal gas constant (8.3145 10 3 kJ/K mol) and T is the reaction temperature in K. The values of ln(k), calculated using Eq. (8) are also reported in Table 3. By plotting ln(k) vs. 1/T for tests C2, C4, and C5 in Fig. 10, the parameters of Eq. (10) were obtained as follows: E=R 8670 KZ E 72:1 kJ=mol
o

11 12

ln A 18:217

In general, the activation energy of a physical process, e.g. diffusion is less than 20 kJ/mol while that of a chemical process exceeds 40 kJ/mol (Lee et al., 2005). For instance, the activation energies of chromium extraction from sludge (Lee et al., 2005) and metallic copper dissolution in nitric acid (Demir et al., 2004) have been reported as 47 and 48 kJ/mol, respectively. As a result, the calculated value of 72.1 kJ/mol for the activation energy of platinum dissolution in aqua-regia suggests that the overall extraction rate must be controlled by the surface chemical reaction (Levenspiel, 1999). To verify the kinetic modeling work, Eq. (6) was used to predict the platinum extraction from the tested spent catalyst. In Figs. 2A, 3, 4A, and 5A, the predicted values are compared with the experimental data. In general, there is a good agreement between the predictions and the experimental data. Test S2 in Fig. 2A and test C6 in Fig. 4A show some small differences between the predictions and the experimental data. This may be due to some small variation in the acidity during those tests, in contrast to the simplifying assumption of constancy of mH+ in Eq. (7). 5. Conclusion Decoking did not enhance platinum extraction from the spent reforming catalyst signicantly. Catalyst particle sizes b 100 m and agitation speeds N 700 rpm eliminated the internal and external masstransfer resistances, respectively. Pt extraction rate was signicantly increased by increasing liquid-to-solid mass ratio and the reaction temperature. Through a kinetics modeling using powerlaw rate equation for Pt extraction, the reaction order was calculated as 1.5 for Pt concentration in solid and 1.3 for the hydrogen ion molarity in solution. The effect of temperature on Pt extraction kinetics was modeled using Arrhenius equation. The activation energy for the platinum extraction was obtained as 72.1 kJ/mol. This large value

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