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Ind. Eng. Chem. Res. 2005, 44, 7738-7745

Reaction Kinetics and Mechanisms of Zeolite Dissolution in Hydrochloric Acid

Ryan L. Hartman and H. Scott Fogler*
Department of Chemical Engineering, The University of Michigan, 2300 Hayward St., Ann Arbor, Michigan 48109-2136

The kinetics of zeolite dissolution in aqueous hydrochloric acid was investigated over a strongly acidic pH range (for pH e 1 and [H+] ) 0.1-6 M) in a batch reactor. The apparent reaction order with respect to hydrogen ion concentration decreased with increasing pH. Existing models do not predict this trend. A fundamental rate model derived from an adsorption and surface reaction mechanism is consistent with the experimental dissolution rates. The correlated model parameters suggest that the hydrogen ion strongly adsorbs onto zeolite surfaces and that zeolite dissolution follows Langmuir-Hinshelwood kinetics. A comparison of the Langmuir-Hinshelwood kinetic parameters reveals that the zeolite dissolution rates are dependent on the Si/Al ratio in the zeolite framework. Nonstoichiometric dissolution is observed for analcime and type Y zeolites, indicating a unique mechanism in which aluminum atoms are selectively removed. The ratio of the measured silicon dissolution rate to the stoichiometric dissolution rate ranges from 0 to 1 and increases with decreasing Si/Al ratios in the range of 1-2.6, suggesting that the zeolite dissolution phenomenon is controlled by the framework composition.
1. Introduction Solid-liquid dissolution phenomena play a vital role in processes throughout the pharmaceutical, petrochemical, water treatment, and electronics industries. The dissolution of zeolites has been investigated in a number of different processes, including wastewater stream treatment, radioactive waste immobilization, and petroleum reservoir acidization. This research is motivated by the acidization of reservoirs in the Gulf of Mexico that contain the zeolite analcime. Acidization is a mineral dissolution technique used to enhance petroleum recovery. Here, acid is injected into a porous, lowpermeability, geologic formation in order to dissolve aluminosilicate minerals and, thereby, increase nearwell bore permeability. Mineral precipitation can occur during acidization and constitutes a significant risk of pore blockage, which leads to production losses of considerable economic magnitude.1 A fundamental understanding of zeolite dissolution science is crucial in order to design acidization treatments, which maximize mineral dissolution while mitigating precipitation risks. 2. Zeolite Mineralogy Oil-bearing geologic formations can contain clays, carbonates, quartz, feldspar, mica, and zeolites.2 Formations containing zeolites are composed primarily of quartz (50-90 wt %), which is considered to be virtually inert, or undissolvable, to acid treatments. The remaining 10 wt % is composed of zeolites, feldspar, clay, and mica, which are all dissolvable.3 Acid formulations are selected on the basis of the reservoir mineralogy,2 and hydrochloric acid, hydrochloric/hydrofluoric acid mixtures, and organic acid mixtures are commonly used as stimulation fluids.4-6 Severe mineral precipita* To whom correspondence should be addressed. Tel.: +1 (734) 763-1361. Fax: +1 (734) 763-0459. E-mail: sfogler@ umich.edu.

tion has been documented when reservoirs composed of zeolites were treated with hydrochloric acid.1 Hydrochloric acid was, therefore, used as the primary solvent in this study. Naturally occurring zeolites exist in mineral formations throughout the world.7 The zeolite of primary economic concern is analcime because it is dissolvable and exists within oil-bearing formations in the Gulf of Mexico.1 Analcime can be found in geologic formations elsewhere, from Ireland to New Jersey and from Wyoming to Arizona, as well as in the deep sea floor, increasing the chance of encountering the zeolite during reservoir stimulation treatments.3 Zeolites are a class of minerals characterized by crystalline composition and structure.3 The structure of zeolite minerals consists of a network of silicon and aluminum tetrahedra. Each oxygen atom within a tetrahedron shares bonds with a neighboring tetrahedron, resulting in a continuous framework of silicon and aluminum tetrahedra. The crystal structures of zeolites are microporous, whereas those of clays and feldspars are not. Micropores in analcime contain Na+ ions (dpore ) 2.6 ),8 and the Si/Al ratio in the framework may range from 1.8 to 2.8, as shown in Figure 1a.3 Synthetic zeolites, which play important roles in a number of industrial applications, exhibit properties similar to those of naturally occurring zeolites. Type A zeolites, shown in Figure 1b, are commonly synthesized for use as detergents and adsorbents. The characteristics of type A zeolites are dependent on the absorbed cation species,9 and the Si/Al ratio may range from 0.7 to 1.2.3 For example, a Na+ exchanged type A zeolite, known as a type 4A, will permit the adsorption of molecules with a minimum effective diameter of about 4.0 .9 Type 3A zeolites are prepared by exchanging Na+ with K+, resulting in effective pore diameters of approximately 3.0 .3,9 Similarly, type 5A zeolites, prepared by exchanging Na+ with Ca2+, exhibit effective pore diameters of 4.9 .3,9 Type Y zeolites are manu-

10.1021/ie0504349 CCC: $30.25 2005 American Chemical Society Published on Web 08/26/2005

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Figure 1. Crystal structures of (a) analcime, (b) synthetic type A, and (c) synthetic type Y. (Modified from International Zeolite Association, Atlas of Zeolite Structure Types: ANA, LTA, and FAU, 2003. http://www.iza-structure.org/databases/.)

factured for use as reaction catalysts or molecular sieves in gas separations. The pore diameter of a type Y zeolite is 7.4 , with Si/Al ratios ranging from 1.5 to 3, as shown in Figure 1c.3 3. Previous Work Fundamental knowledge of the mechanism of zeolite dissolution in acidic solutions is limited as previous investigations have focused on dissolution in alkaline and near-neutral pH solutions.10-18 In one such study, Yamamoto et al.15 hypothesized that hydrogen and hydroxide ions diffuse into heulandite (a natural zeolite) crystals and remove the outermost aluminosilicate layer in dilute sulfuric acid and sodium hydroxide solutions, respectively. Measurement of the aqueous product concentrations, however, was not performed, nor was a rate law model developed to support this hypothesis. The research in the present study addresses zeolite dissolution from a fundamental perspective by developing a rate law model based on surface adsorption and reaction phenomena. While lacking fundamental derivation, an empirical approach has been taken with a number of empirical rate expressions having been applied to describe zeolite dissolution,10,14,17 such as the one given by Gdanski:19

Figure 2. Experimental batch reactor.

al.10 were empirically fit to experimental data over a limited range and cannot be accurately extrapolated to high H+ concentrations. In addition, no reaction mechanism was applied to develop a rate model. Kline and Fogler20 demonstrated that hydrofluoric acid attack on feldspar, kaolinite, and montmorillonite takes place on crystalline, planar surfaces and edges and applied a fundamental mechanism to develop a rate law model. The characteristic mechanism includes both HCl (H+) and HF adsorption on the surface followed by a dissolution step.21 For the case when the surface reaction is rate-limiting, the rate law was shown to be of the form

rproducts )

ka[HF] 1 + KA[HF]

1+

kb[H+] 1 + KB[H+]

(3)

This approach from first principles is an example that can be applied to other systems in order to reveal dissolution mechanisms. 4. Experimental Methods 4.1. Materials. Research grade analcime was obtained from Mt. St. Hilaire, Quebec (Ward Science). The crystals were crushed for approximately 10 min using an automated crusher and sieved into 0.2-38 m particle sizes. The analcime crystals appeared to range from colorless to white. Ultrapure type 4A and type Y zeolites were obtained from the PQ Corporation and Zeolyst International, respectively. Type 4A zeolite was dispersed into 0.5 M KCl and 0.5 M CaCl2 solutions for approximately 20 min at room temperature in order to prepare type 3A and type 5A zeolites, respectively. The particles were subsequently filtered through a 0.2 m membrane filter and washed with deionized water to remove excess Ca or K. Each sample was then dissolved in acid and analyzed using an inductively coupled plasma spectrophotometer (ICP) in order to monitor the removal of Na+ from the lattice. The process was repeated until the Na+ was completely exchanged with K+ or Ca2+. Reactant solutions were prepared with deionized water and trace-metal-grade hydrochloric acid. 4.2. Dissolution Experiments. Zeolite dissolution experiments were carried out in concentrations of hydrochloric acid ranging from 0.1 to 6 M using the batch reactor shown schematically in Figure 2. A total of 1 g of zeolite was dissolved in 300 mL of acid solution at temperatures of 5.4, 8.0, and 10.3 C and a stirring

rproducts ) k[HF]R[HCl]

(1)

where, [HF] and [HCl] are the concentrations of molecular HF and HCl (H+), respectively. In the absence of HF, the empirical rate law reduces to a power-law relationship with respect to the HCl concentration (i.e., R ) 0). However, the reaction mechanism of zeolite dissolution in HCl must be accurately established before symbiosis between HF and HCl can be investigated. Other researchers have used empirical models to predict zeolite dissolution as well. Murphy et al.14 and Ragnarsdottir17 both assumed a power-law dependence of the rate law on hydrogen ion activity. Ragnarsdottir17 demonstrated empirically that the reaction order, n, with respect to hydrogen ion activity is a linear function of the Al/Si ratio within an aluminosilicate framework for pHs from 2 to 7:

n ) 0.25 + 0.75

(Al) Si

(2)

Cizmek et al.10-12 studied the dissolution kinetics of type A, type X, and synthetic mordenite zeolites in aqueous sodium hydroxide solutions. A rate law model was developed to estimate zeolite dissolution in the nearequilibrium regime, which cannot be applied to the results in this study. Rate models proposed by Gdanski,19 Murphy et al.,14 Ragnarsdottir,17 and Cizmek et

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Table 1. Physical Properties of Zeolites3 mineral analcime type 3A type 4A type 5A type Y
a

Si/Al 2.09 1.03 1.06 1.02 2.56

b

M/Al 1.01 0.93 1.00 0.46 1.07

Fs (g/cm3) 2.27 2.08 1.99 2.05 1.92

c

ion exchange capacity (meq/g) 4.47 4.94 5.37 5.46 3.43

dpore () 2.6 3 4.2 4.9 7.4

calculated external as (m2/g) 0.68 1.23 0.95 1.28 1.34

N2 BET as (m2/g) 1.33 2.26c 848

Cerius2 N2 as (m2/g)a 0 836 836 836 808

Cerius2 H3O+ as (m2/g)b 516 906 906 906 845

dN2 ) 2.78 .30

dH3O+ ) 2.34 .30

Insufficient time for nitrogen adsorption.

rate of approximately 500 rpm. Samples were obtained using micropipets and drawn through membrane filters (dpore ) 0.2 m) at short time intervals. Filtration of the suspended particles stopped the dissolution reaction. Hence, filtrate samples were representative of dissolved mineral concentrations as a function of reaction time. The samples were analyzed for dissolved Al, Si, and Na (or Ca, K) using an ICP spectrophotometer. Dissolution rates were quantified by the method of initial rates. Details of this method are described in a previous investigation.22 5. Results and Discussion 5.1. Zeolite Characterization. Two samples each of analcime and type 4A, 3A, 5A, and Y zeolites were dissolved overnight in a 2.5 M HCl/0.5 M HF mixture at 70 C in order to facilitate structural and compositional characterization. Each sample was drawn through a 0.2 m membrane filter, diluted with deionized water, and analyzed using an ICP spectrophotometer. Table 1 shows the Si/Al ratio, cation/Al ratio, density, cation exchange capacity, pore dimensions, and surface areas for each zeolite. External surface areas for each sample were calculated on the basis of particle shape factors estimated from scanning electron microscope micrographs and from the particle size distribution. The particle shape factor is the ratio of the surface area of a sphere to that of a nonspherical particle having the same volume. Details of how to calculate the specific surface area for a given shape factor and particle size distribution, as well as examples, are reported by Geankoplis.23 External surface areas of all samples were estimated to be approximately 1 m2/g. The specific surface area is an important property that can be used to compare dissolution rates of different zeolites. This property is commonly measured by nitrogen Brunauer-Emmett-Teller (BET) adsorption for macroporous zeolites and nonporous surfaces.24,25 As shown in Table 1, nitrogen BET surface area measurements of analcime and type 4A and Y zeolites yielded values of 1.33, 2.26, and 848 m2/g, respectively. Internally accessible surface areas were theoretically estimated by constructing zeolite unit cells using molecular modeling software26 for two cases: (1) N2 adsorption and (2) H3O+ adsorption. Table 1 demonstrates that theoretically predicted N2 BET internal surface areas were 2 orders of magnitude greater than the measured values for type A zeolites, indicating that insufficient time was allowed for adsorption because N2 diffusion rates within type A zeolites are very small, as reported by Karger.25 In analcime, the effective window for diffusion is less than that required for N2 adsorption, which resulted in a theoretically predicted internal surface area of 0 m2/ g. The internally accessible surface areas for all zeolites were estimated to be on the order of 100 m2/g, assuming H3O+ adsorption. The results demonstrate conclusively that N2 BET measurements of type 4A and analcime

reflect external surface area measurements while measurements of type Y reflect internal and external areas, as shown in Table 1. Given that excess protons in water exist as hydrated complexes (e.g., H9O4+ or H5O2+), as described by Marx et al.,27 it is unlikely that the hydronium ion diffuses into the porous framework of analcime or type A zeolite because the effective window for diffusion is smaller than the effective diameter of a hydrated complex. Recent investigations by Ryder et al.28 and Franke and Simon29 demonstrate a Grotthus-type mechanism for proton transport within ZSM-5 zeolite frameworks. Ryder et al.28 showed that the presence of water within ZSM-5 micropores catalyzes proton migration rates via a water-facilitated proton hopping mechanism. Excess protons in the bulk migrate to the external surface of zeolite particles where either a surface reaction takes place or further migration into the porous framework occurs. As a result, protons penetrate and attack internal framework sites. Consequently, the surface area measured by N2 BET adsorption is not representative of the true reactive surface area. In the current investigation, a reaction site is defined as either a Si-O or Al-O bond. In zeolites, there exist two reaction sites per framework atom. If a constant reaction site surface density is assumed, then the dissolution rate can be normalized to m2 exposed surface and compared for different zeolites. The total number of accessible reaction sites was estimated from the accessible surface areas calculated using the molecular simulations software package26 for two limiting cases: (1) accessible internal reaction sites and (2) only accessible external reaction sites. The results show that the reaction site density varies between zeolites, as shown in Figure 3. The analysis was, therefore, extended to describe zeolite dissolution as a function of reaction site density in addition to surface area. 5.2. Zeolite Dissolution. In the first series of experiments, initial dissolution rates of both Si and Al were determined as a function of H+ concentration. Figure 4 shows dissolution rates of analcime as a function of acid concentration. Under stoichiometric dissolution conditions, Si and Al dissolution rates expressed as moles dissolved per reaction sites per unit time are identical. The selective removal of Al atoms results in dissimilar Si and Al dissolution rates, as shown in Figure 4. Selective removal is defined as the removal of one atomic species at a faster rate than another from the zeolite framework. One observes from Figure 4 that the apparent reaction order with respect to the H+ concentration is approximately 1 at low concentrations (<0.5 mol/dm3) and decreases with increasing concentration as Si and Al dissolution rates approach a plateau. A plateau of this type can be explained by an adsorption step in the reaction mechanism.31 At high H+ concentrations, the dissolution rate is constrained by the number of avail-

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Figure 3. Internal (a) and external (b) surface reaction site densities.

able surface adsorption sites. Writing these observations in terms of reaction steps we have

Adsorption

H+ + S 9 H+S 8 H+S 9 H+ + S 8
k2

k1

Surface Reaction

H+S 9 products 8

k3

Assuming the surface reaction is rate limiting, the initial rate law is

-r*i,0 )

k1k3ST[H+] k2 + k3 + k1[H+]

(4)
Figure 4. Analcime dissolution rates for different hydrogen ion concentrations at 5.4 C.

The rate law can be rearranged to take a form

-r*i,0 )

Vmax[H+] k3ST[H+] ) k2 + k3 Km + [H+] + [H+] k1

(5)

where

Vmax ) k3ST
and

(6)

Km )

k2 + k3 k1

(7)

Those familiar with enzymatics will recognize eq 5 as the rate law for Michaelis-Menten kinetics, and k3 is equivalent to the turnover number, kcat.32 The analogous Michaelis-Menten constant, Km, and the maximum rate of dissolution, Vmax, provide fundamental insight into the reaction mechanism. To test the suggested mechanism, the experimental data is linearized by the Hanes-Woolf method and plotted in Figure 5.32 The constant, Km, in eq 5 was estimated to be on the same order as the H+ concentration (Km,Al ) 1.75 and Km,Si ) 1.31 mol/dm3), which is consistent with adsorption being a fundamental step in the reaction mechanism of analcime (a natural zeolite) dissolution in hydrochloric acid. Figure 6 shows an Eadie-Hofstee analysis32 of the analcime dissolution data along with a comparison of

Figure 5. Hanes-Woolf plot for analcime dissolution.

the empirical rate models proposed by Gdanski,19 Ragnarsdottir,17 and Murphy et al.14 One readily observes the empirical models are not able to describe the data, while Langmuir-Hinshelwood kinetics provide an excellent fit. Figure 7 shows a comparison of experimental data (pH <1) with Ragnarsdottirs power-law model, eq 2,17 applicable to conditions of pH 2-7. The experimental reaction order was determined for each zeolite by a linearized regression of the data to a rate law of the form -r*i,0 ) k(aH+)n. The results illustrate that the reaction order is not at all linearly dependent on the Al/Si ratio for the investigated zeolites. One observes a poor fit of the data to an extrapolation of Ragnars-

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Figure 6. Empirical rate model compared to analcime dissolution.14,17,19

Figure 9. Linearized rate law for type 3A dissolution at 5.4 C.

Figure 7. Ragnarsdottirs model applicable for pH 2-7 extrapolated to pH <1.17

Figure 10. Linearized rate law for type 5A dissolution at 5.4 C.

Figure 11. Linearized rate law for type Y dissolution at 5.4 C. Figure 8. Linearized rate law for type 4A dissolution at 5.4 C.

dottirs empirical model, demonstrating that a power rate law cannot be used to model the dissolution of zeolites for pH <1 because it does not accurately capture the reaction mechanism. Establishing a mechanistic rate model for analcime dissolution provides insight into synthetic zeolite dissolution. In the second series of experiments, type 4A, 3A, 5A, and Y dissolution rates in hydrochloric acid were measured under analogous conditions. The experimental data are linearized and shown in Figures 8-10. Dissolution rates of type A and Y zeolites follow a rate law analogous to the Michaelis-Menten equation. The

Si and Al dissolution rates are stoichiometric in type 3A, 4A, and 5A zeolites, as shown in Figures 8-10. Figure 11 shows unambiguous evidence of the selective removal of Al during type Y zeolite dissolution. The measured Al dissolution rate is approximately 1 order of magnitude greater than the Si dissolution rate at all H+ concentrations. In all cases, the dissolution of both natural and synthetic zeolites is influenced by hydrogen ion adsorption and subsequent surface reaction. The kinetic dissolution parameters were determined for each zeolite using nonlinear regression.33 The maximum rates of dissolution given by the ratios Vmax/Km are shown in Table 2 for each zeolite. The maximum dissolution rates are normalized to the values of type

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Table 2. Evaluation of the Kinetic Parameters Vmax,Al (mol/1016 sites min) 4.51 4.14 3.77 0.588 0.209 Vmax,Al/Vmax,4A 1.0 0.92 0.84 0.13 0.046 Vmax,Si (mol/1016 sites min) 4.32 3.80 3.61 0.452 0.007 Km,Al (mol/dm3) 0.296 0.382 0.330 1.75 0.093 Km,Si (mol/dm3) 0.283 0.337 0.337 1.31 0.121 kcat,Al (min-1) 543 499 454 70.9 25.2 kcat,Si (min-1) 520 458 435 54.5 0.829 (Vmax,Al/Km,Al) 106 (dm3/1016 sites min) 15.2 10.8 11.4 0.336 2.26 kcat,Al/Km,Al (dm3/mol/min) 1830 1300 1370 40.4 273 (Vmax,Si/Km,Si) 106 (dm3/1016 sites min) 15.2 11.3 10.7 0.345 0.057 kcat,Si/Km,Si (dm3/mol/min) 1840 1360 1290 41.5 6.86

T (C)

zeolite type 4A type 3A type 5A analcime type Y zeolite type 4A type 3A type 5A analcime type Y

Si/Al 1.06 1.03 1.02 2.09 2.56 Si/Al 1.06 1.03 1.02 2.09 2.56

5.4

T (C)

Vmax,Si/Vmax,4A 1.0 0.88 0.84 0.10 0.002

5.4

Table 3. Selective Removal Parameter Values for Each Zeolite values of a [H+] (mol/dm3) 0.10 0.25 0.50 1.00 2.00 4.01 6.00
a

T (C) 5.4 8.0 10.3 5.4 8.0 10.3 5.4 8.0 10.3 5.4 5.4 5.4 5.4

type 5A 0 ) 1.02 1.02 X 1.03 1.04 X 1.03 0.956 X 1.01 1.01 X X X

type 3A 0 ) 1.03 0.997 X 1.04 1.07 X 1.08 1.07 X 0.980 0.866 X X X

type 4A 0 ) 1.06 0.935 0.900 1.01 0.960 0.991 0.988 0.929 0.945 0.955 0.919 X X X

analcime 0 ) 2.09 0.770 0.851 0.820 0.828 0.850 0.860 0.854 0.885 0.891 0.936 0.928 0.858 0.787

type Y 0 ) 2.56 0.027 0.018 0.011 0.032 0.028 0.018 0.032 0.028 0.025 0.011 X X X

X ) analysis not carried out.

4A zeolites, which exhibit the highest dissolution rates under all experimental conditions. One observes in Table 2 that Vmax values decrease with increasing Si/Al ratios. Silicon and aluminum dissolution rates of type A zeolites are 1 order of magnitude greater than dissolution rates of analcime or type Y. Silicon dissolution rates of analcime are 1 order of magnitude greater than that of type Y, while aluminum dissolution rates are approximately on the same order of magnitude in both zeolites. Analogous trends are observed for the turnover number, kcat, which is a ratio of framework atoms removed per framework atoms bound per unit time. Michaelis-Menten-type rate constants, shown in Table 2, are consistent with hydrogen ion adsorption onto each zeolite. A quantitative description of the selective removal of Al is provided in order to further investigate the controlling mechanisms of zeolite dissolution. The selective removal of Al atoms occurs when the resulting Si/ Al ratio in solution is less than the stoichiometric ratio within the zeolite framework, 0. When there is no precipitation of Si, the ratio of the measured Si dissolution rate to the stoichiometric Si dissolution rate (based on Al) can be expressed in terms of the parameter

rSi measured Si dissolution rate ) 0rAl stoichiometric Si dissolution rate

(8)

which can be used to quantitatively describe the selective removal of Al. Table 3 shows the selective removal parameter value for each zeolite. Figures 8-10 show that Si and Al dissolution rates of type A zeolites are nearly equal,

resulting in 1. For analcime, ranges from 0.770 to 0.936, indicating an increased Al removal selectivity. Figure 11 and Table 2 show that rAl . rSi for type Y zeolites, resulting in , 1, as can be seen in Table 3. For type Y zeolites, values range from 0.011 to 0.032, confirming that Al atoms are selectively removed. The selective removal of Al has previously been observed by Kerr,34 who estimated that 100% of framework Al in type Y zeolites may be removed by treatment with ethylenediaminetetraacetic acid, a weak acid. The results in Table 3 also show that the extent to which Al atoms undergo selective removal is strongly dependent on the zeolite Si/Al ratio. A comparison of the selective removal parameter values in Table 3 shows the following Al selective removal trend: type Y > analcime > type A. A decrease in with increasing 0 indicates variations in the silicate framework stability. Zeolites with large values of the stoichiometric ratio of Si/Al, 0, (i.e., 2.6 > 0 > 2) are resistant to framework destruction, which is consistent with the work of Carland and Aplan.18 The general model for synthetic and natural zeolite dissolution rates can be applied to field operations, which can encompass a number of naturally occurring zeolites (e.g., analcime, clinoptilolite, heulandite, etc.).7 Typical field operation formulations (e.g., 9 wt % HCl/1 wt % HF) can incorporate pH conditions of less than 1, and the fluids are injected in stages. For example, an HCl preflush is generally followed by treatment with HCl/HF and the subsequent injection of an inert fluid as the last stage, all done in dynamic mode. To minimize the shutdown period and raw material usage, it is critical that the appropriate amounts and strength of

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Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 n ) empirical reaction order with respect to hydrogen ion activity -r* ) initial dissolution rate rproducts ) rate of product formation Vmax ) maximum rate of dissolution Greek Letters R ) empirical reaction order with respect to molecular HF ) empirical reaction order with respect to molecular HCl ) ratio of measured Si dissolution rate to stoichiometric Si dissolution rate 0 ) Si/Al ratio in zeolite before dissolution Subscripts 0 ) denotes initial dissolution rates 4A ) type 4A zeolite Al ) aluminum species i ) framework atom species or zeolite Si ) silicon species

the acid are determined prior to injection at the well head. First-order rate law models with respect to the H+ concentration overpredict dissolution rates in the low pH regime, as shown in Figure 6, resulting in overestimated amounts of dissolved formation and inaccurate permeability/porosity estimates. Empirical rate models developed by Gdanski,19 Ragnarsdottir,17 and Murphy et al.14 also fail to predict the dissolution rate. Figure 5 indicates accurate predictions of the dissolution rate by a Michaelis-Menten-type kinetic analysis, which can lead to more accurate models for acidization treatment formulation. To design effective acidization treatments, the appropriate rate model and kinetic parameters for zeolite dissolution must be applied. 6. Conclusions Experiments were performed to elucidate the mechanism of zeolite dissolution in hydrochloric acid solutions at pH conditions e 1 (or [H+] ) 0.1-6 M). Previous empirical models cannot be used to accurately predict the reaction rate as a function of pH. In this work, a fundamental kinetic model was developed and applied to the experimental results, demonstrating that zeolite dissolution rates can be estimated using a form of the Langmuir-Hinshelwood rate law analogous to the Michaelis-Menten equation. A mechanism involving adsorption of the hydrogen ion followed by a surface reaction, which is rate-limiting, is consistent with experimental data. Empirical zeolite dissolution models are inconsistent with experimental data and should not be used as the basis for the design of reservoir acidization treatments. Quantitative analysis of the selective removal of Al demonstrates that zeolite dissolution exhibits a strong dependence on the Si/Al framework ratio. The ratio of measured Si dissolution rate to stoichiometric Si dissolution rate increases with decreasing Si/Al ratio. Type A zeolites dissolve stoichiometrically, whereas type Y and analcime dissolve nonstoichiometrically at a temperature of 5.4 C. Nonstoichiometric dissolution can result in undissolvable silicate particles; consequently, one cannot assume that treating zeolites with hydrochloric acid at 5.4 C will always result in complete structural dissolution. Acknowledgment The authors acknowledge financial support from the following members of the Industrial Affiliates Program on Flow and Reaction in Porous Media at the University of Michigan: Baker Petrolite Corporation, ChevronTexaco Energy Technology Company, ConocoPhillips Company, Schlumberger Ltd., Shell International Exploration & Production, and Total. Nomenclature
aH+ ) hydrogen ion activity dpore ) pore diameter KA ) equilibrium constant for HF adsorption KB ) equilibrium constant for H+ adsorption Km ) analogous Michaelis-Menten constant ka ) specific reaction rate for dissolution by HF kb ) specific reaction rate for dissolution by H+ kcat ) turnover number [H+] ) hydrogen ion concentration [HF] ) molecular HF concentration [HCl] ) molecular HCl concentration

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Received for review April 8, 2005 Revised manuscript received July 22, 2005 Accepted July 29, 2005 IE0504349